Sensitivity of meteorological input and soil properties in simulating aerosols (dust, PM10, and BC) using CHIMERE chemistry transport model

The objective of this study is to evaluate the ability of a European chemistry transport model, `CHIMERE' driven by the US meteorological model MM5, in simulating aerosol concentrations dust, PM10 and black carbon (BC)] over the Indian region. An evaluation of a meteorological event (dust storm); impact of change in soil-related parameters and meteorological input grid resolution on these aerosol concentrations has been performed. Dust storm simulation over Indo-Gangetic basin indicates ability of the model to capture dust storm events. Measured (AERONET data) and simulated parameters such as aerosol optical depth (AOD) and Angstrom exponent are used to evaluate the performance of the model to capture the dust storm event. A sensitivity study is performed to investigate the impact of change in soil characteristics (thickness of the soil layer in contact with air, volumetric water, and air content of the soil) and meteorological input grid resolution on the aerosol (dust, PM10, BC) distribution. Results show that soil parameters and meteorological input grid resolution have an important impact on spatial distribution of aerosol (dust, PM10, BC) concentrations.

Polymorphic phase transition among the titania crystal structures using a solution-based approach: from precursor chemistry to nucleation process

Nanocrystalline titania are a robust candidate for various functional applications owing to its non-toxicity, cheap availability, ease of preparation and exceptional photochemical as well as thermal stability. The uniqueness in each lattice structure of titania leads to multifaceted physico-chemical and opto-electronic properties, which yield different functionalities and thus influence their performances in various green energy applications. The high temperature treatment for crystallizing titania triggers inevitable particle growth and the destruction of delicate nanostructural features. Thus, the preparation of crystalline titania with tunable phase/particle size/morphology at low to moderate temperatures using a solution-based approach has paved the way for further exciting areas of research. In this focused review, titania synthesis from hydrothermal/solvothermal method, conventional sol-gel method and sol-gel-assisted method via ultrasonication, photoillumination and ILs, thermolysis and microemulsion routes are discussed. These wet chemical methods have broader visibility, since multiple reaction parameters, such as precursor chemistry, surfactants, chelating agents, solvents, mineralizer, pH of the solution, aging time, reaction temperature/time, inorganic electrolytes, can be easily manipulated to tune the final physical structure. This review sheds light on the stabilization/phase transformation pathways of titania polymorphs like anatase, rutile, brookite and TiO2(B) under a variety of reaction conditions. The driving force for crystallization arising from complex species in solution coupled with pH of the solution and ion species facilitating the orientation of octahedral resulting in a crystalline phase are reviewed in detail. In addition to titanium halide/alkoxide, the nucleation of titania from other precursors like peroxo and layered titanates are also discussed. The nonaqueous route and ball milling-induced titania transformation is briefly outlined; moreover, the lacunae in understanding the concepts and future prospects in this exciting field are suggested.

Influence of source concentration on structural and optical properties of SnO2 nanoparticles prepared by chemical precipitation method

In present work, a systematic study has been carried out to understand the influence of source concentration on structural and optical properties of the SnO2 nanoparticles. SnO2 nanoparticles have been prepared by using chemical precipitation method at room temperature with aqueous ammonia as a stabilizing agent. X-ray diffraction analysis reveals that SnO2 nanoparticles exhibit tetragonal structure and the particle size is in range of 4.9-7.6 nm. High resolution transmission electron microscopic image shows that all the particles are nearly spherical in nature and particle size lies in range of 4.6-7 nm. Compositional analysis indicates the presence of Sn and O in samples. Blue shift has been observed in optical absorption spectra due to quantum confinement and the bandgap is in range of 4-4.16 eV. The origin of photoluminescence in SnO2 is found to be due to recombination of electrons in singly occupied oxygen vacancies with photo-excited holes in valance band.

