Controls on intense silicate weathering in a tropical river, southwestern India

The Silicate Weathering Rate (SWR) and associated Carbon dioxide Consumption Rate (CCR) in tropical silicate terrain is assessed through a study of the major ion chemistry in a small west flowing river of Peninsular India, the Nethravati River. The specific features of the river basin are high mean annual rainfall and temperature, high runoff and a Precambrian basement composed of granitic-gneiss, charnockite and minor metasediments. The water samples (n = 56) were collected from three locations along the Nethravati River and from two of its tributaries over a period of twelve months. Chemical Weathering Rate (CWR) for the entire watershed is calculated by applying rainwater correction using river chloride as a tracer. Chemical Weathering Rate in the Nethravati watershed is estimated to 44 t.km(-2).y(-1) encompassing a SWR of 42 t.km(-2).y(-1) and a maximum carbonate contribution of 2 t.km(-2).y(-1). This SWR is among the highest reported for granito-gneissic terrains. The assessed CCR is 2.9 . 10(5) mol.km(-2).y(-1). The weathering index (Re). calculated from molecular ratios of dissolved cations and silica in the river, suggests an intense silicate weathering leading to kaolinite-gibbsite precipitation in the weathering covers. The intense SWR and CCR could be due to the combination of high runoff and temperature along with the thickness and nature of the weathering cover. The comparison of silicate weathering fluxes with other watersheds reveals that under similar morpho-climatic settings basalt weathering would be 2.5 times higher than the granite-gneissic rocks. (C) 2012 Elsevier B.V. All rights reserved.

Thermoluminescence and EPR studies of nanocrystalline Nd2O3:Ni2+ phosphor

Nanocrystalline Nd2O3:Ni2+ (2 mol%) phosphor has been prepared by a low temperature (similar to 400 degrees C) solution combustion method, in a very short time (<5 min). Powder X-ray diffraction results confirm the single hexagonal phase of nanopowders. Scanning electron micrographs show that nanophosphor has porous nature and the particles are agglomerated. Transmission electron microscopy confirms the nanosize (20-25 nm) of the crystallites. The electron paramagnetic resonance (EPR) spectrum exhibits a symmetric absorption at g approximate to 2.77 which suggests that the site symmetry around Ni2+ ions is predominantly octahedral. The number of spins participating in resonance (N) and the paramagnetic susceptibility (chi) has been evaluated. Raman study show major peaks, which are assigned to F-g and combination of A(g) + E-g modes. Thermoluminescence (TL) studies reveal well resolved glow peaks at 169 degrees C along with shoulder peak at around 236 degrees C. The activation energy (E in eV), order of kinetics (b) and frequency factor (s) were estimated using glow peak shape method. It is observed that the glow peak intensity at 169 degrees C increases linearly with gamma-dose which suggest that Nd2O3:Ni2+ is suitable for radiation dosimetry applications. (C) 2012 Elsevier B.V. All rights reserved.

Swift heavy ion induced structural, iono and photoluminescence properties of beta-CaSiO3:Dy3+ nanophosphor

CaSiO3:Dy3+ (1-5 mol%) nanophosphors have been prepared by a low temperature solution combustion method. The structural and luminescence (ionoluminescence; IL and photoluminescence; PL) studies have been carried out for pristine and ion irradiated samples. The XRD patterns of pristine sample show a prominent peak at (320) for the monoclinic structure of beta-CaSiO3. Upon ion irradiation, the intensity of the prominent peak is decreased at the fluence of 7.81 x 10(12) ions cm(-2) and at higher fluence of 15.62 x 10(12) ions cm(-2), the prominent peak completely vanishes. The decrease in peak intensity might be due to the stress induced point defects. On-line IL and in situ PL studies have been carried out on pelletized samples bombarded with 100 MeV Si7+ ions with fluences in the range (7.81-15.62) x 10(12) ions cm(-2). The characteristic emission peaks at 481,574, 664 and 754 nm recorded in both IL and PL are attributed to the luminescence centers activated by Dy3+ ions. It is found that IL and PL emissions intensity decreases with increase in Si7+ ion fluence. The decrease in intensity can be due to the destruction of Si-O-Si and O-Si-O type species present on the surface of the sample. FTIR studies also confirm the Si-O-Si and O-Si-O type species observed to be sensitive for swift heavy ion (SHI) irradiated samples. (C) 2012 Elsevier B.V. All rights reserved.

