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.     

New paleomagnetic results on $$\sim $$2367 Ma Dharwar giant dyke swarm,Dharwar craton,southern India: implications for Paleoproterozoic continental reconstruction

Here we report new paleomagnetic results and precise paleopole position of the extensional study on \(\sim \)2367 Ma mafic giant radiating dyke swarm in the Dharwar craton, southern India. We have sampled 29 sites on 12 dykes from NE–SW Karimnagar–Hyderabad dykes and Dhone–Gooty sector dykes, eastern Dharwar craton to provide unambiguous paleomagnetism evidence on the spectacular radiating dyke swarm and thereby strengthening the presence of single magmatic event at \(\sim \)2367 Ma. A total of 158 samples were subjected to detailed alternating field and thermal demagnetization techniques and the results are presented here along with previously reported data on the same dyke swarm. The remanent magnetic directions are showing two components, viz., seven sites representing four dykes show component (A) with mean declination of \(94{{}^{\circ }}\) and mean inclination of \(-\,70{{}^{\circ }}\) (\(\hbox {k}=87\), \(\upalpha _{95}=10{{}^{\circ }}\)) and corresponding paleopole at \(16{{}^{\circ }}\hbox {N}\), \(41{{}^{\circ }}\hbox {E}\) (\(\hbox {dp}=15{{}^{\circ }}\) and \(\hbox {dm}=17{{}^{\circ }}\)) and 22 sites representing 8 dykes yielded a component (B) with mean declination of \(41{{}^{\circ }}\) and mean inclination of \(-\,21{{}^{\circ }}\) (\(\hbox {k}=41\), \(\upalpha _{95}=9{{}^{\circ }}\)) with a paleopole at \(41{{}^{\circ }}\hbox {N}\), \(200{{}^{\circ }}\hbox {E}\) (\(\hbox {dp}=5{{}^{\circ }}\) and \(\hbox {dm}=10{{}^{\circ }}\)). Component (A) results are similar to the previously reported directions from the \(\sim \)2367 Ma dyke swarm, which have been confirmed fairly reliably to be of primary origin. The component (B) directions appear to be strongly overprinted by the 2080 Ma event. The grand mean for the primary component (A) combined with earlier reported studies gives mean declination of \(97{{}^{\circ }}\) and mean inclination of \(-\,79{{}^{\circ }}\) (\(\hbox {k}=55\), \(\upalpha _{95}=3{{}^{\circ }}\)) with a paleopole at \(15{{}^{\circ }}\hbox {N}\), \(57{{}^{\circ }}\hbox {E}\) (\(\hbox {dp}=5{{}^{\circ }}\), \(\hbox {dm}=6{{}^{\circ }}\)). Paleogeographical position for the Dharwar craton at \(\sim \)2367 Ma suggests that there may be a chance to possible spatial link between Dharwar dykes of Dharwar craton (India), Widgemooltha and Erayinia dykes of Yilgarn craton (Australia), Sebanga Poort Dykes of Zimbabwe craton (Africa) and Karelian dykes of Kola-Karelia craton (Baltica Shield).     

Indian summer monsoon forcing on the deglacial polar cold reversals

The deglacial transition from the last glacial maximum at \(\sim \)20 kiloyears before present (ka) to the Holocene (11.7 ka to Present) was interrupted by millennial-scale cold reversals, viz., Antarctic Cold Reversal (\(\sim \)14.5–12.8 ka) and Greenland Younger Dryas (\(\sim \)12.8–11.8 ka) which had different timings and extent of cooling in each hemisphere. The cause of this synchronously initiated, but different hemispheric cooling during these cold reversals (Antarctic Cold Reversal \(\sim \)3\(^{\circ }\hbox {C}\) and Younger Dryas \(\sim \)10\(^{\circ }\hbox {C}\)) is elusive because \(\hbox {CO}_{2}\), the fundamental forcing for deglaciation, and Atlantic meridional overturning circulation, the driver of antiphased bipolar climate response, both fail to explain this asymmetry. We use centennial-resolution records of the local surface water \(\delta ^{18}\hbox {O}\) of the Eastern Arabian Sea, which constitutes a proxy for the precipitation associated with the Indian Summer Monsoon, and other tropical precipitation records to deduce the role of tropical forcing in the polar cold reversals. We hypothesize a mechanism for tropical forcing, via the Indian Summer Monsoons, of the polar cold reversals by migration of the Inter-Tropical Convergence Zone and the associated cross-equatorial heat transport.     

