Geochemical assessment of fluoride enrichment and nitrate contamination in groundwater in hard-rock aquifer by using graphical and statistical methods

This systematic study was carried out with objective to delineate the various sources responsible for \(\hbox {NO}_{3}^{-}\) contamination and \(\hbox {F}^{-}\) enrichment by utilizing statistical and graphical methods. Since Central Ground Water Board, India, indicated susceptibility of \(\hbox {NO}_{3}^{-}\) contamination and \(\hbox {F}^{-}\) enrichment, in most of the groundwater, \(\hbox {NO}_{3}^{-}\) and \(\hbox {F}^{-}\) concentration primarily observed \({>}45\) and \({>}1.5~\hbox {mg/L}\), respectively, i.e., higher than the permissible limit for drinking water. Water Quality Index (WQI) indicates \({\sim }22.81\%\) groundwater are good-water, \({\sim }71.14\%\) groundwater poor-water, \({\sim }5.37\%\) very poor-water and 0.67% unsuitable for drinking purpose. Piper diagram indicates \({\sim }59.73\%\) groundwater hydrogeochemical facies are Ca–Mg–\(\hbox {HCO}_{3 }\) water-types, \({\sim }28.19\%\) Ca–Mg–\(\hbox {SO}_{4}\)–Cl water-types, \({\sim }8.72\%\) Na–K–\(\hbox {SO}_{4}\)–Cl water-types and 3.36% Na–K–\(\hbox {HCO}_{3 }\) water-types. This classification indicates dissolution and mixing are mainly controlling groundwater chemistry. Salinity diagram indicate \({\sim }44.30\%\) groundwater under in low sodium and medium salinity hazard, \({\sim }49.66\%\) groundwater fall under low sodium and high salinity hazard, \({\sim }3.36\%\) groundwater fall under very-high salinity hazard. Sodium adsorption ratio indicates \({\sim }97\%\) groundwater are in excellent condition for irrigation. The spatial distribution of \(\hbox {NO}_{3}^{-}\) indicates significant contribution of fertilizer from agriculture lands. Fluoride enrichment occurs in groundwater through the dissolution of fluoride-rich minerals. By reducing the consumption of fertilizer and stress over groundwater, the water quality can be improved.     

Application of environmental isotopes and hydrochemistry in the identification of source of seepage and likely connection with lake water in Lesser Himalaya,Uttarakhand, India

Oxygen (\({\updelta }^{18}\hbox {O}\)) and hydrogen (\({\updelta }^{2}\hbox {H}\) and \(^{3}\hbox {H}\)) isotopes of water, along with their hydrochemistry, were used to identify the source of a newly emerged seepage water in the downstream of Lake Nainital, located in the Lesser Himalayan region of Uttarakhand, India. A total of 57 samples of water from 19 different sites, in and around the seepage site, were collected. Samples were analysed for chemical tracers like \(\hbox {Ca}^{++}\), \(\hbox {Mg}^{++}\), \(\hbox {Na}^{+}\), \(\hbox {K}^{+}\), \({\hbox {SO}_{4}}^{--}\) and \(\hbox {Cl}^{-}\) using an Ion Chromatograph (Dionex IC-5000). A Dual Inlet Isotope Ratio Mass Spectrometer (DIIRMS) and an Ultra-Low Level Liquid Scintillation Counter (ULLSC), were used in measurements of stable isotopes (\({\updelta }^{2}\hbox {H}\) and \({\updelta }^{18}\hbox {O}\)) and a radioisotope (\(^{3}\hbox {H}\)), respectively. Results obtained in this study repudiate the possibility of any likely connection between seepage water and the lake water, and indicate that the source of seepage water is mainly due to locally recharged groundwater. The study suggests that environmental isotopes (\({\updelta }^{2}\hbox {H}\), \({\updelta }^{18}\hbox {O}\) and \(^{3}\hbox {H}\)) can effectively be used as ‘tracers’ in the detection of the source of seepage water in conjunction with other hydrochemical tracers, and can help in water resource management and planning.     

