Evaluation of laser induced breakdown spectroscopy for cadmium determination in soils

Cadmium is known to be a toxic agent that accumulates in the living organisms and present high toxicity potential over lifetime. Efforts towards the development of methods for microanalysis of environmental samples, including the determination of this element by graphite furnace atomic absorption spectrometry (GFAAS). inductively coupled plasma optical emission spectrometry (ICP OES), and inductively coupled plasma-mass spectrometry (ICP-MS) techniques, have been increasing. Laser induced breakdown spectroscopy (UBS) is an emerging technique dedicated to microanalysis and there is a lack of information dealing with the determination of cadmium. The aim of this work is to demonstrate the feasibility of LIBS for cadmium detection in soils. The experimental setup was designed using a laser Q-switched (Nd:YAG, 10 Hz, lambda = 1064 nm) and the emission signals were collimated by lenses into an optical fiber Coupled to a high-resolution intensified charge-coupled device (ICCD)-echelle spectrometer. Samples were cryogenically ground and thereafter pelletized before LIBS analysis. Best results were achieved by exploring a test portion (i.e. sampling spots) with larger surface area, which contributes to diminish the uncertainty due to element specific microheterogeneity. Calibration curves for cadmium determination were achieved using certified reference materials. The metrological figures of merit indicate that LIBS can be recommended for screening of cadmium contamination in soils. (C) 2009 Elsevier B.V. All rights reserved.

Morphological and mechanical properties of hybrid matrices of polysiloxane-polyvinyl alcohol prepared by sol-gel technique and their potential for immobilizing enzyme

Hybrid matrices of polysiloxane-polyvinyl alcohol (POS-PVA) were prepared by sol-gel technique using different concentrations of the organic component (polyvinyl alcohol, PVA) in the synthesis medium. The goal was to prepare carriers for immobilizing enzyme by taking into consideration properties as hardness, mean pore diameter, specific surface area and pore size distribution. The matrices were activated with sodium metaperiodate to render functional groups for binding the lipase from Candida rugosa, used here as a study model. Results showed that low proportion of PVA gave POS-PVA with low surface area and pore volume, although with higher hardness. The chemical activation decreased the pore volume and increased the pore size with a decrease on the surface area of about 60-75%. The matrices for enzyme immobilization were chosen considering the best combination of high surface area and hardness. Thus, the POS-PVA prepared with 5.56 x 10(-5) M of PVA with a surface area of 123 m(2)/g and hardness of 71 HV (50 gf 30 s) was shown to be suitable to immobilize the lipase, with an immobilization yield of about 40%. (c) 2008 Elsevier B.V. All rights reserved.

Strength improvement of LPS-SiC ceramics by oxidation treatment

In this work, SiC ceramics were liquid phase sintered (LPS), using AIN-Y(2)O(3) as additives, and oxidized at 1400 degrees C in air for up to 120 h. Oxidation was monitored by the weight gain of the samples as function of exposition time and temperature. A parabolic growth of the oxidation layer has been observed and the coefficient of the growth rate has been determined by relating the weight gain and the surface area. The effect of oxidation on strength has been determined by 4-point bending tests. Phase analysis by Xray diffraction and microstructural observation by scanning electron microscopy indicated the formation of a uniform and dense oxidation layer. The elimination of surface flaws and pores and the generation of compressive stresses in the surface resulted in a strength increase of the oxidized samples. (C) 2009 Published by Elsevier Ltd.

Gelcasting of alumina-chitosan beads

Several papers have reported the advantageous combination of chitosan and ceramic particles for such applications as biomimetic scaffolds, membranes, pollution remediation and gelcasting complex shapes. This work presents a novel gelcasting consolidation mechanism, based on the effects of pH changes on chitosan solubility and zeta potential of alumina particles. Unlike other chitosan-based gelcasting methods, it employs a small content of organic material (lower than 3 wt%) and does not require crosslinking agents (such as glutaraldehyde). With this new method alumina beads with 0.5-1 mm diameter could be produced, whose porosity and specific surface area could be tuned for various applications. (C) 2011 Elsevier Ltd and Techna Group S.r.l. All rights reserved.