Phase diagram and thermodynamic properties of AIPO<Subscript>4</Subscript> based on first-principles calculations and the quasiharmonic approximation

We calculated the phase diagram of \(\hbox {AlPO}_{4}\) up to 15 GPa and 2,000 K and investigated the thermodynamic properties of the high-pressure phases. The investigated phases include the berlinite, moganite-like, \(\hbox {AlVO}_{4},\, P2_1/c\), and \(\hbox {CrVO}_{4}\) phases. The computational methods used include density functional theory, density functional perturbation theory, and the quasiharmonic approximation. The investigated thermodynamic properties include the thermal equation of state, isothermal bulk modulus, thermal expansivity, and heat capacity. With increasing pressure, the ambient phase berlinite transforms to the moganite-like phase, and then to the \(\hbox {AlVO}_{4}\) and \(P2_1/c\) phases, and further to the \(\hbox {CrVO}_{4}\) phase. The stability fields of the \(\hbox {AlVO}_{4}\) and \(P2_1/c\) phases are similar in pressure but different in temperature, as the \(\hbox {AlVO}_{4}\) phase is stable at low temperatures, whereas the \(P2_1/c\) phase is stable at high temperatures. All of the phase relationships agree well with those obtained by quench experiments, and they support the stabilities of the moganite-like, \(\hbox {AlVO}_{4}\), and \(P2_1/c\) phases, which were not observed in room-temperature compression experiments.     

Near InfraRed Imaging Spectrograph (NIRIS) for ground-based mesospheric OH(6-2) and $$\hbox {O}_{2}$$(0-1) intensity and temperature measurements

This paper describes the development of a new Near InfraRed Imaging Spectrograph (NIRIS) which is capable of simultaneous measurements of OH(6-2) Meinel and \(\hbox {O}_{2}\)(0-1) atmospheric band nightglow emission intensities. In this spectrographic technique, rotational line ratios are obtained to derive temperatures corresponding to the emission altitudes of 87 and 94 km. NIRIS has been commissioned for continuous operation from optical aeronomy observatory, Gurushikhar, Mount Abu (\(24.6^{\circ }\hbox {N}\), \(72.8^{\circ }\hbox {E}\)) since January 2013. NIRIS uses a diffraction grating of 1200 lines \(\hbox {mm}^{-1}\) and 1024\(\times \)1024 pixels thermoelectrically cooled CCD camera and has a large field-of-view (FOV) of \(80^{\circ }\) along the slit orientation. The data analysis methodology adopted for the derivation of mesospheric temperatures is also described in detail. The observed NIRIS temperatures show good correspondence with satellite (SABER) derived temperatures and exhibit both tidal and gravity waves (GW) like features. From the time taken for phase propagation in the emission intensities between these two altitudes, vertical phase speed of gravity waves, \(c_{z}\), is calculated and along with the coherent GW time period ‘\(\tau \)’, the vertical wavelength, \(\lambda _{z}\), is obtained. Using large FOV observations from NIRIS, the meridional wavelengths, \(\lambda _{y}\), are also calculated. We have used one year of data to study the possible cause(s) for the occurrences of mesospheric temperature inversions (MTIs). From the statistics obtained for 234 nights, it appears that in situ chemical heating is mainly responsible for the observed MTIs than the vertical propagation of the waves. Thus, this paper describes a novel near infrared imaging spectrograph, its working principle, data analysis method for deriving OH and \(\hbox {O}_{2}\) emission intensities and the corresponding rotational temperatures at these altitudes, derivation of gravity wave parameters (\(\tau \), \(c_{z}\), \(\lambda _{z}\), and \(\lambda _{y})\), and results on the statistical study of MTIs that exist in the earth’s mesospheric altitudes.     

