Intermolecular vibrations and fast relaxations in supercooled ionic liquids

Short-time dynamics of ionic liquids has been investigated by low-frequency Raman spectroscopy (4 < omega < 100 cm(-1)) within the supercooled liquid range. Raman spectra are reported for ionic liquids with the same anion, bis(trifluoromethylsulfonyl)imide, and different cations: 1-butyl-3-methylimidazolium, 1-hexyl-3-methylimidazolium, 1-butyl-1-methylpiperidinium, trimethylbutylammonium, and tributylmethylammonium. It is shown that low-frequency Raman spectroscopy provides similar results as optical Kerr effect (OKE) spectroscopy, which has been used to study intermolecular vibrations in ionic liquids. The comparison of ionic liquids containing aromatic and non-aromatic cations identifies the characteristic feature in Raman spectra usually assigned to librational motion of the imidazolium ring. The strength of the fast relaxations (quasi-elastic scattering, QES) and the intermolecular vibrational contribution (boson peak) of ionic liquids with non-aromatic cations are significantly lower than imidazolium ionic liquids. A correlation length assigned to the boson peak vibrations was estimated from the frequency of the maximum of the boson peak and experimental data of sound velocity. The correlation length related to the boson peak (similar to 19 angstrom) does not change with the length of the alkyl chain in imidazolium cations, in contrast to the position of the first-sharp diffraction peak observed in neutron and X-ray scattering measurements of ionic liquids. The rate of change of the QES intensity in the supercooled liquid range is compared with data of excess entropy, free volume, and mean-squared displacement recently reported for ionic liquids. The temperature dependence of the QES intensity in ionic liquids illustrates relationships between short-time dynamics and long-time structural relaxation that have been proposed for glass-forming liquids. (C) 2011 American Institute of Physics. [doi: 10.1063/1.3604533]

Mechanism and model of the oscillatory electro-oxidation of methanol

A mechanism for the kinetic instabilities observed in the galvanostatic electro-oxidation of methanol is suggested and a model developed. The model is investigated using stoichiometric network analysis as well as concepts from algebraic geometry (polynomial rings and ideal theory) revealing the occurrence of a Hopf and a saddle-node bifurcation. These analytical solutions are confirmed by numerical integration of the system of differential equations. (C) 2010 American Institute of Physics

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.

Toxicity-directed approach of polyester manufacturing industry wastewater provides useful information for conducting treatability studies

A broader characterization of industrial wastewaters, especially in respect to hazardous compounds and their potential toxicity, is often necessary in order to determine the best practical treatment (or pretreatment) technology available to reduce the discharge of harmful pollutants to the environment or publicly owned treatment works. Using a toxicity-directed approach, this paper sets the base for a rational treatability study of polyester resin manufacturing. Relevant physical and chemical characteristics were determined. Respirometry was used for toxicity reduction evaluation after physical and chemical effluent fractionation. Of all the procedures investigated, only air stripping was significantly effective in reducing wastewater toxicity. Air stripping in pH 7 reduced toxicity in 18.2%, while in pH 11 a toxicity reduction of 62.5% was observed. Results indicated that toxicants responsible for the most significant fraction of the effluent`s instantaneous toxic effect to unadapted activated sludge were organic compounds poorly or not volatilized in acid conditions. These results led to useful directions for conducting treatability studies which will be grounded on actual effluent properties rather than empirical or based on the rare specific data on this kind of industrial wastewater. (C) 2008 Elsevier B.V. All rights reserved.

MODELING ELECTRODIALYSIS AND A PHOTOCHEMICAL PROCESS FOR THEIR INTEGRATION IN SALINE WASTEWATER TREATMENT

Oxidation processes can be used to treat industrial wastewater containing non-biodegradable organic compounds. However, the presence of dissolved salts may inhibit or retard the treatment process. In this study, wastewater desalination by electrodialysis (ED) associated with an advanced oxidation process (photo-Fenton) was applied to an aqueous NaCl solution containing phenol. The influence of process variables on the demineralization factor was investigated for ED in pilot scale and a correlation was obtained between the phenol, salt and water fluxes with the driving force. The oxidation process was investigated in a laboratory batch reactor and a model based on artificial neural networks was developed by fitting the experimental data describing the reaction rate as a function of the input variables. With the experimental parameters of both processes, a dynamic model was developed for ED and a continuous model, using a plug flow reactor approach, for the oxidation process. Finally, the hybrid model simulation could validate different scenarios of the integrated system and can be used for process optimization.

