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.

Geochemistry of fluoride rich groundwater in Kolar and Tumkur Districts of Karnataka

Groundwater is a significant water resource in India for domestic, irrigation, and industrial needs. By far the most serious natural groundwater-quality problem in India, in terms of public health, derives from high fluoride, arsenic, and iron concentrations. Hydrogeochemical investigation of fluoride contaminated groundwater samples from Kolar and Tumkur Districts in Karnataka are undertaken to understand the quality and potability of groundwater from the study area, the level of fluoride contamination, the origin and geochemical mechanisms driving the fluoride enrichment. Majority of the groundwater samples did not meet the potable water criteria as they contained excess (>1.5 mg/L) fluoride, dissolved salts (>500 mg/L) and total hardness (75-924 mg/L). Hydrogeochemical facies of the groundwater samples suggest that rock weathering and evaporation-crystallization control the groundwater composition in the study area with 50-67% of samples belonging to the Ca-HCO3 type and the remaining falling into the mixed Ca-Na-HCO3 or Ca-Mg-Cl type. The saturation index values indicated that the groundwater in the study area is oversaturated with respect to calcite and under-saturated with respect to fluorite. The deficiency of calcium ion concentration in the groundwater from calcite precipitation favors fluorite dissolution leading to excess fluoride concentration.

Bioremediation of diesel oil contaminated soil and water

Diesel spills contaminate aquatic and terrestrial environments. To prevent the environmental and health risks, the remediation needs to be advanced. Bioremediation, i.e., degradation by microbes, is one of the suitable methods for cleaning diesel contamination. In monitored natural attenuation technique are natural processes in situ combined, including bioremediation, volatilization, sorption, dilution and dispersion. Soil bacteria are capable of adapting to degrade environmental pollutants, but in addition, some soil types may have indigenous bacteria that are naturally suitable for degradation. The objectives for this work were (1) to find a feasible and economical technique to remediate oil spilled into Baltic Sea water and (2) to bioremediate soil contaminated by diesel oil. Moreover, the aim was (3) to study the potential for natural attenuation and the indigenous bacteria in soil, and possible adaptation to degrade diesel hydrocarbons. In the aquatic environment, the study concentrated on diesel oil sorption to cotton grass fiber, a natural by-product of peat harvesting. The impact of diesel pollution was followed in bacteria, phytoplankton and mussels. In a terrestrial environment, the focus was to compare the methods of enhanced biodegradation (biostimulation and bioaugmentation), and to study natural attenuation of oil hydrocarbons in different soil types and the effect that a history of previous contamination may have on the bioremediation potential. (1) In the aquatic environment, rapid removal of diesel oil was significant for survival of tested species and thereby diversity maintained. Cotton grass not only absorbed the diesel but also benefited the bacterial growth by providing a large colonizable surface area and hence oil-microbe contact area. Therefore use of this method would enhance bioremediation of diesel spills. (2) Biostimulation enhances bioremediation, and (3) indigenous diesel-degrading bacteria are present in boreal environments, so microbial inocula are not always needed. In the terrestrial environment experiments, the combination of aeration and addition of slowly released nitrogen advanced the oil hydrocarbon degradation. Previous contamination of soil gives the bacterial community the potential for rapid adaptation and efficient degradation of the same type of contaminant. When the freshly contaminated site needs addition of diesel degraders, previously contaminated and remediated soil could be used as a bacterial inoculum. Another choice of inoculum could be conifer forest soil, which provides a plentiful population of degraders, and based on the present results, could be considered as a safe non-polluted inoculum. According to the findings in this thesis, bioremediation (microbial degradation) and monitored natural attenuation (microbial, physical and chemical degradation) are both suitable techniques for remediation of diesel-contaminated sites in Finland.

Compositional dependence of crystallization of As-Te glasses

Thermal crystallization studies have been carried out on bulk, semiconducting AsxTe100−x glasses of different compositions using Differential Scanning Caloritmery. AsxTe100−x glasses with x < 40, are found to exhibit one glass transition and one crystallization. On the other hand, glasses with composition 40 less-than-or-equals, slantxless-than-or-equals, slant 50 show one glass transition and two crystallization reactions. It has been found that in glasses with x greater-or-equal, slanted 40, the two crystallization reactions progressively merge with an increase in arsenic concentration. Consequently AsxTe100−x glasses with x greater-or-equal, slanted 50 show only one crystallization. The composition dependence of crystallization temperatures and activation energies for crystallization estimated by Kissinger's method, show marked deviations at a composition x = 40. These observations can be explained in terms of the changes in the local structure of the material with composition.