Phylogeny of the Asian Eutropis (Squamata: Scincidae) reveals an `into India' endemic Indian radiation

Recent generic rearrangement of the circumtropical distributed skink genus `Mabuya' has raised a lot of debate. According to this molecular phylogeny based rearrangement, the tropical Asian members of this genus have been assigned to Eutropis. However, in these studies the Asian members of `Mabuya' were largely sampled from Southeast (SE) Asia with very few species from Indian subcontinent. To test the validity of this assignment and to determine the evolutionary origin of Indian members of this group we sequenced one nuclear and two mitochondrial genes from most of the species from the Indian subregion. The nuclear and mitochondrial trees generated from these sequences confirmed the monophyly of the tropical Asian Eutropis. Furthermore, in the tree based on the combined mitochondrial and nuclear dataset an endemic Indian radiation was revealed that was nested within a larger Asian clade. Results of dispersal-vicariance analysis and molecular dating suggested an initial dispersal of Eutropis from SE Asia into India around 5.5-17 million years ago, giving rise to the extant members of the endemic Indian radiation. This initial dispersal was followed by two back dispersals from India into SE Asia. We also discuss the relationships within the endemic Indian radiation and its taxonomic implications. (c) 2012 Elsevier Inc. All rights reserved.

Synthesis, characterization, thermo- and photoluminescence properties of Bi3+ co-doped Gd2O3:Eu3+ nanophosphors

Gd2O3:Eu3+ (4 mol%) co-doped with Bi3+ (Bi = 0, 1, 3, 5, 7, 9 and 11 mol%) ions were synthesized by a low-temperature solution combustion method. The powders were calcined at 800A degrees C and were characterized by powder X-ray diffraction (PXRD), transmission electron microscopy (TEM), Fourier transform infrared and UV-Vis spectroscopy. The PXRD profiles confirm that the calcined products were in monoclinic with little cubic phases. The particle sizes were estimated using Scherrer's method and Williamson-Hall plots and are found to be in the ranges 40-60 nm and 30-80 nm, respectively. The results are in good agreement with TEM results. The photoluminescence spectra of the synthesized phosphors excited with 230 nm show emission peaks at similar to 590, 612 and 625 nm, which are due to the transitions D-5(0)-> F-7(0), D-5(0)-> F-7(2) and D-5(0)-> F-7(3) of Eu3+, respectively. It is observed that a significant quenching of Eu3+ emission was observed under 230 nm excitation when Bi3+ was co-doped. On the other hand, upon 350 nm excitation, the luminescent intensity of Eu3+ ions was enhanced by incorporation of Bi3+ (5 mol%) ions. The introduction of Bi3+ ions broadened the excitation band of Eu3+ of which a new strong band occurred ranging from 320 to 380 nm. This has been attributed to the 6s(2)-> 6s6p transition of Bi3+ ions, implying a very efficient energy transfer from Bi3+ ions to Eu3+ ions. The gamma radiation response of Gd2O3:Eu3+ exhibited a dosimetrically useful glow peak at 380A degrees C. Using thermoluminescence glow peaks, the trap parameters have been evaluated and discussed. The observed emission characteristics and energy transfer indicate that Gd2O3:Eu3+, Bi3+ phosphors have promising applications in solid-state lighting.

Electrochemical Detection of Bisphenol A Using Graphene-Modified Glassy Carbon Electrode