Single step process for particles surface modification or thin film composite production

Adsorbent materials and composites are quite useful for sensor development. Therefore, the aim of this work is the surface modification of particulates and/or composite formation. The material was produced by plasma polymerization of HMDS (hexamethyldisilazane) in a single step. SEM analysis shows good surface coverage of particulates with a plasma polymerized film formed by several clusters that might increase adsorption. Particles (starch. 5 5 mu m) recovered with HMDS films show good properties for retention of medium-size Organic molecules, such as dye. Thin films formed by a mixture of particles and plasma polymerized thin film HMDS species were obtained in a single step and can be used for retention of organic compounds, in liquid or gaseous phase. (C) 2009 Elsevier B.V. All rights reserved.

Montmorillonite/carbon nanocomposites prepared from sucrose for catalytic applications

Sucrose was used to prepare montmorillonite/carbon nanocomposites by calcination in a reduced atmosphere. The aim was to investigate the changes derived from varying the clay and sucrose content in the resulting material and to change the adsorption properties to evaluate its potential to be used in catalytic applications. X-ray diffraction patterns revealed the formation of an intercalated nanostructure composed of carbon-filled clay mineral layers, which was confirmed by the Fourier transform infrared spectra and thermogravimetry curves. Differences in composition and texture surface were detected by scanning electron microscopy images and were supported by viscosity measurements. These measurements were helpful in understanding why the sample prepared with the highest sucrose content presented the lowest gasoline and methylene blue adsorption results and why the highest adsorption properties were attributed to the sample with the highest clay content. Moreover, BET and BJH studies allowed understanding oleic acid catalytic conversion. Finally, a water flux simulation test was performed to determine the mechanical resistance in comparison to an activated carbon. It was found that the nanocomposites were more resistant, supporting their use in catalytic applications for a longer period of time. (C) 2011 Elsevier B.V. All rights reserved.

Acidity and Aluminum Speciation as Affected by Surface Liming in Tropical No-Till Soils

Aluminum toxicity is one of the major soil factors limiting root growth in acidic soils. Because of the increase in organic matter content in the upper few centimeters of soils under no-till systems (NTS), most Al in soil solution may be complexed to dissolved organic C (DOC), thus decreasing its bioavailability. The aim of this study was to evaluate the effects of surface liming on Al speciation in soil solution in Brazilian sites under NTS. Field experiments were performed in two regions with contrasting climates and levels of soil acidity: Rondonopolis, Mato Grosso State, on a Rhodic Haplustox, and Ponta Grossa, Parana State, on a Typic Hapludox. The treatments consisted of a control and three lime rates, surface applied to raise the base saturation to 50, 70, and 90%. Soil solution was obtained at soil water equilibrium (1:1 w/w soil/water ratio). The effects of surface liming on soil chemical attributes and on the composition of the soil solution were dependent on weather conditions, time under NTS, and soil weathering. Most Al in soil solution was complexed to DOC, representing about 70 to 80% of the total Al at pH <5.0, and about 30 to 4096 at pH >5.0. Under pH 5.5, the results were closely correlated with the solubility line for amorphous Al. Organic complexes may control Al(3+) release into soil solution at pH <5.5. Results suggest that in areas under NTS for a long period of time, Al toxicity might decrease due to its complexation to high-molecular-weight organic compounds.

Podzolization as a deferralitization process: dynamics and chemistry of ground and surface waters in an Acrisol-Podzol sequence of the upper Amazon Basin