Porous alumina-spinel ceramics for high temperature applications

In order to reduce energy costs, high-temperature insulation porous refractory ceramics have been subjected to increasing demands. Among the techniques used to produce these materials (such as the addition of foaming agents and organic compounds), the pore generation via phase transformation presents key aspects, such as easy processing and the absence of toxic volatiles. In this study, this technique was applied to produce porous ceramics by decomposing an aluminum magnesium hydro-carbonate known as hydrotalcite (Mg(6)Al(2)(CO(3))(OH)(16)center dot 4H(2)O). It was found out that by using this complex compound, a large fraction of pores can be generated and kept at high temperatures (above 1300 degrees C) due to the in situ formation of spinel-like phases (MgAl(2)O(4)). (C) 2011 Elsevier Ltd and Techna Group S.r.l. All rights reserved.

Pellets prepared with mechanically activated iron ore

This work analyses pellets prepared with iron ore that has been mechanically activated by high energy ball milling. Pellet feed iron ore was submitted to high-energy ball milling for 60 minutes, and the resulting material was analysed through measurements of particle size and specific surface area, as well as X-ray diffraction. Pellets were prepared from this material. The pellets were heated at temperatures ranging from 1000 to 1250 degrees C in a muffle furnace, and submitted to the maximum temperature during 10 - 12 minutes. The samples were then tested regarding crushing strength, densification and porosity, and were examined in a scanning electronic microscope. The results were compared to those obtained with similar samples made from non-milled pellet feed. It has been shown that through high-energy ball milling of iron ore it is possible to achieve pellets presenting high densification and compressive strength at firing temperatures lower than the usual ones.

Regeneration of Activated Carbon by (Photo)-Fenton Oxidation

This work aims to study the adsorption of phenol on activated carbons (ACs) and the consecutive in situ regeneration of carbon by Fenton oxidation. Two different operations have been carried Out: (1) a batch procedure in order to investigate the influence of Fe(2+) and H(2)O(2) concentrations; (2) continuous fixed bed adsorption, followed by a batch circulation of the Fenton`s reagent through the saturated AC bed. to examine the efficiency of the real process. Two different activated carbons have been also studied: a both micro- and mesoporous AC (L27) and an only microporous One (S23). In the batch reactor the best conditions found for pollutant mineralization in the homogeneous Fenton system are not the best For AC regeneration: a continuous reduction of adsorption capacity of L27 is observed after 3 oxidations, due to the decrease of both AC weight and surface area. Higher concentration of Fe(2+) and lower concentration of H(2)O(2) (2 times the stoichiometry) lead to a 50% recovery of the initial adsorption capacity during at least four consecutive cycles for L27, while about 20% or less for S23. In the consecutive continuous adsorption/batch Fenton oxidation process, the regeneration efficiency reaches 30-40% for L27 after two cycles whatever the feed concentration and less than 10% for S23. A photo-Fenton test performed on L27 shows almost complete mineralization (contrary to ""dark"" Fenton) and further improves recovery of AC adsorption capacity although not complete (56% after two cycles).

Biogenic modified silica as a sorbent of cadmium ions: Preparation and characterization

This work describes the preparation and characterization of biogenic modified silica from rice hull ash and its use as a sorbent of cadmium ions. Thus, an agro-industrial residue has been used to produce a new adsorbent product which is able to remove toxic elements. Mesoporous biogenic silica was obtained by alkaline extraction of sodium silicate by hydrolysis with the sol-gel process, and it was modified with salen using 1,2-dichloroethane as a spacer. The surface area of the silica was measured by nitrogen adsorption/desorption analysis. Surface modification was measured by Fourier transform infrared spectroscopy. The degree of functionalization was obtained by elemental analysis. This work showed that biogenic modified silica can be produced in aqueous media from rice hull ash using a simple method, providing an alternative method for adsorbent preparation. Thermogravimetric analysis showed that the salen-modified silica is stable up to 209 C. The modified silica displays appropriate structural characteristics for an adsorbent. The cylindrical pores, open at both ends, allow free diffusion of cadmium ions to the adsorption sites on the silica surface. The surface modification increases cadmium adsorption on the silica surface 100-fold. The salen-modified silica showed specific adsorption for Cd2+ of 44.52 mg/g SiO2 at cadmium concentration of 100 mg/l.