Effect of solar flare on the equatorial electrojet in eastern Brazil region

The effect of solar flare, sudden commencement of magnetic storm and of the disturbances ring current on the equatorial electrojet in the Eastern Brazil region, where the ground magnetic declination is as large as \(20^{^{\circ }}\hbox {W}\) is studied based on geomagnetic data with one minute resolution from Bacabal during November–December 1990. It is shown that the mean diurnal vector of the horizontal field was aligned along \(2{^{\circ }}\hbox {E}\) of north at Huancayo and \(30{^{\circ }}\hbox {W}\) of north at Bacabal during the month of December 1990. Number of solar flares that occurred on 30 December 1990 indicated the direction of solar flare related \(\Delta H\) vector to be aligned along \(5{^{\circ }}\hbox {E}\) of north at Huancayo and \(28{^{\circ }}\hbox {W}\) of north at Bacabal. This is expected as the solar flare effects are due to the enhanced conductivity in the ionosphere. The SC at 2230 UT on 26 November 1990 produced a positive impulse in \(\Delta X\) and negative impulse in \(\Delta Y\) at Bacabal with \(\Delta H\) vector aligned along \(27{^{\circ }}\hbox {W}\) of north. At Huancayo the \(\Delta H\) vector associated with SC is aligned along \(8{^{\circ }}\hbox {E}\) of north, few degrees east to the alignment of the diurnal vector of H. The magnetic storm that followed the SC had a minimum Dst index of –150 nT. The corresponding storm time disturbance in \(\Delta X\) at Huancayo as well as at Bacabal were about –250 nT but \(\Delta Y\) at Bacabal was about +70 nT and very small at Huancayo, that give the alignment of the H vector due to ring current about \(16{^{\circ }}\hbox {W}\) of north at Bacabal and almost along N–S at Huancayo. Thus alignment of the \(\Delta H\) vector due to ring current at Bacabal is \(14{^{\circ }}\hbox {E}\) of the mean direction of \(\Delta H\) vector during December 1990. This is consistent with the direction of ring current dependent on the dipole declination at the ring current altitude which is about \(5{^{\circ }}\hbox {W}\) of north over Bacabal and the deviation of declination due to the ring current during disturbed period given by the angle (\(\psi \)-D).     

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.     

Early Neoarchaean A-type granitic magmatism by crustal reworking in Singhbhum craton: Evidence from Pala Lahara area,Orissa

Several volumetrically minor \(\sim \)2.8 Ga anorogenic granites and rhyolites occur along the marginal part of the Singhbhum craton whose origin and role in crustal evolution are poorly constrained. This contribution presents petrographic, geochemical, zircon U–Pb and trace element, and mineral chemical data on such granites exposed in the Pala Lahara area to understand their petrogenesis and tectonic setting. The Pala Lahara granites are calc-alkaline, high-silica rocks and define a zircon U–Pb age of 2.79 Ga. These granites are ferroan, weakly metaluminous, depleted in Al, Ca and Mg and rich in LILE and HFSE. They are classified as A2-type granites with high Y/Nb ratios. Geochemical characteristics (high \(\hbox {SiO}_{2}\) and \(\hbox {K}_{2}\hbox {O}\), very low MgO, Mg#, Cr, Ni and V, negative Eu anomaly, flat HREE and low Sr/Y) and comparison with melts reported by published experimental studies suggest an origin through high-temperature, shallow crustal melting of tonalitic/granodioritic source similar to the \(\sim \)3.3 Ga Singhbhum Granite. Intrusion of the Pala Lahara granites was coeval with prominent mafic magmatism in the Singhbhum craton (e.g., the Dhanjori mafic volcanic rocks and NNE–SSW trending mafic dyke swarm). It is suggested that the \(\sim \)2.8 Ga A-type granites in the Singhbhum craton mark a significant crustal reworking event attendant to mantle-derived mafic magmatism in an extensional tectonic setting.     

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.     