Hydrochemical processes involved in the development of hydromorphic Podzols are a major concern for the upper Amazon Basin because of the extent of the areas affected by such processes and the large amounts of organic carbon and associated metals exported to the rivers. The dynamics and chemical composition of ground and surface waters were studied along an Acrisol-Podzol sequence lying in an open depression of a plateau. Water levels were monitored along the sequence over a period of 2 years by means of piezometers. Water was sampled in zero-tension lysimeters for groundwater and for surface water in the drainage network of the depression. The pH and concentrations of organic carbon and major elements (Si, Fe and Al) were determined. The contrasted changes reported for concentrations of Si, organic carbon and metals (Fe, Al) mainly reflect the dynamics of the groundwater and the weathering conditions that prevail in the soils. Iron is released by the reductive dissolution of Fe oxides, mostly in the Bg horizons of the upslope Acrisols. It moves laterally under the control of hydraulic gradients and migrates through the iron-depleted Podzols where it is exported to the river network. Aluminium is released from the dissolution of Al-bearing minerals (gibbsite and kaolinite) at the margin of the podzolic area but is immobilized as organo-Al complexes in spodic horizons. In downslope positions, the quick recharge of the groundwater and large release of organic compounds lead to acidification and a loss of metals (mainly Al), previously stored in the Podzols.

Characterization of humic substances in salt marsh soils under sea rush (Juncus maritimus)

Humic substances (HS) from salt marsh soils were characterized and the relationships among HS composition and some geochemical factors were analysed. For this, three salt marshes with the same vegetation cover (Juncus maritimus), but with different geochemical characteristics, were selected. The qualitative characterization of the soil humic acids and fulvic acids was carried out by elemental analysis, FTIR spectroscopy, fluorescence spectroscopy and VACP/MAS (13)C NMR spectroscopy. HS from salt marsh soils under sea rush (Juncus maritimus) displayed some shared characteristics such as low degree of humification, low aromatic content and high proportion of labile compounds, mainly polysaccharides and proteins. However, although the three salt marsh soils under study were covered by the same type of vegetation, the HS showed some important differences. HS composition was found to be determined not only by the nature of the original organic material, but also by environmental factors such as soil texture, redox conditions and tidal influence. In general. an increase in the humification process appeared to be related to aerobic conditions and predominance of sand in the mineral fraction of the soil, while the preservation of labile organic compounds may be associated with low redox potential values and fine soil texture. (C) 2008 Elsevier Ltd. All rights reserved.

Electrocatalytic oxidation of ethanol on Sn((1-x))Ir((x))O(2) electrodes in acid medium

The electrochemical oxidation of ethanol at Sn((1-x))Ir (x) O(2) electrodes (with x = 0.01, 0.05, 0.1 and 0.3) was studied in 0.1 mol L(-1) HClO(4) solution. Electrolysis experiments were carried out and the reaction products were analyzed by Liquid Chromatography. It was found that the amounts of the reaction products depended on the composition of the electrode. In situ infrared reflectance spectroscopy measurements were performed to identify the adsorbed intermediates and to postulate a reaction mechanism for ethanol electrooxidation on these electrode materials. As evidence, acetaldehyde and acetic acid were formed through a successive reaction process. Carbon dioxide was also identified as the end product, showing that the cleavage of the carbon-carbon bond occurred. These results indicate that the synthesized catalysts are able to lead to the total combustion of organic compounds. Analysis of the water bending band at different potentials illustrated its role at the electrode interface.

Gas-phase dissociation of 1,4-naphthoquinone derivative anions by electrospray ionization tandem mass spectrometry

Gas-phase dissociation pathways of deprotonated 1,4-naphthoquinone (NQ) derivatives have been investigated by electrospray ionization tandem mass spectrometry (ESI-MS/MS). The major decomposition routes have been elucidated on the basis of quantum chemical calculations at the B3LYP/6-31+G(d,p) level. Deprotonation sites have been indicated by analysis of natural charges and gas-phase acidity. NQ anions underwent an interesting reaction under collision-induced dissociation conditions, which resulted in the radical elimination of the lateral chain, in contrast with the even-electron rule. Possible pathways have been suggested, and their mechanisms have been elucidated on the basis of Gibbs energy and enthalpy values for the anions previously described at each pathway. Copyright (C) 2009 John Wiley & Sons, Ltd.

