Environmental remediation by photocatalysis

Photocatalysis refers to the oxidation and reduction reactions on semiconductor surfaces, mediated by the valence band holes and conduction band electrons, which are generated by the absorption of ultraviolet or visible light radiation. Photocatalysis is widely being practiced for the degradation and mineralization of hazardous organic compounds to CO2 and H2O, reduction of toxic metal ions to their non-toxic states, deactivation and destruction of water borne microorganisms, decomposition of air pollutants like volatile organic compounds, NOx, CO and NH3, degradation of waste plastics and green synthesis of industrially important chemicals. This review attempts to showcase the well established mechanism of photocatalysis, the use of photocatalysts for water and air pollution control,visible light responsive modified-TiO2 and non-TiO2 based materials for environmental and energy applications, and the importance of developing reaction kinetics for a comprehensive understanding and design of the processes.

Photocatalytic degradation of dimethoate using LbL fabricated TiO2/polymer hybrid films

Degradation of dimethoate under UV irradiation using TiO2/polymer films prepared by the layer-by-layer (LbL) method was investigated. The thin films were fabricated on glass slides and the surface morphology and roughness of the thin films were characterized using X-ray diffraction (XRD), scanning electron microscopy (SEM) and atomic force microscopy (AFM). The effect of lamp intensity, catalyst loading in the layers, number of bilayers, pH and initial dimethoate concentration on the degradation of dimethoate was systematically studied. The degradation was monitored using high performance liquid chromatography (HPLC) analysis and total organic carbon (TOC) measurements as a function of irradiation time, to see the change in concentration of dimethoate and mineralization, respectively. Complete degradation of dimethoate was achieved under TiO2 optimum loading of 4 g/L at an UV irradiation time of 180 min. Increase in the lamp intensity, catalyst loading and number of bilayers increased the rate of degradation. At a pH of 4.62, complete degradation of dimethoate was observed. The degradation efficiency decreased with increase in initial dimethoate concentration. The degradation byproducts were analyzed and confirmed by gas chromatography-mass spectra (GC-MS). Toxicity of the irradiated samples was measured using the luminescence of bacteria Vibrio fischeri after 30 min of incubation and the results showed more toxicity than the parent compound. Catalyst reusability studies revealed that the fabricated thin films could be repeatedly used for up to ten times without affecting the photocatalytic activity of the films. The findings of the present study are very useful for the treatment of wastewaters contaminated with pesticides. (C) 2011 Elsevier B.V. All rights reserved.

Spin-Electron-Phonon Excitation in Re-based Half-Metallic Double Perovskites

A remarkable hardening (similar to 30 cm(-1)) of the normal mode of vibration associated with the symmetric stretching of the oxygen octahedra for the Ba2FeReO6 and Sr2CrReO6 double perovskites is observed below the corresponding magnetic ordering temperatures. The very large magnitude of this effect and its absence for the antisymmetric stretching mode provide evidence against a conventional spin-phonon coupling mechanism. Our observations are consistent with a collective excitation formed by the combination of the vibrational mode with oscillations of Fe or Cr 3d and Re 5d occupations and spin magnitudes.

The hazard potential of the western segment of the Makran subduction zone, northern Arabian Sea

Evaluating the hazard potential of the Makran subduction zone requires understanding the previous records of the large earthquakes and tsunamis. We address this problem by searching for earthquake and tectonic proxies along the Makran Coast and linking those observations with the available constraints on historical seismicity and the tell-tale characteristics of sea floor morphology. The earthquake of Mw 8.1 of 1945 and the consequent tsunami that originated on the eastern part of the Makran are the only historically known hazardous events in this region. The seismic status of the western part of the subduction zone outside the rupture area of the 1945 earthquake remains an enigma. The near-shore shallow stratigraphy of the central part of Makran near Chabahar shows evidence of seismically induced liquefaction that we attribute to the distant effects of the 1945 earthquake. The coastal sites further westward around Jask are remarkable for the absence of liquefaction features, at least at the shallow level. Although a negative evidence, this possibly implies that the western part of Makran Coast region may not have been impacted by near-field large earthquakes in the recent past-a fact also supported by the analysis of historical data. On the other hand, the elevated marine terraces on the western Makran and their uplift rates are indicative of comparable degree of long-term tectonic activity, at least around Chabahar. The offshore data suggest occurrences of recently active submarine slumps on the eastern part of the Makran, reflective of shaking events, owing to the great 1945 earthquake. The ocean floor morphologic features on the western segment, on the contrary, are much subdued and the prograding delta lobes on the shelf edge also remain intact. The coast on the western Makran, in general, shows indications of progradation and uplift. The various lines of evidence thus suggest that although the western segment is potentially seismogenic, large earthquakes have not occurred there in the recent past, at least during the last 600 years. The recurrence period of earthquakes may range up to 1,000 years or more, an assessment based on the age of the youngest dated coastal ridge. The long elapsed time points to the fact that the western segment may have accumulated sufficient slip to produce a major earthquake.