Graphene's nano-dimensional nature and excellent electron transfer properties underlie its electrocatalytic behavior towards certain substances. In this light, we have used graphene in the electrochemical detection of bisphenol A. Graphene sheets were produced via soft chemistry route involving graphite oxidation and chemical reduction. X-ray diffraction, Fourier transform infra-red (FT-IR) and Raman spectroscopy were used for the characterization of the as-synthesized graphene. Graphene exhibited amorphous structure in comparison with pristine graphite from XRD spectra. FTIR showed that graphene exhibits OH and COOH groups due to incomplete reduction. Raman spectroscopy revealed that multi-layered graphene was produced due to low intensity of the 2D-peak. Glassy carbon electrode was modified with graphene by a simple drop and dry method. Cyclic voltammetry was used to study the electrochemical properties of the prepared graphene-modified glassy carbon electrode using potassium ferricyanide as a redox probe. The prepared graphene- modified glassy carbon electrode exhibited more facile electron kinetics and enhanced current of about 75% when compared to the unmodified glassy carbon electrode. The modified electrode was used for the detection of bisphenol A. Under the optimum conditions, the oxidation peak current of bisphenol A varied linearly with concentration over a wide range of 5 x 10(-8) mol L-1 to 1 x 10(-6) mol L-1 and the detection limit of this method was as low as 4.689 x 10(-8) M. This method was also employed to determine bisphenol A in a real sample

Surfactant solubility and micellization in ternary eutectic melt (acetamide plus urea plus ammonium nitrate)

Cationic surfactants such as dodecyltrimethylammonium bromide (DTAB), tetradecyltrimehtylammonium bromide (TTAB) and hexadecyltrimethylammonium bromide (HTAB); and anionic surfactants such as sodium decyl sulphate (SDeS), sodium dodecyl sulphate (SDS) and sodium tetradecyl sulphate (STDS) have been used to determine their solubility and micellization in ternary eutectic melt (acetamide + urea + ammonium nitrate) at 50 degrees C. We employed the electrical conductivity and the surface tension measurement techniques to determine the critical micelle concentration (CMC). The deviation in the slope of the specific conductance/surface tension against surfactant concentration plots indicated the aggregations of surfactants and hence, their CMC. CMC decreases with increase of alkyl chain length due to the increased van der Waals forces. The calculated increment in Gibb's energy per methylene group for cationic and anionic surfactants is about -6 kJ mol(-1) and -4 kJ mol(-1) respectively. It is found that, the CMCs of the surfactants in the ternary melt are higher than the CMCs of same surfactants in water (similar to 25 degrees C). (C) 2012 Elsevier B.V. All rights reserved.

Tailoring the Magnetic and Optical Characteristics of Nanocrystalline BiFeO3 by Ce Doping

The Ce-doped BiFeO3 (BFO) nanoparticles (NPs) were synthesized using a facile solgel route with varying Ce concentrations in the range of 15 mol%. Ferroelectric transition temperature was found to shift from 723 degrees C +/- 5 degrees C for pristine BFO NPs to 534 degrees C +/- 3 degrees C for 5 mol% Ce-doped BFO NPs. UVVis absorption spectra of BFO NPs showed a significant blue shift of similar to 100 nm on Ce doping. The Fourier transformed infrared (FTIR) spectrum centered similar to 550 cm(-1) becomes considerably broadened on Ce doping which is due to additional closely spaced vibrational peaks as revealed by the second derivative FTIR analysis. High-frequency EPR measurements indicated that clustering occurs at high dopant levels, and that Fe is present as Fe(3+)corroborating Mossbauer measurements. The values of saturation and remanent magnetization for 3% Ce-doped BFO NPs are 3.03 and 0.49 emu/g, respectively, which are quite significant at room temperature, making it more suitable for technological applications.

Thermoluminescence, photoluminescence and EPR studies on Mn2+ activated yttrium aluminate (YAlO3) perovskite

Thermoluminescence (TL) measurements were carried out on undoped and Mn2+ doped (0.1 mol%) yttrium aluminate (YAlO3) nanopowders using gamma irradiation in the dose range 1-5 kGy. These phosphors have been prepared at furnace temperatures as low as 400 degrees C by using the combustion route. Powder X-ray diffraction confirms the orthorhombic phase. SEM micrographs show that the powders are spherical in shape, porous with fused state and the size of the particles appeared to be in the range 50-150 nm. Electron Paramagnetic Resonance (EPR) studies reveal that Mn ions occupy the yttrium site and the valency of manganese remains as Mn2+. The photoluminescence spectrum shows a typical orange-to-red emission at 595 nm and suggests that Mn2+ ions are in strong crystalline environment. It is observed that TL intensity increases with gamma dose in both undoped and Mn doped samples. Four shouldered TL peaks at 126, 240, 288 and 350 degrees C along with relatively resolved glow peak at 180 degrees C were observed in undoped sample. However, the Mn doped samples show a shouldered peak at 115 degrees C along with two well defined peaks at similar to 215 and 275 degrees C. It is observed that TL glow peaks were shifted in Mn doped samples. The kinetic parameters namely activation energy (E), order of kinetics (b), frequency factor (s) of undoped, and Mn doped samples were determined at different gamma doses using the Chens glow peak shape method and the results are discussed in detail. (C) 2012 Elsevier B.V. All rights reserved.