Semi-empirical model for retrieval of soil moisture using RISAT-1 C-Band SAR data over a sub-tropical semi-arid area of Rewari district,Haryana (India)

We have estimated soil moisture (SM) by using circular horizontal polarization backscattering coefficient (\(\sigma ^{\mathrm{o}}_{\mathrm{RH}}\)), differences of circular vertical and horizontal \(\sigma ^{\mathrm{o}} \, (\sigma ^{\mathrm{o}}_{\mathrm{RV}} {-} \sigma ^{\mathrm{o}}_{\mathrm{RH}})\) from FRS-1 data of Radar Imaging Satellite (RISAT-1) and surface roughness in terms of RMS height (\({\hbox {RMS}}_{\mathrm{height}}\)). We examined the performance of FRS-1 in retrieving SM under wheat crop at tillering stage. Results revealed that it is possible to develop a good semi-empirical model (SEM) to estimate SM of the upper soil layer using RISAT-1 SAR data rather than using existing empirical model based on only single parameter, i.e., \(\sigma ^{\mathrm{o}}\). Near surface SM measurements were related to \(\sigma ^{\mathrm{o}}_{\mathrm{RH}}\), \(\sigma ^{\mathrm{o}}_{\mathrm{RV}} {-} \sigma ^{\mathrm{o}}_{\mathrm{RH}}\) derived using 5.35 GHz (C-band) image of RISAT-1 and \({\hbox {RMS}}_{\mathrm{height}}\). The roughness component derived in terms of \({\hbox {RMS}}_{\mathrm{height}}\) showed a good positive correlation with \(\sigma ^{\mathrm{o}}_{\mathrm{RV}} {-} \sigma ^{\mathrm{o}}_{\mathrm{RH}} \, (R^{2} = 0.65)\). By considering all the major influencing factors (\(\sigma ^{\mathrm{o}}_{\mathrm{RH}}\), \(\sigma ^{\mathrm{o}}_{\mathrm{RV}} {-} \sigma ^{\mathrm{o}}_{\mathrm{RH}}\), and \({\hbox {RMS}}_{\mathrm{height}}\)), an SEM was developed where SM (volumetric) predicted values depend on \(\sigma ^{\mathrm{o}}_{\mathrm{RH}}\), \(\sigma ^{\mathrm{o}}_{\mathrm{RV}} {-} \sigma ^{\mathrm{o}}_{\mathrm{RH}}\), and \({\hbox {RMS}}_{\mathrm{height}}\). This SEM showed \(R^{2}\) of 0.87 and adjusted \(R^{2}\) of 0.85, multiple R=0.94 and with standard error of 0.05 at 95% confidence level. Validation of the SM derived from semi-empirical model with observed measurement (\({\hbox {SM}}_{\mathrm{Observed}}\)) showed root mean square error (RMSE) = 0.06, relative-RMSE (R-RMSE) = 0.18, mean absolute error (MAE) = 0.04, normalized RMSE (NRMSE) = 0.17, Nash–Sutcliffe efficiency (NSE) = 0.91 (\({\approx } 1\)), index of agreement (d) = 1, coefficient of determination \((R^{2}) = 0.87\), mean bias error (MBE) = 0.04, standard error of estimate (SEE) = 0.10, volume error (VE) = 0.15, variance of the distribution of differences \(({\hbox {S}}_{\mathrm{d}}^{2}) = 0.004\). The developed SEM showed better performance in estimating SM than Topp empirical model which is based only on \(\sigma ^{\mathrm{o}}\). By using the developed SEM, top soil SM can be estimated with low mean absolute percent error (MAPE) = 1.39 and can be used for operational applications.     

Fluvial geochemistry of Subarnarekha River basin,India

The fluvial geochemistry of the Subarnarekha River and its major tributaries has been studied on a seasonal basis in order to assess the geochemical processes that explain the water composition and estimate solute fluxes. The analytical results show the mildly acidic to alkaline nature of the Subarnarekha River water and the dominance of \(\hbox {Ca}^{2+}\) and \(\hbox {Na}^{+}\) in cationic and \(\hbox {HCO}_{3}^{-}\) and \({\hbox {Cl}}^{-}\) in anionic composition. Minimum ionic concentration during the monsoon and maximum concentration in the pre-monsoon seasons reflect concentrating effects due to decrease in the river discharge and increase in the base flow contribution during the pre-monsoon and dilution effects of atmospheric precipitation in the monsoon season. The solute acquisition processes are mainly controlled by weathering of rocks, with minor contribution from marine and anthropogenic sources. Higher contribution of alkaline earth \((\hbox {Ca}^{2+}{+}\,\hbox {Mg}^{2+})\) to the total cations \((\hbox {TZ}^{+})\) and high \((\hbox {Na}^{+}+\hbox {K}^{+})/\hbox {Cl}^{-}\), \((\hbox {Na}^{+}+\hbox {K}^{+})/\hbox {TZ}^{+}\), \(\hbox {HCO}_{3}^{-}/(\hbox {SO}_{4}^{2-}+\hbox {Cl}^{-})\) and low \((\hbox {Ca}^{2+}+\hbox {Mg}^{2+})/(\hbox {Na}^{+}+\hbox {K}^{+})\) equivalent ratios suggest that the Subarnarekha River water is under the combined influence of carbonate and silicate weathering. The river water is undersaturated with respect to dolomite and calcite during the post-monsoon and monsoon seasons and oversaturated in the pre-monsoon season. The pH–log \(\hbox {H}_{4}\hbox {SiO}_{4}\) stability diagram demonstrates that the water chemistry is in equilibrium with the kaolinite. The Subarnarekha River annually delivered \(1.477\times 10^{6}\) ton of dissolved loads to the Bay of Bengal, with an estimated chemical denudation rate of \(77\hbox { ton km}^{-2}\hbox { yr}^{-1}\). Sodium adsorption ratio, residual sodium carbonate and per cent sodium values placed the studied river water in the ‘excellent to good quality’ category and it can be safely used for irrigation.     