A Compact and Compliant External Pipe-Crawling Robot

The focus of this paper is on the practical aspects of design, prototyping, and testing of a compact, compliant external pipe-crawling robot that can inspect a closely spaced bundle of pipes in hazardous environments and areas that are inaccessible to humans. The robot consists of two radially deployable compliant ring actuators that are attached to each other along the longitudinal axis of the pipe by a bidirectional linear actuator. The robot imitates the motion of an inchworm. The novel aspect of the compliant ring actuator is a spring-steel compliant mechanism that converts circumferential motion to radial motion of its multiple gripping pads. Circumferential motion to ring actuators is provided by two shape memory alloy (SMA) wires that are guided by insulating rollers. The design of the compliant mechanism is derived from a radially deployable mechanism. A unique feature of the design is that the compliant mechanism provides the necessary kinematic function within the limited annular space around the pipe and serves as the bias spring for the SMA wires. The robot has a control circuit that sequentially activates the SMA wires and the linear actuator; it also controls the crawling speed. The robot has been fabricated, tested, and automated. Its crawling speed is about 45 mm/min, and the weight is about 150 g. It fits within an annular space of a radial span of 15 mm to crawl on a pipe of 60-mm outer diameter.

Low-thermal-budget solution processing of thin films of zinc ferrite and other complex oxides

Further miniaturization of magnetic and electronic devices demands thin films of advanced nanomaterials with unique properties. Spinel ferrites have been studied extensively owing to their interesting magnetic and electrical properties coupled with stability against oxidation. Being an important ferrospinel, zinc ferrite has wide applications in the biological (MRI) and electronics (RF-CMOS) arenas. The performance of an oxide like ZnFe2O4 depends on stoichiometry (defect structure), and technological applications require thin films of high density, low porosity and controlled microstructure, which depend on the preparation process. While there are many methods for the synthesis of polycrystalline ZnFe2O4 powder, few methods exist for the deposition of its thin films, where prolonged processing at elevated temperature is not required. We report a novel, microwave-assisted, low temperature (<100°C) deposition process that is conducted in the liquid medium, developed for obtaining high quality, polycrystalline ZnFe2O4 thin films on technologically important substrates like Si(100). An environment-friendly solvent (ethanol) and non-hazardous oxide precursors (β-diketonates of Zn and Fe in 1:2 molar ratio), forming a solution together, is subjected to irradiation in a domestic microwave oven (2.45 GHz) for a few minutes, leading to reactions which result in the deposition of ZnFe2O4 films on Si (100) substrates suspended in the solution. Selected surfactants added to the reactant solution in optimum concentration can be used to control film microstructure. The nominal temperature of the irradiated solution, i.e., film deposition temperature, seldom exceeds 100°C, thus sharply lowering the thermal budget. Surface roughness and uniformity of large area depositions (50x50 mm2) are controlled by tweaking the concentration of the mother solution. Thickness of the films thus grown on Si (100) within 5 min of microwave irradiation can be as high as several microns. The present process, not requiring a vacuum system, carries a very low thermal budget and, together with a proper choice of solvents, is compatible with CMOS integration. This novel solution-based process for depositing highly resistive, adherent, smooth ferrimagnetic films on Si (100) is promising to RF engineers for the fabrication of passive circuit components. It is readily extended to a wide variety of functional oxide films.

