Electrocatalysis of hydrogen evolution reaction on Pt electrode surface-modified by S-2 chemisorption

Kinetic studies of hydrogen evolution reaction (HER) at the surface of Pt in alkaline conditions, reported in this paper, show that electrocatalytic activity is enhanced after adsorption of S-2 ions. EIS and steady-state polarization curve data pointed to an undoubted improvement in performance with the Pt-S cathode that was attributed to higher adsorbed hydrogen coverage. Experimental findings suggested an increase in the electronic density of the modified surface sites that may strengthen the interaction between H2O and the adsorption site and, consequently, accelerates the Volmer step. (c) 2006 International Association for Hydrogen Energy. Published by Elsevier Ltd. All rights reserved.

Effect of tillage on fractal indices describing soil surface microrelief of a Brazilian Alfisol

Soil surface roughness is known to influence water infiltration, runoff and erosion. Soil surface roughness changes with management and weather and its mathematical description still remains an important issue. The main objective of this study was to investigate the effect of tillage on the two fractal indices, fractal dimension, D, and crossover length, 1, currently used in characterizing soil surface microrelief. The statistical index random roughness, RR, was also assessed. Field experiments were done on an Alfisol located at Rio Grande do Sul State (Brazil). Two tillage treatments (conventional versus direct drilling) were tested. The soil surface microrelief was assessed by point elevation measurements in 16 plots for each treatment. The sampling scheme was a square grid with 20 x 20 mm between point spacing and the plot size was 280 x 280 mm, so that each data set consisted of 225 individual elevation points. All indices were calculated after trend removal, both by slope correction, i.e., oriented microrelief, and by slope plus tillage marks correction, i.e., random microrelief. The implemented algorithm for estimating D and 1 consisted in evaluating the roughness around the local root mean square deviation (RMS) of the point elevation values. Irrespective of tillage treatment and detrending procedure, fractal behavior extended only over a bounded range of scales, from 40 to 100 mm, due to the experimental setup. In these conditions, assessing fractal indices was not always straightforward. The statistical index RR and the fractal index I were significantly different between tillage treatments for oriented and random surface conditions. D values of random soil surfaces were not affected by tillage treatment, whereas D values of oriented microrelief were significantly lower in the direct drilled plots. Removal of tillage marks trend resulted in a significant increase in D values. Within each tillage treatment, 1 and D were significantly correlated. (c) 2006 Elsevier B.V. All rights reserved.

Solid state reactions in the platinum-mercury system

Thermogravimetry, Differential Scanning Calorimetry and other analytical techniques (Energy Dispersive X-ray Analysis; Scanning Electron Microscopy; Mapping Surface; X-ray Diffraction; Inductively Coupled Plasma Atomic Emission Spectroscopy and Cold Vapor Generation Atomic Absorption Spectroscopy) have been used to study the reaction of mercury with platinum foils. The results suggest that, when heated, the electrodeposited Hg film reacts with Pt to form intermetallic compounds each having a different stability, indicated by at least three mass loss steps. Intermetallic compounds such as PtHg4, PtHg and PtHg2 were characterized by XRD. These intermetallic compounds were the main products formed on the surface of the samples after partial removal of bulk mercury via thermal desorption. The Pt(Hg) solid solution formation caused great surface instability, attributed to the atomic size factor between Hg and Pt, facilitating the acid solution's attack to the surface.

Sources of atmospheric acidity in an agricultural-industrial region of São Paulo State, Brazil