Determining shallow aquifer vulnerability by the DRASTIC model and hydrochemistry in granitic terrain,southern India

Shallow aquifer vulnerability has been assessed using GIS-based DRASTIC model by incorporating the major geological and hydrogeological factors that affect and control the groundwater contamination in a granitic terrain. It provides a relative indication of aquifer vulnerability to the contamination. Further, it has been cross-verified with hydrochemical signatures such as total dissolved solids (TDS), \(\hbox {Cl}^{-},\, \hbox {HCO}_{3}^{-},\, \hbox {SO}_{4}^{2-}\) and \(\hbox {Cl}^{-}/\hbox {HCO}_{3}^{-}\) molar ratios. The results show four zones of aquifer vulnerability (i.e., negligible, low, moderate and high) based on the variation of DRASTIC Vulnerability Index (DVI) between 39 and 132. About 57% area in the central part is found moderately and highly contaminated due to the 80 functional tannery disposals and is more prone to groundwater aquifer vulnerability. The high range values of TDS (2304–39,100 mg/l); \(\hbox {Na}^{+}\)(239– 6,046 mg/l) and \(\hbox {Cl}^{-}\) (532–13,652 mg/l) are well correlated with the observed high vulnerable zones. The values of \(\hbox {Cl}^{-}/\hbox {HCO}_{3}^{-}\) (molar ratios: 1.4–106.8) in the high vulnerable zone obviously indicate deterioration of the aquifer due to contamination. Further cumulative probability distributions of these parameters indicate several threshold values which are able to demarcate the diverse vulnerability zones in granitic terrain.     

Carbon dioxide,water vapour and energy fluxes over a semi-evergreen forest in Assam,Northeast India

The eddy covariance method is a powerful technique for quantification of \(\hbox {CO}_{2},\) \(\hbox {H}_{2}\)O and energy fluxes in natural ecosystems. Leaf area index (LAI) and its changes are significant drivers of \(\hbox {CO}_{2}\) and \(\hbox {H}_{2}\)O exchange in a forest ecosystem due to their role in photosynthesis. The present study reports the seasonal variation of \(\hbox {CO}_{2}\) and energy fluxes and their relationship with other meteorological parameters of a semi-evergreen primary forest of Kaziranga National Park, Assam, India during February 2016–January 2017. The diurnal pattern of half hourly average \(\hbox {CO}_{2 }\) fluxes over the forest was found to be mostly dominated by the incident photosynthetically active radiation. During the period of study, diurnal variations of \(\hbox {CO}_{2}\) flux showed a maximum value of \(-9.97\,\upmu \)mol \(\hbox {m}^{-2}\hbox {s}^{-1}\) in the month of June during summer which is also the beginning of the monsoon season. The monthly averaged diurnal \(\hbox {CO}_{2}\) flux and variation in LAI of the forest canopy closely followed each other. The annual net ecosystem exchange of the forest estimated from the \(\hbox {CO}_{2}\) flux data above the canopy is 84.21 g C \(\hbox {m}^{-2}\,\hbox {yr}^{-1}\). Further studies are in progress to confirm these findings. The estimated average annual evapotranspiration of the semi-evergreen forest is 2.8 ± 0.19 mm \(\hbox {day}^{-1}\). The study of partitioning of energy fluxes showed the dominance of latent heat fluxes over sensible heat fluxes. The energy balance closure was found to increase with an increase in instability and the highest closure of around 83% was noted under neutral conditions.     