Analytical model for stress-strain response of plastic waste mixed soil

Recycling plastic water bottles has become one of the major challenges world wide. The present study provides an approach for the use of plastic waste as reinforcement material in soil, which can be used for ground improvement, subbases, and subgrade preparation in road construction. The experimental results are presented in the form of stress-strain-pore water pressure response and compression paths. On the basis of experimental test results, it is observed that the strength of soil is improved and compressibility reduced significantly with the addition of a small percentage of plastic waste to the soil. In this paper, an analytical model is proposed to evaluate the response of plastic waste mixed soil. It is noted that the model captures the stress-strain and pore water pressure response of all percentages of plastic waste adequately. The paper also provides a comparative study of failure stress obtained from different published models and the proposed model, which are compared with experimental results. The improvement in strength attributable to the inclusion of plastic waste can be advantageously used in ground improvement projects.

Iodide Retention by Modified Kaolinite in the Context of Safe Disposal of High Level Nuclear Waste

Bentonite clay is identified as potential buffer in deep geological repositories (DGR) that store high level radioactive wastes (HLW) as the expansive clay satisfies the expected mechanical and physicochemical functions of the buffer material. In the deep geological disposal of HLW, iodine-129 is one of the significant nuclides, attributable to its long half-life (half life 1⁄4 1:7 × 107 years). However, the negative charge on the basal surface of bentonite particles precludes retention of iodide anions. To render the bentonite effective in retaining hazardous iodide species in DGR, improvement of the anion retention capacity of bentonite becomes imperative. The iodide retention capac-ity of bentonite is improved by admixing 10 and 20% Ag-kaolinite (Ag-K) with bentonite (B) on a dry mass basis. The present study produced Ag-kaolinite by heating silver nitrate-kaolinite mixes at 400°C. Marginal release of iodide retained by Ag-kaolinite occurred under extreme acidic (pH 1⁄4 2:5) and alkaline (pH 1⁄4 12:5) conditions. The swell pressure and iodide etention results of the B-Ag-K specimens bring out that mixing Ag-K with bentonite does not chemically modify the expansive clay; the mixing is physical in nature and Ag-K presence only contributes to iodide retention of the admixture. DOI: 10.1061/(ASCE)HZ.2153-5515.0000121. © 2012 American Society of Civil Engineers.

Biogenic nanosilver incorporated reverse osmosis membrane for antibacterial and antifungal activities against selected pathogenic strains: An enhanced eco-friendly water disinfection approach

Reverse osmosis (RO) membranes have been used extensively in water desalination plants, waste water treatment in industries, agricultural farms and drinking water production applications. The objective of this work is to impart antibacterial and antifungal activities to commercially available RO membrane used in water purification systems by incorporating biogenic silver nanoparticles (AgNPs) synthesized using Rosa indica wichuriana hybrid leaf extract. The morphology and surface topography of uncoated and AgNPs-coated RO membrane were studied using Scanning Electron Microscopy (SEM) and Atomic Force Microscopy (AFM). Elemental composition of the AgNPs-coated RO membrane was analyzed by energy-dispersive X-ray spectroscopy (EDAX). The functional groups were identified by Fourier Transform Infrared spectroscopy (FT-IR). Hydrophilicity of the uncoated and AgNPs-coated RO membrane was analyzed using water contact angle measurements. The thermal properties were studied by thermogravimetric analysis (TGA). The AgNPs incorporated RO membrane exhibited good antibacterial and antifungal activities against pathogenic bacterial strains such as E. coli, S. aureus, M. luteus, K. pneumoniae, and P. aeruginosa and fungal strains such as Candida tropicalis, C. krusei, C. glabrata, and C. albicans.