Coupled substitution of niobium and silicon in potassium titanyl phosphate and arsenate (KTiOPO4 and KTiOAsO4. Synthesis and nonlinear optical properties of KTi1-xNbxOX1-xSixO4 (X = P, As)

Coupled substitution of Nb(V) and Si(IV) for Ti(IV) and P(V)/As(V) in KTiOP04 (KTP) and KTiOAsO4 (KTA) giving new series of nonlinear optical materials, KTi1-xNbxOX1-xSixO4 (X=P,As), has been investigated. Substitution up to x = 0.40 readily occurs, the members retaining the orthorhombic (Pna2(1)) structure of KTP. The second harmonic generation (SHG) property of the parent KTP and KTA is not adversely affected by the coupled substitution. SHG intensity of the powder samples of the X = P series shows a slight increase with x up to x = 0.15; for 0.15 < x less-than-or-equal-to 0.40, there is a decrease in SHG intensity as compared to that for KTP. A similar trend in SHG intensity is seen for the arsenic analogs.

Electrical switching and short-range order in As-Te glasses

The local structural order in chalcogenide network glasses is known to change markedly at two critical compositions, namely, the percolation and chemical thresholds. In the AsxTe100-x glassy system, both the thresholds coincide at the composition x = 40 (40 at. % of arsenic). It is demonstrated that the electrical switching fields of As-Te glasses exhibit a distinct change at this composition.

Mo3O5(OH)(2)(AsO4)2: A new solid with a structure related to beta VOPO4

Mo3O5(OH)(2)(AsO4)(2) was prepared at 100 degrees C from an aqueous solution of MoO3 containing arsenic and nitric acids. It crystallises in the monoclinic system, a = 13.024(1)Angstrom, b = 7.2974 (2) Angstrom, c = 13.281(1) Angstrom, beta = 121.124(8)degrees, Z = 4, space group C2/c. The structure was determined by Rietveld refinement from X-ray powder diffraction data. The three-dimensional structure is built up from MoO6 and MoO5OH octahedra and AsO4 tetrahedra sharing corners. The octahedra share two opposite vertices forming zigzag chains that run parallel to [10(1) over bar]. Each AsO4 tetrahedron is connected to four octahedra, two of which belong to the same chain, thus linking three chains. The resulting covalent framework is similar to that of beta VOPO4 in which one tetrahedral P site for every three is empty. The two protons are likely to be bonded to two (out of four) unshared oxygen atoms surrounding this empty site. All the Mo atoms are strongly off-centred in the octahedra; and the off-centring is disordered. The disorder is discussed in terms of Mo shifts perturbed by a disordered hydrogen bonding scheme.

Removal of As(V) by adsorption onto mixed rare earth oxides

Arsenic pollution of water is a major problem faced worldwide. Arsenic is a suspected carcinogen in human beings and is harmful to other living beings. In the present study, a novel adsorbent was used to remove arsenate [As(V)] from synthetic solutions. The adsorbent, which is a mixture of rare earth oxides, was found to adsorb As(V) rapidly and effectively. The effect of various parameters such as contact time, initial concentration, pH, and adsorbent dose on adsorption efficiency was investigated. More than 90% of the adsorption occurred within the first 10 min and the kinetic rate constant was found to be about 3.5 mg min(-1). Adsorption efficiency was found to be dependent on the initial As(V) concentration, and the adsorption behavior followed the Langmuir adsorption model. The optimum pH was found to be 6.5. The presence of other ions such as nitrate, phosphate, sulphate, and silicate decreased the adsorption of As(V) by about 20-30%. The adsorbed As(V) could be desorbed easily by washing the adsorbent with pH 12 solution. This study demonstrates the applicability of naturally occurring rare earth oxides as selective adsorbents for As(V) from solutions.

Structural, optical, and electrical properties of bulk single crystals of InAsxSb(1-x) grown by rotatory Bridgman method

Radially-homogeneous and single-phase InAsxSb(1−x) crystals, up to 5.0 at. % As concentration, have been grown using the rotatory Bridgman method. Single crystallinity has been confirmed by x-ray and electron diffraction studies. Infrared transmission spectra show a continuous decrease in optical energy gap with the increase of arsenic content in InSb. The measured values of mobility and carrier density at room temperature (for x = .05) are 5.6×104 cm2/V s and 2.04×1016 cm−3, respectively.

Assessment of treatment capabilities of Varthur Lake, Bangalore, India

Manmade waterbodies have traditionally been used for domestic and irrigation purposes. Unplanned urbanization and ad-hoc approaches have led to these waterbodies receiving untreated sewage. This enriches and eutrophies the waterbody. A physicochemical and biological analysis of sewage-fed Varthur Lake in Bangalore was carried out and its treatment capabilities in terms of BOD removal, nutrient assimilation and self-remediation were assessed. Anaerobic conditions (0 mg/L) prevail at the inlet which improves towards the outlets due to algal aeration. This removed > 50% BOD in the monsoon season but was inhibited by floating macrophytes in all other seasons. Alkalinity, TDS, conductivity and hardness values were higher when compared to earlier studies. This study shows the lake behaves as an anaerobic~aerobic lagoon with a residence time of 4.8 d treating the wastewater to a considerable extent. Further research is required to optimise the system performance.

Non-linear electrical response of chalcogenide glasses: Memory state phenomena

Investigations on the switching behaviour of arsenic-tellurium glasses with Ge or Al additives, yield interesting information about the dependence of switching on network rigidity, co-ordination of the constituents, glass transition & ambient temperature and glass forming ability.