Characteristics of surface ozone in Agra,a sub-urban site in Indo-Gangetic Plain

In the present study, measurements of surface ozone (\(\hbox {O}_{3}\)) and its precursors (NO and \(\hbox {NO}_{2}\)) were carried out at a sub-urban site of Agra (\(27{^{\circ }}10'\hbox {N}\), \(78{^{\circ }}05'\hbox {E}\)), India during May 2012–May 2013. During the study period, average concentrations of \(\hbox {O}_{3}\), NO, and \(\hbox {NO}_{2}\) were \(39.6 \pm 25.3\), \(0.8 \pm 0.8\) and \(9.1 \pm 6.6 \, \hbox {ppb}\), respectively. \(\hbox {O}_{3}\) showed distinct seasonal variation in peak value of diurnal variation: summer \({>}\) post-monsoon \({>}\) winter \({>}\) monsoon. However, \(\hbox {NO}_{2}\) showed highest levels in winter and lowest in monsoon. The average positive rate of change of \(\hbox {O}_{3}\) (08:00–11:00 hr) was highest in April (16.3 ppb/hr) and lowest in August (1.1 ppb/hr), while average negative rate of change of \(\hbox {O}_{3}\) (17:00–19:00 hr) was highest in December (–13.2 ppb/hr) and lowest in July (–1.1 ppb/hr). An attempt was made to identify the \(\hbox {VOC--NO}_{\mathrm{x}}\) sensitivity of the site using \(\hbox {O}_{3}/\hbox {HNO}_{3}\) ratio as photochemical indicator. Most of the days this ratio was above the threshold value (12–16), which suggests \(\hbox {NO}_{\mathrm{x}}\) sensitivity of the site. The episodic event of ozone was characterized through meteorological parameters and precursors concentration. Fine particles (\(\hbox {PM}_{2.5}\)) cause loss of ozone through heterogeneous reactions on their surface and reduction in solar radiation. In the study, statistical analyses were used to estimate the amount of ozone loss.     

Crystallochemical studies on davidite from Bichun,Jaipur District,Rajasthan, India

Crystallochemical data on metamict davidite from albitites and albitised rocks from the Bichun area (Jaipur district, Rajasthan, India) of Banded Gneissic Complex (BGC) are provided. Davidite occurs as euhedral, subhedral to anhedral crystals in the form of disseminated grains and also as fracture filled veins. The crystals of davidite are up to 8 cm in length and 6 cm in width. The powder X-ray diffraction (XRD) pattern of the heat-treated davidite (at \(900{^{\circ }}\hbox {C}\)) reveals well-defined reflections of crystallographic planes. The calculated unit-cell parameters of the heat treated davidite are: \(\hbox {a}_{0} = \hbox {b}_{0} = 10.3556 \, \text {\AA }\) and \(\hbox {c}_{0} = 20.9067 \, \text {\AA }\), with unit-cell volume \(\hbox {(V)} = 1941.6385 \, \text {\AA }^{3}\); and \({\upalpha }={\upbeta }= 90^{\circ }\) and \({\upgamma }= 120^{\circ }\), which are in agreement with the values of davidite standard. Geochemical data reveals that the investigated davidite contains 51.5–52.6% \(\hbox {TiO}_{2}\), 14.8–15.1% \(\hbox {Fe}_{2} \hbox {O}_{3}\), 9.8–10.2% FeO, 6.97–7.12% \(\hbox {U}_{3} \hbox {O}_{8}\), 6.72–6.92% \(\hbox {RE}_{2} \hbox {O}_{3}\), 3.85–3.61% \(\hbox {K}_{2}\hbox {O}\), 0.9–1.4% \(\hbox {Al}_{2} \hbox {O}_{3}\), and 0.8–1.2% \(\hbox {SiO}_{2}\). The calculated structural formulae of the two davidite crystals are: D-1: \(\hbox {K}_{0.0044/0.004} \hbox {Ba}_{0.0044/0.005} \hbox {Ca}_{0.20/0.20} \hbox {Na}_{0.012/0.012} \hbox {Mn}_{0.053/0.053} \hbox {Mg}_{0.14/0.14} \hbox {Pb}_{0.0076/0.008} \hbox {Fe}_{2.675/2.675} \hbox {Fe}_{1.59/1.59} \hbox {Y}_{0.1175/0.118} \hbox {P}_{0.053/0.053} \hbox {Nb}_{0.008/0.008} \hbox {Sn}_{0.001/0.001} \hbox {Zr}_{0.033/0.033} \hbox {U}_{0.468/0.468} \hbox {Th}_{0.009/0.009} \,\,\hbox {REE}_{0.6829/0.683})_{6.05/6.05} (\hbox {Ti}_{12.15/12.15}\,\, \hbox {Fe}_{1.9022/1.903} \hbox {Si}_{0.372/0.372}\,\, \hbox {Al}_{0.517/0.517}\,\, \hbox {Cr}_{0.018/0.018} \hbox {Co}_{0.009/0.009} \hbox {Ni}_{0.027/0.027})_{15/15} \hbox {O}_{36/36} (\hbox {OH}_{0.319/0.319[]1.681/1.681})_{2/2}\) and D-2: \((\hbox {K}_{0.004/0.004} \hbox {Ba}_{0.005/0.005} \hbox {Ca}_{0.20/0.20} \hbox {Na}_{0.012/0.012} \hbox {Mn}_{0.05/0.05} \hbox {Mg}_{0.094/0.094} \hbox {Pb}_{0.007/0.007} \hbox {Fe}_{2.58/2.58} \hbox {Fe}_{1.71/1.71} \hbox {Y}_{0.112/0.112} \hbox {P}_{0.106/0.106} \hbox {Nb}_{0.006/0.006} \hbox {Sn}_{0.001/0.001} \hbox {Zr}_{0.03/0.03} \hbox {U}_{0.48/0.48} \hbox {Th}_{0.009/0.009} \hbox {REE}_{0.665/0.665})_{6.088/6.088} (\hbox {Ti}_{12.48/12.48} \hbox {Fe}_{1.87/1.87} \hbox {Si}_{0.249/0.249} \hbox {Al}_{0.334/0.334} \hbox {Cr}_{0.019/0.019} \hbox {Co}_{0.008/0.008} \hbox {Ni}_{0.04/0.04})_{15/15} \hbox {O}_{36/36} (\hbox {OH}_{0.098/0.098[]1.90/1.90})_{2/2}\). The calculated structural formulae are not fully stoichiometric, which could be due to metamict nature of davidite. The characteristic feature of distribution pattern of REE in davidite is unusually high concentration of LREE and HREE and substantially low content of MREE. It may be due to the occupation of REEs in two distinct crystallographic sites in davidite structure, i.e., M(1) and M(O) sites. Chondrite-normalised plot of davidite reveals a pronounced negative Eu-anomaly (\(\hbox {Eu}/\hbox {Eu}^{*} = 0.30{-}0.39\)), which suggests extremely fractionated nature of the metasomatising fluids from which davidite had crystallized. Metamict davidite-bearing U ores not only from Rajasthan, but also from other parts of India are likely to yield very high U leachability, thereby making them attractive sources of U, which otherwise are ignored by mineral engineers as uneconomic U ores.     