Development and Evaluation of Statistical Downscaling Models for Monthly Precipitation

Several statistical downscaling models have been developed in the past couple of decades to assess the hydrologic impacts of climate change by projecting the station-scale hydrological variables from large-scale atmospheric variables simulated by general circulation models (GCMs). This paper presents and compares different statistical downscaling models that use multiple linear regression (MLR), positive coefficient regression (PCR), stepwise regression (SR), and support vector machine (SVM) techniques for estimating monthly rainfall amounts in the state of Florida. Mean sea level pressure, air temperature, geopotential height, specific humidity, U wind, and V wind are used as the explanatory variables/predictors in the downscaling models. Data for these variables are obtained from the National Centers for Environmental Prediction-National Center for Atmospheric Research (NCEP-NCAR) reanalysis dataset and the Canadian Centre for Climate Modelling and Analysis (CCCma) Coupled Global Climate Model, version 3 (CGCM3) GCM simulations. The principal component analysis (PCA) and fuzzy c-means clustering method (FCM) are used as part of downscaling model to reduce the dimensionality of the dataset and identify the clusters in the data, respectively. Evaluation of the performances of the models using different error and statistical measures indicates that the SVM-based model performed better than all the other models in reproducing most monthly rainfall statistics at 18 sites. Output from the third-generation CGCM3 GCM for the A1B scenario was used for future projections. For the projection period 2001-10, MLR was used to relate variables at the GCM and NCEP grid scales. Use of MLR in linking the predictor variables at the GCM and NCEP grid scales yielded better reproduction of monthly rainfall statistics at most of the stations (12 out of 18) compared to those by spatial interpolation technique used in earlier studies.

Seleno-Nucleobases and Their Water-Soluble Ruthenium-Arene Half-Sandwich Complexes: Chemistry and Biological Activity

Half-sandwich organometallic ruthenium complexes of seleno-nucleobases, 3 and 4, were synthesized and characterized. The structures of both complexes were determined by X-ray crystallography and are the first crystal structures of ruthenium complexes with seleno-nucleobases. Interestingly, 3 self-assembles aided by adventitious water in DMF to give a tetranuclear square 3a center dot 6H(2)O. Complex 4 is active against Jurkat and Molt-4 cell lines but inactive against the K562 cell line, whereas 3 is completely inactive against all three cell lines. The free ligand 6-selenopurine (1) and 6-selenoguanine (2) are highly active against these cell lines. Compound 2, like its thio analogue, is unstable under UVA light, whereas 4 is stable under similar conditions, which suggests that the ruthenium complex could reduce problems associated with the instability of the free ligand, 2, under irradiation.

Precipitation response of the magnesium alloy WE43 in strained and unstrained conditions

The precipitation behavior of the magnesium alloy WE43 (Mg-4%Y-2.3%Nd-0.5%Zr) has been studied in strained and unstrained conditions using Transmission Electron Microscopy (TEM). Ageing treatments were carried out at three temperatures, namely 210 degrees C, 230 degrees C and 260 degrees C. The precipitation sequence during static aging of solution treated (ST) samples has been identified as ST —> beta'' —> beta' followed by the formation of beta(1) and equilibrium beta precipitates form after very long ageing periods. Dynamic precipitation was observed during high temperature deformation, leading to the formation of beta' and intermediate beta(1) precipitates. The strained samples, when further heat treated, resulted in the transformation of beta(1) into beta equilibrium precipitates. The sequence of dynamic precipitation is ST —> beta(1) —> beta and ST —> beta'. (C) 2014 Elsevier B.V. All rights reserved.