Photocatalytic degradation of gaseous toluene by using immobilized titania/silica on aluminum sheets

The aim of this study was to prepare a highly active immobilized titania/silica photocatalyst and to test its performance in situ toward degradation of toluene as one of the major toxic indoor contaminants. In this work, two different titania layers immobilized on Al sheets were synthesized via low temperature sol-gel method employing presynthesized highly active titania powders (Degussa P25 and Millennium PC500, mass ratio 1:1): (a) with a silica/titania binder and a protective layer and (b) without the binder. The photocatalysts were characterized by X-ray diffraction, nitrogen sorption measurements, scanning electron microscopy (SEM), infrared spectroscopy, and UV-vis diffuse reflectance spectroscopy (DRS). The in situ photocatalytic degradation of gaseous toluene was selected as a probe reaction to test photocatalytic activity and to verify the potential application of these materials for air remediation. Results show that nontransparent highly photocatalytically active coatings based on the silica/titania binder and homogeneously dispersed TiO2 powders were obtained on the Al sheets. The crystalline structure of titania was not altered upon addition of the binder, which also prevented inhomogeneous agglomeration of particles on the photocatalyst surface. The photoactivity results indicate that the adsorption properties and photocatalytic activity of immobilized photocatalysts with the silica/titania binder and an underlying protective layer were very effective and additionally, they exhibited considerably improved adhesion and uniformity. We present a new highly photocatalytically active immobilized catalyst on a convenient metallic support, which has a potential application in an air cleaning device.

Influence of anthropogenic contamination on fluoride concentration in groundwater: A study of Mulbagal town, Kolar district, Karnataka

Groundwater contamination is a serious concern in India. Major geogenic contaminants include fluoride, arsenic and iron, while common anthropogenic contaminants include nitrate, metals, organics and microbial contamination. Besides, known point and diffuse sources, groundwater c ontamination from inf iltration of pit to ilet leachate is an emerging concern. The study area of this paper is Kolar district in Karnataka that is hot spot of fluoride contamination. The absence of fluoride contamination in Mulbagal town and the alterations in groundwater chemistry from infiltration of pit toilet leachate motivated the author to examine the possible linkages between anthropogenic contamination and fluoride concentration in groundwater of Mulbagal town. Analysis of the groundwater chemistry revealed that the groundwater in Mulbagal town is under saturated with respect to calcite that suppresses the dissolution of fluorite and the fluoride concentration in the groundwater. The slightly acidic pH of the groundwater is considered responsible to facilitate calcite dissolution under saturation.

Comparative Studies on the Bioremediation of Hexavalent and Trivalent Chromium using Citrobacter freundii: Part I-Effect of parameters controlling Biosorption

The potential of Citrobacter freundii, a Gram negative bacteria for the remediation of hexavalent chromium (Cr(VI)) and trivalent chromium (Cr(III))) from aqueous solutions was investigated. Bioremediation of Cr(VI) involved both biosorption and bioreduction processes, as compared to only biosorption process observed with respect to Cr(III) bioremediation. In the case of Cr(VI) bioremediation studies, about 59 % biosorption was achieved at an equilibrium time of 2 h, initial Cr(VI) concentration of 4 mg/L, pH 1 and a biomass loading of 5x10(11) cells/mL. The remainder, 41 %, was found to be in the form of Cr(111) ions owing to bioreduction of Cr(VI) by the bacteria resulting in the absence of Cr(VI) ions in the residue, there by meeting the USEPA specifications. Similar studies were carried out using Cr(III) solution for an equilibrium time of 2 h, Cr(III) concentration of 4 mg/L, pH 3 and a biomass loading of 6.3x10(11) cells/mL., wherein a maximum biosorption of about 30 % was achieved.

Production and characterization of bioflocculants for mineral processing applications

A comparative study of two bacterial strains namely, Bacillus licheniformis and Bacillus firmus in the production of bioflocculants was made. The highest bioflocculant yield of 16.55 g/L was obtained from B. licheniformis (L) and 10 g/L from B. firmus (F). The bioflocculants obtained from the bacterial species were water soluble and insoluble in organic solvents. FTIR spectral analysis revealed the presence of hydroxyl, carboxyl and sugar derivatives in the bioflocculants. Thermal characterization by differential scanning calorimetry (DSC) showed the crystalline transition and the melting point (T-m) at 90-100 degrees C. Effects of bioflocculant dosage and pH on the flocculation of clay fines were evaluated. Highest bioflocculation efficiency on kaolin clay suspensions was observed at an optimum bioflocculant dosage of 5 g/L. The optimum pH range for the maximum bioflocculation was at pH 7-9. Bioflocculants exhibited high efficiency in dye decolorization. The maximum Cr (VI) removal was found to be 85 % for L (bioflocculant dosage at 2 g/L). This study demonstrates that microbial bioflocculants find potential applications in mineral processing such as selective flocculation of mineral fines, decolorization of dye solutions and in the remediation of toxic metal solutions. (C) 2015 Elsevier B.V. All rights reserved.