Petrography and geochemistry of the Proterozoic sandstones of Somanpalli Group from Pomburna area,Eastern Belt of Pranhita–Godavari Valley,central India: Implications for provenance,weathering and tectonic setting

In this paper, we, for the first time, report geochemistry of sandstone from Somanpalli Group from Pomburna area in the Eastern Belt of Pranhita–Godavari (PG) Valley, central India and studied to infer their provenance, intensity of paleo-weathering and depositional tectonic setting. Petrographic study of sandstones show QFL modal composition of arenite. Chemical results show high \(\hbox {SiO}_{2}\) and CIA but lower \(\hbox {Al}_{2}\hbox {O}_{3}, \hbox {TiO}_{2}\), Rb, Sr, \(\hbox {K}_{2}\hbox {O}\) indicating mixed sources. Major elements chemistry parameters such as, \(\hbox {K}_{2}\hbox {O/Al}_{2}\hbox {O}_{3}\) ratio and positive correlation of Rb with \(\hbox {K}_{2}\hbox {O}\), reflects a warm and humid climate for study area. The tectonic discrimination plots (\(\hbox {SiO}_{2}/20\)–\(\hbox {K}_{2}\hbox {O} + \hbox {Na}_{2}\hbox {O}\)–\(\hbox {TiO}_{2} + \hbox {Fe}_{2}\hbox {O}_{3} + \hbox {MgO};\,\hbox {K}_{2}\hbox {O}/\hbox {Na}_{2}\hbox {O}\) vs. \(\hbox {SiO}_{2}\); Th–Sc–Zr/20) indicate dominantly passive margin and slight active tectonic setting. Concentrations of Zr, Nb, Y, and Th are higher compared to the UCC values and the trends in Th/Cr, Th/Co, La/Sc and Cr/Zr ratios support a felsic and mafic source for these sandstones and deposition in passive margin basin. Chondrite normalized REE pattern reflects LREE depletion, negative Eu anomaly and flat HREE similar to UCC, felsic components. ICV value (0.95) also supports tectonically quiescent passive margin settings. CIA values (74) indicate high degree of chemical weathering and warm and humid paleoclimatic condition.     

Correlation analyses of effects of temperature on physical and mechanical properties of clay

In determining the physical and mechanical parameters of clay, it is sometimes necessary to determine them indirectly from other parameters since they cannot be measured directly from laboratory or field tests. In order to determine the effect of temperature on the behavior of clay, an indirect approach is used here by analyzing the changes of mass (\(\Delta m\)), density (\(\rho\)), porosity (\(\phi\)), P-wave velocity (\({v_p}\)), thermal conductivity (\(\lambda\)), specific heat capacity (c), resistivity (R) and uniaxial compressive strength (f) of clay from eastern China for a temperature range between 20 and 800 °C. The results indicate that temperature has a significant effect on these parameters. Comparisons between \(\Delta m\) and \(\rho\), \(\Delta m\) and \({v_p}\), \(\rho\) and \({v_p}\), \(\phi\) and \(\lambda\), \({v_p}\) and f, R and f show a linear change among these parameters,whereas the relationships among \(\Delta m\) and \(\phi\), \(\phi\) and \({v_p}\), \(\phi\) and R, \({v_p}\) and \(\lambda\), \(\phi\) and f are exponential. It is difficult to obtain these relationships by using regression analysis with high levels of accuracy. Further refinement is therefore required.     

Moisture rainout fraction over the Indian Ocean during austral summer based on $$^{18}\hbox {O}/{}^{16}\hbox {O}$$ ratios of surface seawater,rainwater at latitude range of 10°N–60°S

Oxygen isotope ratios (\(^{18}\hbox {O}/^{16}\hbox {O}\)) of surface seawater and rainwater samples from the Indian Ocean region (10°N–60°S) during austral summer collected onboard ORV Sagar Nidhi during 2011–2013 have been measured along with salinity, sea surface temperature and relative humidity. The rainwater is isotopically lighter (by \(4.6\pm 2.7\permille )\) compared to the equilibrium condensation of the vapour arising from the seawater at the ambient condition. The isotopic composition of the vapour at high altitude responsible for the rain formation at the sampling location is estimated from a global atmospheric water isotope model (IsoGSM2). The apparent deficit of \(\sim \)5\(\permille \) can be explained by invoking a high degree of rainout (on average, about 70% of the overhead atmospheric moisture) during transport of the source vapour to the sampling location undergoing a Rayleigh fractionation. The required rainout fraction is higher (\(\sim \)80%) in the latitude belt 40°–60°S compared to the equatorial belt (\(\sim \)60%). The pattern of variation in the rainout fraction with latitude is consistent with the well-known evaporation/precipitation processes in the Indian Ocean.     