Sources of major ions and processes affecting the geochemical and isotopic signatures of subsurface waters along a tropical river, Southwestern India

Systematic monitoring of subsurface hydrogeochemistry has been carried out for a period of one year in a humid tropical region along the Nethravati-Gurupur River. The major ion and stable isotope (delta O-18 and delta H-2) compositions are used to understand the hydrogeochemistry of groundwater and its interaction with surface water. In the study, it is observed that intense weathering of source rocks is the major source of chemical elements to the surface and subsurface waters. In addition, agricultural activities and atmospheric contributions also control the major ion chemistry of water in the study area. There is a clear seasonality in the groundwater chemistry, which is related to the recharge and discharge of the hydrological system. On a temporal scale, there is a decrease in major cation concentrations during the monsoon which is a result of dilution of sources from the weathering of rock minerals, and an increase in anion concentrations which is contributed by the atmosphere, accompanied by an increase in water level during the monsoon. The stable isotope composition indicates that groundwater in the basin is of meteoric origin and recharged directly from the local precipitation during the monsoonal season. Soon after the monsoon, groundwater and surface water mix in the subsurface region. The groundwater feeds the surface water during the lean river flow season.

Scheelite-type MWO4 (M = Ca, Sr, and Ba) nanophosphors: Facile synthesis, structural characterization, photoluminescence, and photocatalytic properties

Scheelite-type MWO4 (M = Ca, Sr, and Ba) nanophosphors were synthesized by the precipitation method. All compounds crystallized in the tetragonal structure with space group 141/a (No. 88). Scherrer's and TEM results revealed that the average crystallite size varies from 32 to 55 nm. FE-SEM illustrate the spherical (CaWO4), bouquet (SrWO4), and fish (BaWO4) like morphologies. PL spectra indicate the broad emission peak maximum at 436 (CaWO4), 440 (SrWO4), and 433 nm (BaWO4) under UV excitation. The calculated CIE color coordinates of MWO4 nanophosphors are close to the commercial BAM and National Television System Committee blue phosphor. The photocatalytic activities of MWO4 were investigated for the degradation of methylene blue dye under UV illumination. At pH 3, BaWO4 nanocatalyst showed 100% dye degradation within 60 min. The photocatalytic activity was in the decreasing order of BaWO4> CaWO4>SrWO4 under both neutral and acidic conditions. (C) 2014 Elsevier Ltd. All rights reserved.

Facile synthesis of PbWO4: Applications in photoluminescence and photocatalytic degradation of organic dyes under visible light

Stolzite polymorph of PbWO4 catalyst was prepared by the facile room temperature precipitation method. Structural parameters were refined by the Rietveld analysis using powder X-ray data. PbWO4 was crystallized in the scheelite-type tetragonal structure with space group I4(1)/a (No. 88). Field emission scanning electron microscopy revealed leaf like morphology. Photoluminescence spectra exhibit broad blue emission (425 nm) under the excitation of 356 nm. The photocatalytic degradation of Methylene blue, Rhodamine B and Methyl orange dyes were measured under visible illumination. The 100% dye degradation was observed for MB and RhB dyes within 60 and 105 min. The rate constant was found to be in the decreasing order of MB > RhB > MO which followed the 1st order kinetic mechanism. Therefore, PbWO4 can be a potential candidate for blue component in white LEDs and also acts as a catalyst for the treatment of toxic and non-biodegradable organic pollutants in water. (C) 2014 Elsevier B.V. All rights reserved.

Performance evaluation of AR4 Climate Models in simulating daily precipitation over the Indian region using skill scores

The ability of Coupled General Circulation Models (CGCMs) participating in the Intergovernmental Panel for Climate Change's fourth assessment report (IPCC AR4) for the 20th century climate (20C3M scenario) to simulate the daily precipitation over the Indian region is explored. The skill is evaluated on a 2.5A degrees x 2.5A degrees grid square compared with the Indian Meteorological Department's (IMD) gridded dataset, and every GCM is ranked for each of these grids based on its skill score. Skill scores (SSs) are estimated from the probability density functions (PDFs) obtained from observed IMD datasets and GCM simulations. The methodology takes into account (high) extreme precipitation events simulated by GCMs. The results are analyzed and presented for three categories and six zones. The three categories are the monsoon season (JJASO - June to October), non-monsoon season (JFMAMND - January to May, November, December) and for the entire year (''Annual''). The six precipitation zones are peninsular, west central, northwest, northeast, central northeast India, and the hilly region. Sensitivity analysis was performed for three spatial scales, 2.5A degrees grid square, zones, and all of India, in the three categories. The models were ranked based on the SS. The category JFMAMND had a higher SS than the JJASO category. The northwest zone had higher SSs, whereas the peninsular and hilly regions had lower SS. No single GCM can be identified as the best for all categories and zones. Some models consistently outperformed the model ensemble, and one model had particularly poor performance. Results show that most models underestimated the daily precipitation rates in the 0-1 mm/day range and overestimated it in the 1-15 mm/day range.