Structural, EPR, optical and Raman studies of Nd2O3:Cu2+ nanophosphors

Nanocrystalline Nd2O3:Cu2+ (2 mol %) phosphors have been prepared by a low temperature solution combustion technique. Powder X-ray diffraction (PXRD) results confirm that hexagonal A-type Nd2O3 (900 degrees C, 3 h) and the lattice parameters have been evaluated by Rietveld refinement. Surface morphology of as-formed and Cu2+ doped Nd2O3 phosphors show that the particles are irregular in shape and porous in nature. TEM results also confirm the nature and size of the particles. The EPR spectrum exhibits two resonance signals with effective g values at g(parallel to) approximate to 2.12 and g(perpendicular to) approximate to 2.04. The g values indicate that the site symmetry of Cu2+ ions is octahedral symmetry with elongated tetragonal distortion. Raman studies show major peaks, which are assigned, to F-g and combination of A(g) + E-g modes. It is observed that the Raman peaks and intensity have been reduced in Cu2+ doped samples. UV-Visible absorption spectra exhibit a strong and broad absorption band at similar to 240 nm. Further, the absorption peak shifts to similar to 14 nm in Cu2+ doped samples. The optical band gap is estimated to be 5.28 eV for Cu doped Nd2O3 nanoparticles which are higher than the bulk Nd2O3 (4.7 eV). This can be attributed to the quantum confinement effect of the nanoparticles. (C) 2012 Elsevier B.V. All rights reserved.

Enhancing the magnetic characteristics of BiFeO3 nanoparticles by Ca, Ba co-doping

Multiferroic nanoparticles (NPs) of pristine and Ca, Ba co-doped BiFeO3 were synthesized by a facile sal gel route. Co-doping was done by fixing the total dopant concentration at 5 mol% and then the relative concentrations of Ca and Ba was varied. Structural, optical and magnetic properties of the NPs were investigated using different techniques. UV-Vis absorption spectra of BiFeO3 NPs showed a substantial blue shift of similar to 100 nm (530 nm -> 430 nm) on Ca. Ba co-doping which corresponds to increase in band gap by 0.5 eV. Fe-57 Mossbauer spectroscopy confirmed that iron is present only in 3(+) valence state in all co-doped samples. The coercive field increased by 18 times for Bi0.95Ca0.01Ba0.04FeO3 samples, which is the maximum enhancement, observed amongst all the 5 mol% doped samples. At the equimolar (2.5 mol % each) concentration of co-dopants, the coercive field shows a significant enhancement of about 9 times (220 Oe -> 2014 Oe) with concomitant increase in saturation magnetization by 7 times. Thus, equimolar co-doping causes simultaneous enhancement of the twin aspects of magnetic properties thereby making them better suited for device applications. (C) 2012 Elsevier B.V. All rights reserved.

Kinetics of adsorption of methylene blue and rhodamine 6G on acrylic acid-based superabsorbents

Superabsorbent polymers (SAPs) of acrylic acid, sodium acrylate, and acrylamide (AM), crosslinked with ethylene glycol dimethacrylate, were synthesized by inverse suspension polymerization. The equilibrium swelling capacities of the SAPs were determined and these decreased with increasing AM content. The adsorption of the two cationic dyes, methylene blue and rhodamine 6G, on the dry as well as equilibrium swollen SAPs was investigated. The amount of the dye adsorbed at equilibrium per unit weight of the SAPs and the rate constants of adsorption were determined. The amount of the dye adsorbed at equilibrium by the SAPs decreased with increasing mol % of AM in the SAPs. The amount of the dye adsorbed at equilibrium was almost equal for the dry and equilibrium swollen SAPs. However, the equilibrium swollen SAPs adsorbed dyes at a higher rate than the dry SAPs. The higher rate of adsorption was attributed to the availability of all the anionic groups present in the fully elongated conformation of the SAPs in the equilibrium swollen state. The effect of initial dye concentration on the adsorption was also investigated and the adsorption was described by Langmuir adsorption isotherms. (C) 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012