Effect of $$\hbox {CO}_2$$ solubility on dissolution rate of calcite in saline aquifers for temperature range of 50–100 $$^{\circ } \hbox {C}$$∘C and pressures up to 600 bar: alterations of fractures geometry in carbonate rocks by $$\hbox {CO}_2$$-acidified brines

An empirical model is developed to predict the dissolution rate of calcite in saline solutions that are saturated with respect to dissolved \(\hbox {CO}_2\) over a broad range of both subcritical and supercritical conditions. The focus is on determining the rate of calcite dissolution within a temperature range of 50–100 \(^\circ \hbox {C}\) and pressures up to 600 bar, relevant for \(\hbox {CO}_2\) sequestration in saline aquifers. A general reaction kinetic model is used that is based on the extension of the standard Arrhenius equation with an added, solubility-dependent, pH term to account for the saturated concentration of dissolved \(\hbox {CO}_2\). On the basis of this kinetic model, a new rate equation is obtained using multi-parameter, nonlinear regression of experimental data to determine the dissolution of calcite as a function of temperature, pressure and salinity. Different models for the activity coefficient of \(\hbox {CO}_2\) dissolved in saline solutions are accounted for. The new rate equation helps us obtain good agreement with experimental data, and it is applied to study the geochemically induced alterations of fracture geometry due to calcite dissolution.     

Thermodynamics and phonon dispersion of pyrope and grossular silicate garnets from ab initio simulations

The phonon dispersion and thermodynamic properties of pyrope (\(\hbox {Mg}_3\hbox {Al}_2\hbox {Si}_3\hbox {O}_{12}\)) and grossular (\(\hbox {Ca}_3\hbox {Al}_2\hbox {Si}_3\hbox {O}_{12}\) ) have been computed by using an ab initio quantum mechanical approach, an all-electron variational Gaussian-type basis set and the B3LYP hybrid functional, as implemented in the Crystal program. Dispersion effects in the phonon bands have been simulated by using supercells of increasing size, containing 80, 160, 320, 640, 1280 and 2160 atoms, corresponding to 1, 2, 4, 8, 16 and 27 \(\mathbf {k}\) points in the first Brillouin zone. Phonon band structures, density of states and corresponding inelastic neutron scattering spectra are reported. Full convergence of the various thermodynamic properties, in particular entropy (S) and specific heat at constant volume (\(C_\mathrm{{V}}\)), with the number of \(\mathbf {k}\) points is achieved with 27 \(\mathbf {k}\) points. The very regular behavior of the S(T) and \(C_\mathrm{{V}}(T)\) curves as a function of the number of \(\mathbf {k}\) points, determined by high numerical stability of the code, permits extrapolation to an infinite number of \(\mathbf {k}\) points. The limiting value differs from the 27-\(\mathbf {k}\) case by only 0.40 % at 100 K for S (the difference decreasing to 0.11 % at 1000 K) and by 0.29 % (0.05 % at 1000 K) for \(C_\mathrm{{V}}\). The agreement with the experimental data is rather satisfactory. We also address the problem of the relative entropy of pyrope and grossular, a still debated question. Our lattice dynamical calculations correctly describe the larger entropy of pyrope than grossular by taking into account merely vibrational contributions and without invoking “static disorder” of the Mg ions in dodecahedral sites. However, as the computed entropy difference is found to be larger than the experimental one by a factor of 2–3, present calculations cannot exclude possible thermally induced structural changes, which could lead to further conformational contributions to the entropy.     

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.     