Differential response of cholesterol based pyrimidine systems with oxyethylene type spacers to gelation and mesogen formation in the presence of alkali metal ions

A new series of lipophilic cholesteryl derivatives of 2,4,6-trichloro-pyrimidine-5-carbaldehyde has been synthesized. Oxyethylene spacers of variable lengths were inserted between the hydrogen bonding promoting pyrimidine core and the cholesteryl tail in order to understand their effect on the selfassembly of these compounds. Only compound 1a with the shortest spacer formed a gel in organic solvents such as n-butanol and n-dodecane. While other members (1b and c) having longer spacers led to sol formation and precipitation in n-butanol and n-dodecane respectively. The self-assembly phenomena associated with the gelation process were investigated using temperature-dependent UVVis and CD-spectroscopy. The morphological features of the freeze-dried gels obtained from different organic solvents were examined by scanning electron microscopy (SEM) and atomic force microscopy (AFM). The solid phase behaviours of these molecules and their associated alkali metal ion complexes were explored using polarized optical microscopy (POM) and differential scanning calorimetry (DSC). The molecular arrangements in the xerogel and in the solid state were further probed using a wide-angle Xray diffraction (WAXD) technique. Analysis of the wide-angle X-ray diffraction data reveals that this class of molecules adopts a hexagonal columnar organization in the gel and in the solid state. Each slice of these hexagonal columnar structures is composed of a dimeric molecular-assembly as a building block. Significant changes in the conformation of the oxyethylene chains could be triggered via the coordination of selected alkali metal ions. This led to the production of interesting metal ion promoted mesogenic behaviour.

Water Dispersible, Positively and Negatively Charged MoS2 Nanosheets: Surface Chemistry and the Role of Surfactant Binding

Stable aqueous dispersions of atomically thin layered MoS2 nanosheets have been obtained by sonication in the presence of ionic surfactants. The dispersions are stabilized by electrostatic repulsion between the sheets, and we show that the sign of the charge on the MoS2 nanosheets, either positive or negative, can be can be controlled by the choice of the surfactant. Using techniques from solution NMR, we show that the surfactant chains are weakly bound to the MoS2 sheets and undergo rapid exchange with free surfactant chains present in the dispersion. In situ nuclear Overhauser effect spectroscopic measurements provide direct evidence that the surfactant chains lie flat, arranged randomly on the basal plane of the MoS2 nanosheets with their charged headgroup exposed. These results provide a chemical perspective for understanding the stability of these inorganic nanosheets in aqueous dispersions and the origin of the charge on the sheets.

Effects of large-scale deforestation on precipitation in the monsoon regions: Remote versus local effects

In this paper, using idealized climate model simulations, we investigate the biogeophysical effects of large-scale deforestation on monsoon regions. We find that the remote forcing from large-scale deforestation in the northern middle and high latitudes shifts the Intertropical Convergence Zone southward. This results in a significant decrease in precipitation in the Northern Hemisphere monsoon regions (East Asia, North America, North Africa, and South Asia) and moderate precipitation increases in the Southern Hemisphere monsoon regions (South Africa, South America, and Australia). The magnitude of the monsoonal precipitation changes depends on the location of deforestation, with remote effects showing a larger influence than local effects. The South Asian Monsoon region is affected the most, with 18% decline in precipitation over India. Our results indicate that any comprehensive assessment of afforestation/reforestation as climate change mitigation strategies should carefully evaluate the remote effects on monsoonal precipitation alongside the large local impacts on temperatures.