Evaluating responses of maize (Zea mays L.) to soil physical conditions using a boundary line approach

The functional relation between the decline in the rate of a physiological process and the magnitude of a stress related to soil physical conditions is an important tool for uses as diverse as assessment of the stress-related sensitivity of different plant cultivars and characterization of soil structure. Two of the most pervasive sources of stress are soil resistance to root penetration (SR) and matric potential (psi). However, the assessment of these sources of stress on physiological processes in different soils can be complicated by other sources of stress and by the strong relation between SR and psi in a soil. A multivariate boundary line approach was assessed as a means of reducing these cornplications. The effects of SR and psi stress conditions on plant responses were examined under growth chamber conditions. Maize plants (Zea mays L.) were grown in soils at different water contents and having different structures arising from variation in texture, organic carbon content and soil compaction. Measurements of carbon exchange (CE), leaf transpiration (ILT), plant transpiration (PT), leaf area (LA), leaf + shoot dry weight (LSDW), root total length (RTL), root surface area (RSA) and root dry weight (RDW) were determined after plants reached the 12-leaf stage. The LT, PT and LA were described as a function of SR and psi with a double S-shaped function using the multivariate boundary line approach. The CE and LSDW were described by the combination of an S-shaped function for SR and a linear function for psi. The root parameters were described by a single S-shaped function for SR. The sensitivity to SR and psi depended on the plant parameter. Values of PT, LA and LSDW were most sensitive to SR. Among those parameters exhibiting a significant response to psi, PT was most sensitive. The boundary line approach was found to be a useful tool to describe the functional relation between the decline in the rate of a physiological process and the magnitude of a stress related to soil physical conditions. (C) 2009 Elsevier B.V. All rights reserved.

Intrinsic Dissolution as a Tool for Evaluating Drug Solubility in Accordance with the Biopharmaceutics Classification System

The Biopharmaceutics Classification System (BCS) is a tool that was created to categorize drugs into different groups according to their solubility and permeability characteristics. Through a combination of these factors and physiological parameters, it is possible to understand the absorption behavior of a drug in the gastrointestinal tract, thus contributing to cost and time reductions in drug development, as well as reducing exposure of human subjects during in vivo trials. Solubility is attained by determining the equilibrium under conditions of physiological pH, while different methods may be employed for evaluating permeability. On the other hand, the intrinsic dissolution rate (IDR), which is defined as the rate of dissolution of a pure substance under constant temperature, pH, and surface area conditions, among others, may present greater correlation to the in vivo dissolution dynamic than the solubility test. The purpose of this work is to discuss the intrinsic dissolution test as a tool for determining the solubility of drugs within the scope of the Biopharmaceutics Classification System (BCS).

QSAR Modeling of a Set of Pyrazinoate Esters as Antituberculosis Prodrugs

Tuberculosis is an infection caused mainly by Mycobacterium tuberculosis. A first-line antimycobacterial drug is pyrazinamide (PZA), which acts partially as a prodrug activated by a pyrazinamidase releasing the active agent, pyrazinoic acid (POA). As pyrazinoic acid presents some difficulty to cross the mycobacterial cell wall, and also the pyrazinamide-resistant strains do not express the pyrazinamidase, a set of pyrazinoic acid esters have been evaluated as antimycobacterial agents. In this work, a QSAR approach was applied to a set of forty-three pyrazinoates against M. tuberculosis ATCC 27294, using genetic algorithm function and partial least squares regression (WOLF 5.5 program). The independent variables selected were the Balaban index (I), calculated n-octanol/water partition coefficient (ClogP), van-der-Waals surface area, dipole moment, and stretching-energy contribution. The final QSAR model (N = 32, r(2) = 0.68, q(2) = 0.59, LOF = 0.25, and LSE = 0.19) was fully validated employing leave-N-out cross-validation and y-scrambling techniques. The test set (N = 11) presented an external prediction power of 73%. In conclusion, the QSAR model generated can be used as a valuable tool to optimize the activity of future pyrazinoic acid esters in the designing of new antituberculosis agents.

Moisture sorption isotherm characteristics of freeze-dried D-limonene emulsions in modified chitosan and maltodextrin

This article reports on modified chitosan as an alternative substance for protecting loss of volatile compounds during freeze drying. Moisture sorption isotherms of freeze-dried D-limonene emulsions in modified chitosan were determined at 15, 25, and 35 degrees C. The data were adjusted to the GAB model. Maltodextrin was used in a parallel experiment. Flavor released from microcapsules was measured. The monolayer humidity, the sorption heat, the diffusivity coefficients, and the surface area of freeze-dried D-limonene emulsions were determined.