Gibbs Energy of Formation of Ca3Ti8Al12O37 and Phase Relations and Chemical Potentials in the System Al2O3-TiO2-CaO

The quaternary oxide in the system Al2O3-CaO-TiO2 is found to have the composition Ca3Ti8Al12O37 rather than CaTi3Al8O19 as reported in the literature. The standard Gibbs energy of formation of Ca3Ti8Al12O37 from component binary oxides is measured in the temperature range from 900 to 1250 K using a solid-state electrochemical cell incorporating single crystal CaF2 as the solid electrolyte. The results can be represented by the equation: delta G(f(0x))(0) (+/- 70)/J mol(-1) = -248474 - 15.706(T/K). Combining this information with thermodynamic data on calcium aluminates and titanates available in the literature, subsolidus phase relations in the pseudo-ternary system Al2O3-CaO-TiO2 are computed and presented as isothermal sections. The evolution of phase relations with temperature is highlighted. Chemical potential diagrams are computed at 1200 K, showing the stability domains of the various phases in the chemical potential-composition space. In each chemical potential diagram, chemical potential of one component is plotted against the cationic fraction of the other two components. The diagrams are valid at relatively high oxygen potentials where Ti is present in its four-valent state in all the oxide phases.

Synthesis dependent characteristics of Sr1-xMnxTiO3 (x=0.03, 0.05, 0.07 and 0.09)

Sr1-xMnxTiO3 (where x=0.03, 0.05, 0.07 and 0.09) was synthesized via different routes that include solid-state, oxalate precipitation and freeze drying. In oxalate precipitation technique, compositions corresponding to 3 and 5 mol% doping of Mn were monophasic whereas the higher compositions revealed the presence of the secondary phases such as MnO, Mn3O4 etc., as confirmed by high resolution X-ray diffraction (XRD) studies. The decomposition behavior of the precursors prepared using oxalate precipitation method corresponding to the above mentioned compositions was studied. Nanopowders of compositions pertaining to 5 to 9 mol% of Mn doping were obtained using freeze-drying technique. The average crystallite size of these nanopowders was found to be in the 35 to 65 nm range. The microstructural studies carried out on the sintered ceramics, fabricated using powders synthesized by different routes established the fine grained nature ( < 1 mu m) of the one obtained by freeze drying method. Raman scattering studies were carried out in order to complement the observations made from XRD regarding the phase purity. The dielectric properties of the ceramics obtained by different synthesis routes were studied in the 80-300 K temperature range at 100 kHz and the effect of grain size has been discussed. (C) 2012 Elsevier Inc. All rights reserved.

Diffusion mechanism in the mu phase in Nb-X (X = Ni, Co, Fe) systems

Nb is one of the common refractory elements added in Ni, Co and Fe based superalloys. This lead to the formation of brittle topological close packed (tcp) mu phase, which is deleterious to the structure. It mainly grows by interdiffusion and in the present article, the interdiffusion process in different Nb-X (X=Ni, Co, Fe) systems is discussed. The activation energy for interdiffusion is lower in the Co-Nb system (173 kJ/mol) than Fe-Nb system (233 kJ/mol), which is again lower than the value found in the Ni-Nb system (319.7 kJ/mol). The mole fraction of Nb in this phase is less than Fe or Co at stoichiometric compositions in the Nb-Fe (that is Fe7Nb6) and Nb-Co (that is Co7Nb6) systems. On the other hand, the mole fraction of Nb is higher than Ni in the same phase (Ni6Nb2) in Ni-Nb system. However, in all the phases, Nb has lower diffusion rate. Possible diffusion mechanism in this phase is discussed with respect to the crystal structure.