骑田岭A型花岗岩流体包裹体地球化学特征——对芙蓉超大型锡矿成矿流体来源的指示

南岭中段骑田岭A型花岗岩与芙蓉超大型锡矿床具有密切的时间和空间关系。流体包裹体地球化学研究表明,骑田岭A型花岗岩石英斑晶中的流体包裹体类型主要有熔融包裹体、流体-熔融包裹体和流体包裹体。流体-熔融包裹体的显微测温学研究结果显示,骑田岭A花岗岩在岩浆演化过程中可以分异出流体,且岩浆分异出的流体与芙蓉超大型锡矿床流体包裹体所反映的高温和高盐度的CaCl2-NaCl-KCl-H2O流体体系的特征相吻合。综合分析表明,芙蓉超大型锡矿床成矿流体中的高盐度流体应为骑田岭黑云母二长花岗岩结晶过程中分异出的富含Cl等挥发份和成矿物质的高盐度热流体。     

The effect of liquid composition on the partitioning of Ni between olivine and silicate melt

We report the results of experiments designed to separate the effects of temperature and pressure from liquid composition on the partitioning of Ni between olivine and liquid, \(D_{\text{Ni}}^{\text{ol/liq}}\). Experiments were performed from 1300 to 1600 °C and 1 atm to 3.0 GPa, using mid-ocean ridge basalt (MORB) glass surrounded by powdered olivine in graphite–Pt double capsules at high pressure and powdered MORB in crucibles fabricated from single crystals of San Carlos olivine at one atmosphere. In these experiments, pressure and temperature were varied in such a way that we produced a series of liquids, each with an approximately constant composition (~12, ~15, and ~21 wt% MgO). Previously, we used a similar approach to show that \(D_{\text{Ni}}^{\text{ol/liq}}\) for a liquid with ~18 wt% MgO is a strong function of temperature. Combining the new data presented here with our previous results allows us to separate the effects of temperature from composition. We fit our data based on a Ni–Mg exchange reaction, which yields \(\ln \left( {D_{\text{Ni}}^{\text{molar}} } \right) = \frac{{ -\Delta _{r(1)} H_{{T_{\text{ref}} ,P_{\text{ref}} }}^{ \circ } }}{RT} + \frac{{\Delta _{r(1)} S_{{T_{\text{ref}} ,P_{\text{ref}} }}^{ \circ } }}{R} - \ln \left( {\frac{{X_{\text{MgO}}^{\text{liq}} }}{{X_{{{\text{MgSi}}_{ 0. 5} {\text{O}}_{ 2} }}^{\text{ol}} }}} \right).\) Each subset of constant composition experiments displays roughly the same temperature dependence of \(D_{\text{Ni}}^{\text{ol/liq}}\) (i.e.,\(-\Delta _{r(1)} H_{{T_{\text{ref}} ,P_{\text{ref}} }}^{ \circ } /R\)) as previously reported for liquids with ~18 wt% MgO. Fitting new data presented here (15 experiments) in conjunction with our 13 previously published experiments (those with ~18 wt% MgO in the silicate liquid) to the above expression gives \(-\Delta _{r(1)} H_{{T_{\text{ref}} ,P_{\text{ref}} }}^{ \circ } /R\) = 3641 ± 396 (K) and \(\Delta _{r(1)} S_{{T_{\text{ref}} ,P_{\text{ref}} }}^{ \circ } /R\) = ? 1.597 ± 0.229. Adding data from the literature yields \(-\Delta _{r(1)} H_{{T_{\text{ref}} ,P_{\text{ref}} }}^{ \circ } /R\) = 4505 ± 196 (K) and \(\Delta _{r(1)} S_{{T_{\text{ref}} ,P_{\text{ref}} }}^{ \circ } /R\) = ? 2.075 ± 0.120, a set of coefficients that leads to a predictive equation for \(D_{\text{Ni}}^{\text{ol/liq}}\) applicable to a wide range of melt compositions. We use the results of our work to model the melting of peridotite beneath lithosphere of varying thickness and show that: (1) a positive correlation between NiO in magnesian olivine phenocrysts and lithospheric thickness is expected given a temperature-dependent \(D_{\text{Ni}}^{\text{ol/liq}} ,\) and (2) the magnitude of the slope for natural samples is consistent with our experimentally determined temperature dependence. Alternative processes to generate the positive correlation between NiO in magnesian olivines and lithospheric thickness, such as the melting of olivine-free pyroxenite, are possible, but they are not required to explain the observed correlation of NiO concentration in initially crystallizing olivine with lithospheric thickness.     

Competing effects of crystal chemistry and silicate melt composition on trace element behavior in magmatic systems: insights from crystal/silicate melt partitioning of the REE,HFSE, Sn,In, Ga,Ba, Pt and Rh