A chemometric study on the analgesic activity of cannabinoid compounds using SDA, KNN and SIMCA methods

The supervised pattern recognition methods K-Nearest Neighbors (KNN), stepwise discriminant analysis (SDA), and soft independent modelling of class analogy (SIMCA) were employed in this work with the aim to investigate the relationship between the molecular structure of 27 cannabinoid compounds and their analgesic activity. Previous analyses using two unsupervised pattern recognition methods (PCA-principal component analysis and HCA-hierarchical cluster analysis) were performed and five descriptors were selected as the most relevants for the analgesic activity of the compounds studied: R (3) (charge density on substituent at position C(3)), Q (1) (charge on atom C(1)), A (surface area), log P (logarithm of the partition coefficient) and MR (molecular refractivity). The supervised pattern recognition methods (SDA, KNN, and SIMCA) were employed in order to construct a reliable model that can be able to predict the analgesic activity of new cannabinoid compounds and to validate our previous study. The results obtained using the SDA, KNN, and SIMCA methods agree perfectly with our previous model. Comparing the SDA, KNN, and SIMCA results with the PCA and HCA ones we could notice that all multivariate statistical methods classified the cannabinoid compounds studied in three groups exactly in the same way: active, moderately active, and inactive.

Pt-RuO(2) electrodes prepared by thermal decomposition of polymeric precursors as catalysts for direct methanol fuel cell applications

The electrocatalytic activity of Pt and RuO(2) mixed electrodes of different compositions towards methanol oxidation was investigated. The catalysts were prepared by thermal decomposition of polymeric precursors and characterized by energy dispersive X-ray, scanning electronic microscopy, X-ray diffraction and cyclic voltammetry. This preparation method allowed obtaining uniform films with controlled stoichiometry and high surface area. Cyclic voltammetry experiments in the presence of methanol showed that mixed electrodes decreased the potential peak of methanol oxidation by approximately 100 mV (RHE) when compared to the electrode containing only Pt. In addition, voltammetric experiments indicated that the Pt(0.6)Ru(0.4)O(y) electrode led to higher oxidation current densities at lower potentials. Chronoamperometry experiments confirmed the contribution of RuO(2) to the catalytic activity as well as the better performance of the Pt(0.6)Ru(0.4)O(y) electrode composition. Formic acid and CO(2) were identified as being the reaction products formed in the electrolysis performed at 400 and 600 mV. The relative formation of CO(2) was favored in the electrolysis performed at 400 mV (RHE) with the Pt(0.6)Ru(0.4)O(y) electrode. The presence of RuO(2) in Pt-Ru-based electrodes is important for improving the catalytic activity towards methanol electrooxidation. Moreover, the thermal decomposition of polymeric precursors seems to be a promising route for the production of catalysts applicable to DMFC. (C) 2009 International Association for Hydrogen Energy. Published by Elsevier Ltd. All rights reserved.

Impedance characteristics of the diamond/carbon fiber electrodes for electrical double-layer capacitor

The electrochemical performance of carbon fibers (CF) and boron-doped diamond electrodes grown on carbon fiber substrate (BDD/CF) was studied. CF substrates were obtained from polyacrylonitrile precursor heat treated at two different temperatures of 1000 and 2000 degrees C to produce the desirable CF carbon graphitization index. This graphitization process influenced the CF conductivity and its chemical surface, also analyzed from X-ray photoelectron spectroscopy measurements. These three-dimensional CF structures allowed a high incorporation of diamond films compared to other carbon substrates such as glass carbon or HOPG. The electrochemical responses, from these four classes of electrodes, were evaluated focusing their application as electrical double-layer capacitors using cyclic voltammetry and impedance measurements. Cyclic voltammetry results revealed that the electrode formed from BDD grown on CF-2000 presented a typical capacitor behavior with the best rectangular shape, compared to those electrodes of CF or BDD/CF-1000. Furthermore, the BDD/CF-2000 electrode presented the lowest impedance, associated to its significant capacitance value of 1940 mu F/cm(2) taking into account the BDD films. This behavior was attributed to the strong dependence between diamond coating texture and the CF graphitization temperature. The largest surface area of BDD/CF-2000 was promoted by its singular film growth mechanism associated to the substrate chemical surface. (c) 2008 Elsevier B.V. All rights reserved.