Actividades de las autoridades argentinas y la embajada española sobre los anarquistas antes de la Ley de Residencia

Resumen: El presente trabajo investiga la actuación de la Embajada de España con respecto a la entrada a la Argentina de inmigrantes con antecedentes anarquistas durante fines del siglo XIX y los primeros dos años del siglo XX. Registra además el interés por seguir los movimientos de dichos inmigrantes en el país. Se destaca el rol de la documentación diplomática, mediante la cual la Embajada española se mantenía en permanente contacto con el gobierno central, con las autoridades argentinas y con los consulados del interior para intercambiar información. A través de las fuentes se puede observar la labor de “inteligencia ideológica” que se realizó y el detallado conocimiento que se tenía sobre los anarquistas, sus vías de traslado hacia nuestro país, sus profesiones, paraderos, domicilios, relaciones, y las minuciosas descripciones físicas de los sospechados. En esta política se nota la coparticipación entre la Embajada de España y las instituciones argentinas para desligarse de elementos que denominaban “no deseados”. También se consideran las relaciones entre el anarquismo argentino y el español, así como la importancia de la prensa revolucionaria, aun sobre la misma España. La vigilancia que ejercía la Embajada española sobre los inmigrantes, el control sobre los anarquistas españoles en la Argentina y la influencia de éstos sobre los sucesos de la Península demuestran a las claras la preocupación del gobierno hispano en la cuestión.

Esclavos en el reino de Toledo

Resumen: La esclavitud en la Edad Moderna supuso una realidad social muy arraigada. Último eslabón de una sociedad estamental, en este trabajo, enmarcado espacialmente en el reino de Toledo en tierras de Castilla se analizan diversos aspectos de la condición de los esclavos: descripción y aspecto físico, tipología de las causas de esclavitud, comercio de esclavos, ocupaciones y servicios a que se dedicaban, comportamiento y conflictividad social y finalmente la manumisión. Para ello se han utilizado fuentes procedentes de archivos religiosos, de la nobleza y abundante documentación notarial y judicial.

La souffrance émotionnelle des personnels d’intervention : résultats préliminaires de l’étude sur la santé et la qualité de vie au travail dans les métiers du secteur de l’aide et du soin à domicile

Resumen: La prolongación de la edad y el aumento de la expectativa de vida han hecho surgir nuevas necesidades de atención para las personas ancianas y ello ha inducido a la ampliación de las prestaciones de servicios a domicilio. En este sentido, el trabajo de estos profesionales de intervención a domicilio, así como sus misiones, están en plena mutación. Es un sector con dificultades, debido a la dificultad de reclutar un personal especializado y al absentismo inquietante. Después de un análisis sobre el estado de este sector de la profesión en el que se establece la diferencia entre el enfoque físico y el psicológico sobre la salud, nuestra reflexión se centra en los riesgos psicosociales de esta población de profesionales. Se presentan los resultados preliminares de la investigación realizada con una muestra de 38 personas que ejercían laboralmente en este sector. Emerge la expresión de un sufrimiento emocional, en la que el aislamiento de los participantes es uno de los factores que caracterizan los oficios identificados con una fuerte dimensión relacional con personas vulnerables. La dimensión asistencial del trabajo se presenta como fuente de satisfacción del oficio pero, a su vez, puede conducir a una dificultad de gestionar acontecimientos no previstos

Criminalização das ocupações de propriedades rurais por movimentos sociais : reflexões à luz dos princípios de direito penal mínimo

Analisa a pretensão da criminalização primária das ocupações de propriedades públicas e privadas por movimentos sociais, tendo como marco teórico o pensamento de Alessandro Baratta sobre os limites de intervenção penal estatal, especialmente os princípios da “proporcionalidade abstrata” e da “articulação autônoma dos conflitos e das necessidades reais”.

The Impact of Gender Segregation on Male-Female Wage Differentials

This paper presents new evidence on the role of gender segregation and pay structure in explaining gender wage differentials of full-time salaried workers in Spain. Data from the 1995 and 2002 Wage Structure Surveys reveal that raw gender wage gaps decreased from 0.24 to 0.14 over the seven-year period. Average differences in the base wage and wage complements decreased from 0.09 to 0.05 and from 0.59 to 0.40, respectively. However, the gender wage gap is still large after accounting for workers’ human capital, job and pay structure characteristics, and female segregation into low-paying industries, occupations, establishments, and occupations within establishments.

Wage differentials between permanent and temporary workers: Firm and occupational segregation

Published as an article in: Moneda y Crédito (2004), 219, pp.: 43-68.