We present new partition coefficients for the REE, HFSE, Sn, In, Ga, Ba, Pt and Rh between clinopyroxene, olivine and basaltic melt as a function of crystal chemistry and melt composition at temperatures of 1190–1300 °C and 1-bar pressure. Two components, namely \(\mathrm {Al_2O_3}\) and \(\mathrm {Na_2O}\), were chosen to be investigated since they are known to affect the structure of silicate melts and especially clinopyroxene crystal chemistry. The amount of \(^{[4]}\mathrm{Al}\) in clinopyroxene will result in an increase of \(D_i^\mathrm{{cpx/melt}}\) even after applying a correction factor to account for the effect of melt polymerization. Moreover, the positive correlation between \(^{[4]}\mathrm{Al}\) and \(D_i^\mathrm{{cpx/melt}}\) is not restricted to the REE, but also applies for Sn, Ga, In, and Ba. The addition of up to 2.6 wt% \(\mathrm {Na_2O}\) to the silicate melt universally increases the \(D_i^\mathrm{{cpx/melt}}\) without any concomitant change in crystal chemistry or a significant effect in melt polymerization. This compositional effect is likely due to the ability of Na to break REE–Al complexes in the melt. Our results emphasize the importance of considering all variables that affect the behavior of trace elements in magmatic systems before applying the lattice strain model and derive meaningful results for the changes in the parameters of the crystallographic sites.     

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.     

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.     

Synthesis of monticellite–forsterite and merwinite–forsterite symplectites in the CaO–MgO–SiO<Subscript>2</Subscript> model system: influence of temperature and water content on microstructure evolution

Homogeneous single crystals of synthetic monticellite with the composition \({\text{Ca}}_{0.88}{\text{Mg}}_{1.12}{\text{SiO}}_4\) (Mtc I) were annealed in a piston-cylinder apparatus at temperatures between 1000 and \(1200\,^{\circ }\hbox {C}\), pressures of 1.0–1.4 GPa, for run durations from 10 min to 24 h and applying bulk water contents ranging from 0.0 to 0.5 wt% of the total charge. At these conditions, Mtc I breaks down to a fine-grained, symplectic intergrowth. Thereby, two types of symplectites are produced: a first symplectite type (Sy I) is represented by an aggregate of rod-shaped forsterite immersed in a matrix of monticellite with end-member composition (Mtc II), and a second symplectite type (Sy II) takes the form of a lamellar merwinite–forsterite intergrowth. Both symplectites may form simultaneously, where the formation of Sy I is favoured by the presence of water. Sy I is metastable with respect to Sy II and is successively replaced by the latter. For both symplectite types, the characteristic spacing of the symplectite phases is independent of run duration and is only weeakly influenced by the water content, but it is strongly temperature dependent. It varies from about 400 nm at \(1000\,^{\circ }\hbox {C}\) to 1200 nm at \(1100\,^{\circ }\hbox {C}\) in Sy I, and from 300 nm at \(1000\,^{\circ }\hbox {C}\) to 700 nm at \(1200\,^{\circ }\hbox {C}\) in Sy II. A thermodynamic analysis reveals that the temperature dependence of the characteristic spacing of the symplectite phases is due to a relatively high activation energy for chemical segregation by diffusion within the reaction front as compared to the activation energy for interface reactions at the reaction front. The temperature dependence of the characteristic lamellar spacing and the temperature-time dependence of overall reaction progress have potential for applications in geo-thermometry and geo-speedometry.     

