EXAFS studies of arsenic chalcogenide glasses

An EXAFS study at the AsK edge of the ternary glasses As2(S, Se)3 and As2(Se, Te)3 and the binary As2S3, As2Se3 and As2Te3 glasses has been carried out. Radial structure functions show that the environment of As in glasses of intermediate compositions is quite different from that in the binary glasses. In the As2(S, Se)3 system, this might arise from chemical disorder in the network while in the As2(Se, Te)3 system increased ionicity could be the cause of this behaviour. Glasses where the constituent atoms are of similar size seem to exhibit fewer peaks in the radial structure function.

Glass transitions in arsenic-selenium glasses

Glaiis transitions of As-Se glasses have been investigated over a wide range of compositions by using differential scanning calorimetry. The variation of Tg with composition has been interpreted on the basis of a bond-lattice model.

Microbially induced separation of arsenopyrite and bioremediation of arsenic

This paper discusses the role of the mineral-adapted acidiphilic microorganism. Acidithiobacillus ferrooxidans in the beneficiation of arsenopyrite-containing multisulfides (pyrite and chalcopyrite) and the bioremediation of the resulting arsenical waste water. It was found that adaptation to minerals alters the surface properties of the microorganism. Bacterial adaptation to arsenopyrite and controlled bacterial adhesion to mineral surfaces lead to selectivity in arsenopyrite separation. Bioremoval of arsenic ions (both arsenite and arsenate ions) by Acidithiobacillus ferrooxidans is also discussed.

In-situ formation of graphene-lead oxide composite and its use in trace arsenic detection

Reduced graphene oxide-lead dioxide composite is formed when EGO coated surface is electrochemically reduced along with lead ions in the solution. This composite has been shown to be an excellent material for low level detection of arsenic. Various functional groups present on EGO, in a wide pH range of 2-11, are responsible for the favorable interaction between metal ion and the modified electrode surface and subsequent trace level detection. X-ray photoelectron spectroscopy and Raman spectroscopic techniques confirm the formation of composite and its composition. Thin layer of lead dioxide along with reduced exfoliated graphene oxide has been shown to be responsible for the enhanced activity of the surface. The detection limit of arsenic is found to be 10 nM. This study opens up the possibility of using the composites for sensing applications and possibly simultaneous detection of arsenic and lead. (C) 2011 Elsevier B.V. All rights reserved.

Cyclodextrin functionalized magnetic iron oxide nanocrystals: a host-carrier for magnetic separation of non-polar molecules and arsenic from aqueous media

A single-step magnetic separation procedure that can remove both organic pollutants and arsenic from contaminated water is clearly a desirable goal. Here we show that water dispersible magnetite nanoparticles prepared by anchoring carboxymethyl-beta-cyclodextrin (CMCD) cavities to the surface of magnetic nanoparticles are suitable host carriers for such a process. Monodisperse, 10 nm, spherical magnetite, Fe3O4, nanocrystals were prepared by the thermal decomposition of FeOOH. Trace amounts of antiferromagnet, FeO, present in the particles provides an exchange bias field that results in a high superparamagnetic blocking temperature and appreciable magnetization values that facilitate easy separation of the nanocrystals from aqueous dispersions on application of modest magnetic fields. We show here that small molecules like naphthalene and naphthol can be removed from aqueous media by forming inclusion complexes with the anchored cavities of the CMCD-Fe3O4 nanocrystals followed by separation of the nanocrystals by application of a magnetic field. The adsorption properties of the iron oxide surface towards As ions are unaffected by the CMCD capping so it too can be simultaneously removed in the separation process. The CMCD-Fe3O4 nanocrystals provide a versatile platform for magnetic separation with potential applications in water remediation.