Variations of trace gases over the Bay of Bengal during the summer monsoon

In situ measurements of near-surface ozone (\(\hbox {O}_{3})\), carbon monoxide (CO), and methane (\(\hbox {CH}_{4})\) were carried out over the Bay of Bengal (BoB) as a part of the Continental Tropical Convergence Zone (CTCZ) campaign during the summer monsoon season of 2009. \(\hbox {O}_{3}\), CO and \(\hbox {CH}_{4}\) mixing ratios varied in the ranges of 8–54 ppbv, 50–200 ppbv and 1.57–2.15 ppmv, respectively during 16 July–17 August 2009. The spatial distribution of mean tropospheric \(\hbox {O}_{3}\) from satellite retrievals is found to be similar to that in surface \(\hbox {O}_{3}\) observations, with higher levels over coastal and northern BoB as compared to central BoB. The comparison of in situ measurements with the Monitoring Atmospheric Composition & Climate (MACC) global reanalysis shows that MACC simulations reproduce the observations with small mean biases of 1.6 ppbv, –2.6 ppbv and 0.07 ppmv for \(\hbox {O}_{3}\), CO and \(\hbox {CH}_{4}\), respectively. The analysis of diurnal variation of \(\hbox {O}_{3}\) based on observations and the simulations from Weather Research and Forecasting coupled with Chemistry (WRF-Chem) at a stationary point over the BoB did not show a net photochemical build up during daytime. Satellite retrievals show limitations in capturing \(\hbox {CH}_{4}\) variations as measured by in situ sample analysis highlighting the need of more shipborne in situ measurements of trace gases over this region during monsoon.     

Comparison of earthquake source characteristics in the Kachchh Rift Basin and Saurashtra horst,Deccan Volcanic Province,western India

Seismic source parameters of small to moderate sized intraplate earthquakes that occurred during 2002–2009 in the tectonic blocks of Kachchh Rift Basin (KRB) and the Saurashtra Horst (SH), in the stable continental region of western peninsular India, are studied through spectral analysis of shear waves. The data of aftershock sequence of the 2001 Bhuj earthquake (\(M_{w}\) 7.7) in the KRB and the 2007 Talala earthquake (\(M_{w}\) 5.0) in the SH are used for this study. In the SH, the seismic moment (\(M_{o})\), corner frequency \((f_{c})\), stress drop (\(\varDelta \sigma \)) and source radius (r) vary from \(7.8\times 10^{11}\) to \(4.0\times \)10\(^{16}\) N-m, 1.0–8.9 Hz, 4.8–10.2 MPa and 195–1480 m, respectively. While in the KRB, these parameters vary from \(M_{o} \sim 1.24 \,\times \, 10^{11}\) to \(4.1 \times 10^{16}\) N-m, \(f_{c }\sim \) 1.6 to 13.1 Hz, \(\varDelta \sigma \sim 0.06\) to 16.62 MPa and \(r \sim 100\) to 840 m. The kappa (K) value in the KRB (0.025–0.03) is slightly larger than that in the SH region (0.02), probably due to thick sedimentary layers. The estimated stress drops of earthquakes in the KRB are relatively higher than those in SH, due to large crustal stress concentration associated with mafic/ultramafic rocks at the hypocentral depths. The results also suggest that the stress drop value of intraplate earthquakes is larger than the interplate earthquakes. In addition, it is observed that the strike-slip events in the SH have lower stress drops, compared to the thrust and strike-slip events.     

Structural and luminescent characterisation of uraniferous fluorapatite and haematite associated with phosphatic rocks of the Bijawar group in Sagar District,Madhya Pradesh (India)