Geochemistry and geochronology of the mafic dikes in the Taipusi area,northern margin of North China Craton: Implications for Silurian tectonic evolution of the Central Asian Orogen

The Taipusi area in the Bainaimiao Arc Belt is located in the northern margin of the North China Craton, at the southern margin of the middle Central Asian Orogenic Belt. It is characterized by large exposures of mafic dikes. In this contribution, we present first-hand whole-rock major and trace elements, zircon U–Pb geochronology and in situ trace element geochemistry data for these mafic rocks, which reveal their petrogenesis and tectonic evolution. These mafic dikes display varied compositions of \(\hbox {SiO}_{2}\) (49.42–54.29%), \(\hbox {TiO}_{2}\) (0.63–1.08%), \(\hbox {Al}_{2}\hbox {O}_{3}\) (13.94–17.60%), MgO (4.66–10.51%), \(\hbox {Fe}_{2}\hbox {O}_{3}\) (1.59–3.07%), FeO (4.60–6.90%), CaO (4.57–8.91%), \(\hbox {Na}_{2}\hbox {O}\) (1.61–4.26%), \(\hbox {K}_{2}\hbox {O}\) (0.92–2.54%) and \(\hbox {P}_{2}\hbox {O}_{5}\) (0.11–0.29%). They are mainly of high-K calc-alkaline series with indistinct Eu anomalies, enriched in large ion lithophile elements (e.g., Rb, Ba, K and Sr) but depleted in high field strength elements (e.g., Nb, P and Ti). These suggest that the crystallizing magma was derived from enriched mantle altered by metasomatic fluids in a subduction setting with imprints of active continental margin features. The high concentrations of Hf, U, Th, Pb and Y, pronounced positive Ce but slightly negative Eu anomalies in zircons indicating that the magma underwent a fractional crystallization and crustal contamination process, with medium to high \(f\hbox {O}_{2}\). Zircon LA–ICP–MS U–Pb dating yielded concordant ages of 437–442 Ma for these mafic dikes, which is consistent with the early Paleozoic volcanic arc magmatic activity in the Bainaimiao area. Hence, we conclude that the Bainaimiao Arc Belt is a continental arc formed by the southward subduction of the Paleo-Asian ocean during early Paleozoic.     

Quantification of groundwater–surface water interactions using environmental isotopes: A case study of Bringi Watershed,Kashmir Himalayas,India

Environmental isotopes including \({\updelta }^{18}\)O, \({\updelta }^{2}\)H and \(^{3}\)H of precipitation, streams and springs were determined in the mountainous Bringi catchment of Kashmir Himalaya, dominated by carbonate lithology. The isotopic signature of winter precipitation is reflected in stream and spring water in late spring and is, therefore, representative of snow melting. The spring waters in September bear the enriched isotopic signatures of summer rainfall. The strong correlation (\(r^{2} = 0.97\)) between the isotopic composition of streams and springs indicates the streams and springs either share similar catchments or the springs are recharged by the streams. Chloride mass balance and isotopic mass balance studies suggest that the surface recharge component averages 337.35 m\(^{3}\)/s, which is about 75% of total stream discharge during the high flow period. Similarly, the contribution of surface water to groundwater recharge during the low flow period averages 7.5 m\(^{3}\)/s, which is about 18.6% of total stream flow. Furthermore, the mean residence time of the springs calculated from the tritium decay equation is very short (<1 year). The residence time is longer for Kongamnag and short for Achabalnag, which is further supported by dye testing.     