Synthesis, X-ray analysis and DFT study of 2-amino-3-(N-oxipiridin-4-ilsulfanil)-propionic acid dihydrate

The title compound, C(8)H(14)N(2)O(5)S 2(H(2)O), 2-amino-3-(N-oxipiridin-4-ilsulfanil)-propionic acid dihydrate, is obtained by the reaction of cysteine and 4-nitropyridine N-oxide in dimethylformamide, removing the NO(2) group from the benzene ring and releasing nitrous acid into the solution. The molecule exists as a Zwitterion. Hydrogen bond interactions involving the title molecule and water molecules allow the formation of R(5)(5)(23) edge fused rings parallel to (010). Water molecules are connected independently, forming infinite chains (wires), in square wave form, along the b-axis. The chirality of the cysteine molecule used in the synthesis is retained in the title molecule. A density functional theory (DFT) optimized structure at the B3LYP/6-311G(3df,2p) level allows comparison of calculated and experimental IR spectra.

PM(2.5) and PM(10): The influence of sugarcane burning on potential cancer risk

In Brazil, sugarcane fields are often burned to facilitate manual harvesting, and this burning causes environmental pollution from the large amounts of soot released into the atmosphere. This material contains numerous organic compounds such as PAHs. In this study, the concentrations of PAHs in two particulate-matter fractions (PM(2.5) and PM(10)) in the city of Araraquara (SE Brazil, with around 200,000 inhabitants and surrounded by sugarcane plantations) were determined during the sugarcane harvest (HV) and non-harvest (NHV) seasons in 2008 and 2009. The sampling strategy included four campaigns, with 60 samples in the NHV season and 220 samples in the HV season. The PM(2.5) and PM(10) fractions were collected using a dichotomous sampler (10 L min(-1), 24 h) with Teflon (TM) filters. The filter sets were extracted (ultrasonic bath with hexane/acetone (1:1 v/v)) and analyzed by HPLC/Fluorescence. The median concentration for total PAHs (PM(2.5) in 2009) was 0.99 ng m(-3) (NHV) and 3.3 ng m(-3) (HV). In the HV season, the total concentration of carcinogenic PAHs (benz(a)anthracene, benzo(b)fluoranthene, benzo(k)fluoranthene, and benzo(a)pyrene) was 5 times higher than in the NHV season. B(a)P median concentrations were 0.017 ng m(-3) and 0.12 ng m(-3) for the NHV and HV seasons, respectively. The potential cancer risk associated with exposure through inhalation of these compounds was estimated based on the benzo[a]pyrene toxic equivalence (BaP(eq)), where the overall toxicity of a PAR mixture is defined by the concentration of each compound multiplied by its relative toxic equivalence factor (TEF). BaP(eq) median (2008 and 2009 years) ranged between 0.65 and 1.0 ng m(-3) and 1.2-1.4 ng m(-3) for the NHV and HV seasons, respectively. Considering that the maximum permissible BaPeq in ambient air is 1 ng m(-3), related to the increased carcinogenic risk, our data suggest that the level of human exposure to PAHs in cities surrounded by sugarcane crops where the burning process is used is cause for concern. (C) 2010 Published by Elsevier Ltd.

Composition of Diesel Particles Influences Acute Pulmonary Toxicity: An Experimental Study in MICE

Ambient particles have been consistently associated with adverse health effects, yielding mainly high cardiorespiratory morbidity and mortality. Diesel engines represent a major source of particles in the urban scenario. We aimed to modify the composition of diesel particles, by means of different extraction procedures, to relate changes in chemical profile to corresponding indicators of respiratory toxicity. Male BALB/c mice were nasally instilled with saline, or with diesel particles, treated or not, and assigned to five groups: saline ( SHAM), intact diesel particles (DEP), and diesel particles previously treated with methanol ( METH), hexane ( HEX), or nitric acid (NA). Elemental composition and organic compounds were analyzed. Twenty-four hours after nasal instillation, respiratory parameters were measured and lung tissue was collected for histological analysis. Static elastance was significantly increased in groups DEP and MET in relation to the other groups. HEX and NA were different from DEP but not significantly different from SHAM and METH groups. The difference between dynamic and static elastance was increased in DEP, METH, and NA treatments; HEX was not statistically different from SHAM. DEP and METH groups presented significantly increased upper airways resistance, while DEP, METH, and NA showed higher peripheral airways resistance values. All groups had a higher total resistance than SHAM. DEP, METH, and NA showed significant increased infiltration of polymorphonuclear cells. In conclusion, diesel particles treated with hexane ( HEX) resulted in a respiratory-system profile very similar to that in SHAM group, indicating that hexane treatment attenuates pulmonary inflammation elicited by diesel particles.