[1] Surface-based measurements of atmospheric formic acid (HCOOH), acetic acid (CH3COOH), sulfur dioxide (SO2), hydrogen chloride (HCl), and nitric acid (HNO3) were made in central São Paulo State, Brazil, between April 1999 and March 2000. Mean concentrations were 9.0 ppb (HCOOH), 1.3 ppb (CH3COOH), 4.9 ppb (SO2), 0.3 ppb (HCl), and 0.5 ppb (HNO3). Concentrations in sugar cane burning plumes were 1160-4230 ppb (HCOOH), 360-1750 ppb (CH3COOH), 10-630 ppb (SO2), 4-210 ppb (HCl), and 14-90 ppb (HNO3). Higher ambient concentrations of SO2, HCl and HNO3 were measured during the burning season (May-November). Concentrations of SO2 and HCl increased during the evening, and of HCOOH and CH3COOH were lowest in the morning, with peak levels in the afternoon. Ratios obtained between different species showed either nighttime maxima (SO2/HCOOH, SO2/CH3COOH, SO2/HNO3, CH3COOH/HNO3, SO2/HCl and HCOOH/HNO3), daytime maxima (HCOOH/HCl, CH3COOH/HCl and HNO3/HCl), or no clear trends (HCOOH/CH3COOH). Correlation analysis showed that SO2 and HCl were primary emissions from biomass burning and road transport; HCOOH, HNO3 and CH3COOH were products of photochemistry; HCOOH and CH3COOH were emitted directly during combustion as well as from biogenic sources. Biomass burning affected atmospheric acidity on a regional scale, while vehicular emissions had greater impact in urban and adjacent areas. Atmospheric ammonia levels were insufficient to neutralize atmospheric acidity, which was mainly removed by deposition to the surface.

ESR STUDY OF CUCL2 ADSORBED ON A CHEMICALLY-MODIFIED SILICA-GEL SURFACE WITH BENZIMIDAZOLE MOLECULE

The ESR spectrum of CuCl2 adsorbed onto a silica gel surface chemically modified with the benzimidazole molecule showed that the surface complex has an octahedral symmetry with tetragonal distortion. The measured ESR parameters were g(parallel to) = 2.287, g(perpendicular to) = 2.062, A(parallel to) = 153 G and superhyperfine splitting A(N) = 15 G. The fit of the theoretical expressions to the experimental data was very reasonable. The effective spin orbit coupling constant for Cu2+ was reduced from its normal free ion value of lambda = -828 cm(-1) by as much as 30%. This reduction of lambda is normal in the solid state and in frozen solution complexes.

Anthropogenic influences on annual flux of cations and anions at meio stream basin, São Paulo State, Brazil

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Ceramic raw materials from the State of Maranhao, Brazil. Part 1: chemical and mineralogical characterization and technological properties of clays from Sao Luis, Rosario, Pinheiro and Mirinzal

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Surface characterization of absorbing polymer films deposited on transparent glasses

PANI films were deposited on glass substrates by in-situ polymerization and characterized by UV-VIS spectroscopy and atomic force microscopy. A method is developed to accurately analyze ellipsometric data obtained for transparent glass substrates before and after modification with absorbing polymer films. Surface modification was made with an overlayer such as polyaniline ( PANI), which exhibits different optical properties by varying its oxidation state. First, the issue of using transparent substrates for ellipsometry studies was examined and then, spectroscopic ellipsometry was used to characterize absorbing overlayers on transparent glasses. The same methodologies of data analysis can be also applied to other absorbing films on transparent substrates, and deposited by different techniques.

Geothermal investigations in an area of induced seismic activity, northern São Paulo State, Brazil

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Hydrochemistry on a waste disposal area of sand mining activities at Analandia, Sao Paulo State, Brazil, and their implications on the mobilization of uranium

Groundwaters and surface waters from an area of treatment of sand for industrial purposes at Analandia municipality, nearly in the center of Sao Paulo State, Brazil, were chemically and isotopically analyzed with two aims: to evaluate if the anthropogenic activities that has taken place for the last 6 years is affecting the quality of the hydrological resources and to relate the hydrogeochemical behaviour of the uranium isotopes 234U and 238U with the pattern of circulation of groundwaters.

Contribution to the study of the solid-state reaction of mercury with pure rhodium

Thermogravimetry (TG) and other analysis techniques (EDX, SEM, Mapping surface, X-ray diffraction, inductively coupled argon plasma emission spectroscopy and atomic spectrometry with cold vapor generation) were used to study the reaction of Hg with Rh. The results permitted the suggestion that, when subjected to heat, an electrodeposited Hg film reacts with Rh to form intermetallic products with different stabilities, as indicated by at least three mass loss steps. In the first step, between room temperature and 160°C, only the bulk Hg is removed. From this temperature up to about 175°C, the mass loss can be attributed to the desorption of a film of metallic Hg. The last step, from 175 to 240°C, can be ascribed to the removal of Hg from a thin dark film of RhHg2.