The structural and spectroscopic characteristics of phosphatic ferruginous shale samples from the Bijawar Group rocks from Sagar District of Madhya Pradesh (India) have been probed for identification of uranium species. Fluorapatite (\(\hbox {Ca}_{5}\hbox {(PO}_{4})_{3}\hbox {F}\), FAP) and haematite (\(\upalpha \)-\(\hbox {Fe}_{2}\hbox {O}_{3}\)) were identified as the main phases in the separated mineral concentrates. The photoluminescence (PL) and X-ray absorption near edge spectroscopy (XANES) studies pointed to a strong experimental evidence of both U(IV) and U(VI) oxidation states in the mineral concentrate portion obtained from the same parent host rock. The PL spectrum has confirmed the charge transfer (f–d) transition bands in UV and near-UV regions with emission peaks at ca. 290, 313, 336, 399 and 416 nm, which has been attributed to the substitution of \(\hbox {Ca}^{2+}\) ions by U(IV) in FAP and broad structureless emission due to stabilisation of U(VI) as \(\hbox {UO}_{6}^{6-}\) in haematite. Time-resolved spectroscopy studies have revealed biexponential decay components lasting 2–5 ns for U(IV) species and \(10\,\upmu \hbox {s}\) for U(VI) species. These characterisations revealed the fundamental information about the oxidation state and form of uranium in this region. Remediation measures for the Bijawar region are also suggested.     

Fission-track evidence of tectonic evolution in the northwestern Qaidam Basin,China

Fission-track dating was conducted on zircons and apatites from 11 cores of the upper Xiaganchaigou Formation and lower Shangganchaigou Formation (northwestern Qaidam Basin). The obtained apatite fission-track age is 3.1–61.9 Ma, and the zircon fission-track age is 49.2–123.5 Ma. Although the average apatite age is consistent with ages predicted from the stratigraphy, nine of the 11 apatite fission-track ages have \(\hbox {P}(\upchi ^{2}) < 5\%\), indicating that the grains experienced heterogeneous annealing after sedimentation. The average zircon age is greater than that indicated by stratigraphy, and all eight zircon fission ages have \(\hbox {P}(\upchi ^{2})>5\%\), exhibiting consistent characteristics and indicating that zircons retain provenance age information after burial. From the zircon and apatite ages, the fission-track length distribution, and the geological setting, the northwestern Qaidam Basin has experienced two tectonothermal events since the Late Mesozoic, at \(39.1 \pm 9.3\) to \(133.7\,\pm \,6.6\,\hbox {Ma}\) and \(1.2 \pm 0.6\) to \(32.0\,\pm \,3.0\,\hbox {Ma}\). The earlier (39.1–133.7 Ma) tectonothermal event resulted from the initial collision of the Indian and Eurasian plates. As a consequence of the collision, the Altyn Tagh fault, which forms the northwestern boundary of the Qaidam Basin, began to develop. Subsequently, uplift of the Altyn Tagh mountains began and the northwestern depression of the Qaidam Basin started to form. The later (1.2–32.0 Ma) tectonothermal event resulted from further collision of the Indian and Eurasian plates along the Yarlung Tsangpo suture zone. Strata in the Qaidam Basin were further deformed by transpression in this period and this period played a crucial role in petroleum accumulation.     

Interpretation of magnetic fabrics in the Dalma volcanic rocks and associated meta-sediments of the Singhbhum Mobile Belt

The present work deals with the generations of Fe–Ti oxides and the variation in magnetic fabrics of the Dalma lavas and associated meta-sediments of the Singhbhum Mobile Belt (SMB) in relation to tectonics. Generations of the Fe–Ti oxides are different in meta-sediments and volcanics, the former preserving upliftment related oxidised grains, whereas the latter contains fresh grains prompting towards their upliftment due to plume upwelling before the volcanic eruption. In the meta-sediments, the magnetic fabric has close accordance with \(\hbox {D}_{2}/\hbox {F}_{2}\) event revealing synchronous development with \(\hbox {D}_{2}\). The Dalma thrust developed a sudden break in the homogeneity of the magnetic fabrics of the rocks where the magnetic foliations are all parallel to the Dalma thrust. This also causes \(P_{j}\) to be highest in this sector. The magnetic fabrics of volcanic rocks are different from the meta-sediments and record no signature of deformation. The pattern of distribution of susceptibility axes are in accordance with the subaerial lava flows. However, their \(\hbox {K}_{1}\) and \(\hbox {K}_{2}\) dispersed throughout the periphery with \(\hbox {K}_{3}\) clustering at the centre. This infers towards the fact that although the volcanism took place in a subaerial environment, calm aqueous environment was locally present where the oblate grains settled on the eruption surface with their \(\hbox {K}_{3}\) vertical.