Multilayer assemblies of polyelectrolyte-gold nanoparticles for the electrocatalytic oxidation and detection of arsenic(III)

Multilayers of poly(diallyldimethylammonium chloride) (PDDA) and citrate capped Au nanoparticles (AuNPs) anchored on sodium 3-mercapto-1-propanesulfonate modified gold electrode by electrostatic layer-by-layer assembly (LbL) technique are shown to be an excellent architecture for the direct electrochemical oxidation of As(III) species. The growth of successive layers in the proposed LbL architecture is followed by atomic force microscopy, UV-vis spectroscopy, quartz crystal microbalance with energy dissipation, and electrochemistry. The first bilayer is found to show rather different physico-chemical characteristics as compared to the subsequent bilayers, and this is attributed to the difference in the adsorption environments. The analytical utility of the architecture with five bilayers is exploited for arsenic sensing via the direct electrocatalytic oxidation of As(III), and the detection limit is found to be well below the WHO guidelines of 10 ppb. When the non-redox active PDDA is replaced by the redoxactive Os(2,2'-bipyridine)(2)Cl-poly(4-vinylpyridine) polyelectrolyte (PVPOs) in the LbL assembly, the performance is found to be inferior, demonstrating that the redox activity of the polyelectrolyte is futile as far as the direct electro-oxidation of As(III) is concerned. (C) 2012 Elsevier Inc. All rights reserved.

Synthesis of zero valent iron nanoparticles and application to removal of arsenic(III) and arsenic(V) from water

Recently nano scale zero valent iron particles (nZVI) have been considered as smart adsorbent for environmental and groundwater remediation. Although several synthetic methods are available for the preparation of nZVI, air stable nZVI are not available for remediation works. Further, challenges demand synthesis of nZVI without stabilizers and capping agents. A modified methodology for the synthesis of air stable nZVI has been developed without any capping agents and characterized by powder X-Ray Diffraction (XRD), Scanning Electron Microscopy Energy-dispersive X-Ray (SEM-EDS), Transmission Electron Microscopy (TEM) and X-Ray Photoelectron Spectroscopy (XPS). The results of the present study suggest that the synthetic nZVI are air-stable over a period of one year and consists of particles of 30-40 nm in diameter. Although a layer of less than 3 am thick oxide/hydroxide is observed by TEM and XPS, it appears to be due to oxidation of outer surface during analysis. Adsorption study has shown that the synthetic nZVI are more effective adsorbent than the commercial nZVI and can remove simultaneously arsenite As-III] and arsenate As-V] from water without prior reduction of As-V to As-III. The removal process is adsorptive rather than precipitative and the removal of As-III is greater than that of As-V.

Voltammetric detection of arsenic on a bismuth modified exfoliated graphite electrode

We present the application of a bismuth modified exfoliated graphite electrode in the detection of arsenic in water. Bismuth film was electrodeposited onto an exfoliated graphite (EG) electrode at a potential of -600 mV. The modification of EG resulted in an increase in the electroactive surface area of the electrode and consequently peak current enhancement in Ru(NH3)(6)(2+/13+) redox probe. Square wave anodic stripping voltammetry was performed with the modified electrode (EG-Bi) in As (III) solutions at the optimum conditions of pH 6, deposition potential of -600 mV and pre-concentration time of 180s. The EG-Bi was able to detect As (III) to the limit of 5 mu g L-1 and was not susceptible to many interfering cations except Cu (II). The EG-Bi is low cost and easy to prepare. (C) 2013 Elsevier Ltd. All rights reserved.

Graphene Oxide-MnFe2O4 Magnetic Nanohybrids for Efficient Removal of Lead and Arsenic from Water

We show that the hybrids of single-layer graphene oxide with manganese ferrite magnetic nanoparticles have the best adsorption properties for efficient removal of Pb(II), As(III), and As(V) from contaminated water. The nanohybrids prepared by coprecipitation technique were characterized using atomic force and scanning electron microscopies, Fourier transformed infrared spectroscopy, Raman spectroscopy, X-ray diffraction, and surface area measurements. Magnetic character of the nanohybrids was ascertained by a vibrating sample magnetometer. Batch experiments were carried out to quantify the adsorption kinetics and adsorption capacities of the nanohybrids and compared with the bare nanoparticles of MnFe2O4. The adsorption data from our experiments fit the Langmuir isotherm, yielding the maximum adsorption capacity higher than the reported values so far. Temperature-dependent adsorption studies have been done to estimate the free energy and enthalpy of adsorption. Reusability, ease of magnetic separation, high removal efficiency, high surface area, and fast kinetics make these nanohybrids very attractive candidates for low-cost adsorbents for the effective coremoval of heavy metals from contaminated water.