Mineral shock signatures in rocks from Dhala (Mohar) impact structure,Shivpuri district,Madhya Pradesh,India

A concrete study combining optical microscopy, Raman spectroscopy and X-ray diffractometry, was carried out on subsurface samples of basement granite and melt breccia from Mohar (Dhala) impact structure, Shivpuri district, Madhya Pradesh, India. Optical microscopy reveals aberrations in the optical properties of quartz and feldspar in the form of planar deformation feature-like structures, lowered birefringence and mosaics in quartz, toasting, planar fractures and ladder texture in alkali feldspar and near-isotropism in bytownite. It also brings to light incidence of parisite, a radioactive rare mineral in shocked granite. Raman spectral pattern, peak positions, peak widths and multiplicity of peak groups of all minerals, suggest subtle structural/crystallographic deviations. XRD data further reveals minute deviations of unit cell parameters of quartz, alkali feldspar and plagioclase, with respect to standard \({\upalpha }\)-quartz, high- and low albite and microcline. Reduced cell volumes in these minerals indicate compression due to pressure. The \(\hbox {c}_{0}/\hbox {a}_{0}\) values indicate an inter-tetrahedral angle roughly between \(120^{\mathrm{o}}\) and \(144^{\mathrm{o}}\), further pointing to a possible pressure maxima of around 12 GPa. The observed unit cell aberration of minerals may indicate an intermediate stage between crystalline and amorphous stages, thereby, signifying possible overprinting of decompression signatures over shock compression effects, from a shock recovery process.     

H<Subscript>2</Subscript>O diffusion in peralkaline to peraluminous rhyolitic melts

The diffusion of water in a peralkaline and a peraluminous rhyolitic melt was investigated at temperatures of 714–1,493 K and pressures of 100 and 500 MPa. At temperatures below 923 K dehydration experiments were performed on glasses containing about 2 wt% H₂O _t in cold seal pressure vessels. At high temperatures diffusion couples of water-poor (<0.5 wt% H₂O _t ) and water-rich (~2 wt% H₂O _t ) melts were run in an internally heated gas pressure vessel. Argon was the pressure medium in both cases. Concentration profiles of hydrous species (OH groups and H₂O molecules) were measured along the diffusion direction using near-infrared (NIR) microspectroscopy. The bulk water diffusivity () was derived from profiles of total water () using a modified Boltzmann-Matano method as well as using fittings assuming a functional relationship between and Both methods consistently indicate that is proportional to in this range of water contents for both bulk compositions, in agreement with previous work on metaluminous rhyolite. The water diffusivity in the peraluminous melts agrees very well with data for metaluminous rhyolites implying that an excess of Al₂O₃ with respect to alkalis does not affect water diffusion. On the other hand, water diffusion is faster by roughly a factor of two in the peralkaline melt compared to the metaluminous melt. The following expression for the water diffusivity in the peralkaline rhyolite as a function of temperature and pressure was obtained by least-squares fitting:

Stable carbon and oxygen isotope study on benthic foraminifera: Implication for microhabitat preferences and interspecies correlation

Stable isotopes of benthic foraminifera have widely been applied in micropalaeontological research to understand vital effects in foraminifera. Isotopic fractionations are mainly controlled by ontogeny, bottom/pore water chemistry, habitat preference, kinetic effect and respiration. Discontinuous abundance of a species for isotopic analysis has forced us to select multiple species from down-core samples. Thus standardisation factors are required to convert isotopic values of one species with respect to other species. The present study is pursued on isotopic values of different pairs of benthic foraminifera from the Krishna–Godavari basin and Peru offshore to understand habitat-wise isotopic variation and estimation of isotopic correction factors for the paired species (Cibicides wuellerstorfi–Bulimina marginata, Ammonia spp.–Loxostomum amygdalaeformis and Bolivina seminuda–Nonionella auris). Infaunal species (B. marginata, Ammonia spp. and N. auris) show a lighter carbon isotopic excursion with respect to the epifaunal to shallow infaunal forms (C. wuellerstorfi, L. amygdalaeformis and B. seminuda). These lighter \(\updelta ^{13}\) \(\hbox {C}\) values are related to utilisation of \(\hbox {CO}_{2}\) produced by anaerobic remineralisation of organic matter. However, enrichment of \(\updelta ^{18}\) \(\hbox {O}\) for the deeper microhabitat (bearing lower pH and decreased \({\hbox {CO}_{3}}^{2-})\) is only recorded in case of B. marginata. It is reverse in case of N. auris and related to utilisation of respiratory \(\hbox {CO}_{2}\) and internal dissolve inorganic carbon pool. Estimation of interspecies isotopic correction factors for the species pairs (\(\updelta ^{13}\) \(\hbox {C}\) of C. wuellerstorfi–B. marginata, L. amygdalaeformis–Ammonia spp., N. auris–B. seminuda) and \(\updelta ^{18}\) \(\hbox {O}\) of C. wuellerstorfi–B. marginata are statistically reliable and may be used in palaeoecological studies.