Isolation and characterization of a bioflocculant from Bacillus megaterium for turbidity and arsenic removal

A biodegradable flocculant was produced during growth of Bacillus megaterium. The major component of the bioflocculant was found to be a polysaccharide composed of some proteins. Fourier transform infrared (FTIR) spectra analysis revealed the presence of carboxyl and hydroxyl groups in the bioflocculant, and thermal characterization by differential scanning calorimetly (DSC) showed the transition and crystalline melting point at 90-105 degrees C. The effects of bioflocculant dosage and pH on the flocculation of mineral suspensions were evaluated. The bioflocculant exhibited good flocculating capability on mineral suspensions and achieved flocculating efficiencies of 90 percent for k-aolinite and 85 percent for hematite suspensions at a dosage of only 5 mL/L. The maximum arsenite removal was found to be 90 percent at a bioflocculant dosage of 2 g/L, which is better than traditional chemicalflocculants. This study demonstrates that microbial bioflocculants have potential for application in environmental cleanup, such as in the flocculation of mineral fines and in the remediation of solutions that contain toxic heavy metals.

Soft-particle model analysis of effect of LPS on electrophoretic softness of Acidithiobacillus ferrooxidans grown in presence of different metal ions

The effect of Surface lipopolysaccharides (LPS) on the electrophoretic softness and fixed charge density in the ion-penetrable layer of Acidithiobacillus ferrooxidans cells grown in presence of copper or arsenic ions have been discussed, The electrophoretic mobility data were analyzed using the soft-particle electrophoresis theory. Cell surface potentials of all the strains based on soft-particle theory were lower than those estimated using the conventional Smoluchowski theory, Exposure to metal ions increased the Surface electrophoretic softness with decrease in the fixed charge density. Effect of cell surface lipopolysaccharides on the model parameters are investigated and discussed.

Re-use of fluoride contaminated bone char sludge in concrete

Managing sludge generated by treating groundwater contaminated with geogenic contaminants (fluoride, arsenic, and iron) is a major issue in developing nations. Their re-use in civil engineering applications is a possible pathway for reducing the impact on the geo-environment. This paper examines the re-use of one such sludge material, namely, fluoride contaminated bone char sludge, as partial replacement for fine aggregate (river-sand) in the manufacture of dense concrete specimens. Bone char sludge is being produced by defluoridation of contaminated groundwater in Nalagonda District, Andhra Pradesh, India. The impact of admixing 1.5-9% sludge contents on the compression strength and fluoride leaching potential of the sludge admixed concrete (SAC) specimens are examined. The compression strengths of the SAC specimensa re examined with respect to strength criteria for manufacture of dense, load-bearing concrete blocks. The fluoride release potential of the SAC specimens is examined with respect to standards specific to disposal of treated leachate into inland surface water.

Photoacoustic spectroscopy of solids and surfaces

After briefly reviewing the theory and instrumentation, results from a variety of experiments carried out by the authors on the photoacoustic spectroscopy of solids and surfaces by employing an indigenous spectrometer are discussed in the light of the recent literature. Some of the important findings discussed are, phase angle spectroscopy, anomalous behaviour of monolayers, unusual frequency dependence in small cell volumes, spectra of a variety of solids including amorphous arsenic chalcogenides, photoacoustic detection of phase transitions and determination of surface areas and surface acidities of oxides. Recent developments such as piezoelectric photoacoustic spectroscopy, depth profiling and subsurface imaging are also presented.

Dipole moments and structure of organophosphine and organoarsine compounds

The formal charge distributions in and the dipole moments of some organophosphines and arsines have been calculated, and the dipole moments of (p-chlorophenyl)dichlorophosphine (2.28 D) and (p-bromophenyl)dichlorophosphine (2.04 D) have been determined in benzene at 35° C. The differences between the observed and the calculated moments are explained in terms of dπ---pπ back-bonding and hyperconjugative effects in alkylhaloarsines. The mesomeric effects operating in the aromatic systems are evaluated by comparing the moments with those for the corresponding aliphatic systems. In unsaturated compounds the differences are attributed to mesomeric effects involving the expansion of arsenic valence shell.