Pheno and genotyping of Staphylococcus aureus, isolated from bovine milk samples from São Paulo State, Brazil

In the present study, 87 Staphylococcus aureus isolates obtained from milk samples of 87 cows with mastitis in 6 different municipal districts of 2 regions of São Paulo State, Brazil, were compared pheno and genotypically. Pulsed-field gel electrophoresis (PFGE) analysis of the strains was performed, and PCR was carried out to detect genes for a number of staphylococcal cell surface proteins, exoproteins, and 3 classes of agr genes. Nine distinct S. aureus lineages (LA-LI) were identified by PFGE. The lineages LA and LE, which accounted together for 63 strains (72.2%), were prevalent and had been collected from all of the 6 municipal districts, indicating a broad geographic distribution of these lineages; LB, LC, LD, LF, LG, LH, and LI, however, were isolated sporadically and accounted for 24 strains (27.8%). Some characteristics, like penicillin resistance and the presence of cap8 and agr class II genes, were associated with the prevalent lineages (LA and LE), and penicillin susceptibility and the presence of cna and cap5 genes were associated with sporadic lineages. According to the present results, some S. aureus lineages possess a combination of genes that confer the propensity to cause and disseminate infection, and only a limited number of clones are responsible for the cases of bovine mastitis on the various farms. © 2004 NRC Canada.

Some reflections on the future of the water quality of the corumbataí River basin, São Paulo state, Brazil

The waters of Corumbataí River in the middle and eastern part of São Paulo State, Brazil, are extensively used for human consumption; their water quality has been modified mainly due to increasing pressure caused by population growth, accompanied by a more accentuated industrial development for the whole São Paulo State in the early 1970s. The Corumbataí River basin has, over time, received significant emissions of municipal waste products and discharges of wastewater, sludge, sewage, sanitary and industrial effluents, but the first effluent treatment plant at Rio Claro city was only inaugurated at the end of the 1990s. Data on river water quality from two widely spaced locations in the Corumbataí River basin are reported in this paper; they indicate the need for continuous initiatives and efforts by decision makers in order to improve and preserve the water quality in the basin for the 21st century. Copyright © 2007 IAHS Press.

Evaluation of titanium implants with surface modification by laser beam. Biomechanical study in rabbit tibias

The purpose of the present study was to evaluate, using a biomechanical test, the force needed to remove implants with surface modification by laser (Nd:YAG) in comparison with implants with machined surfaces. Twenty-four rabbits received one implant with each surface treatment in the tibia, machined surface (MS) and laser-modified surface (LMS). After 4, 8 and 12 weeks of healing, the removal torque was measured by a torque gauge. The surfaces studied were analyzed according to their topography, chemical composition and roughness. The average removal torque in each period was 23.28, 24.0 and 33.85 Ncm for MS, and 33.0, 39.87 and 54.57 Ncm for LMS, respectively. The difference between the surfaces in all periods of evaluation was statistically significant (p < 0.05). Surface characterization showed that a deep and regular topography was provided by the laser conditioning, with a great quantity of oxygen ions when compared to the MS. The surface micro-topography analysis showed a statistical difference (p < 0.01) between the roughness of the LMS (R a = 1.38 ± 0.23 μm) when compared to that of the MS (R a = 0.33 ± 0.06 μm). Based on these results, it was possible to conclude that the LMS implants' physical-chemical properties increased bone-implant interaction when compared to the MS implants. © 2009 Sociedade Brasileira de Pesquisa Odontológica.

Groundwater quality on a waste disposal area due to sand mining activities in São Paulo state, Brazil

This investigation reports the results of a study realized in an area related to the development of sand mining activities, which belongs to Sibelco Mineração Ltd. The site is located around Analândia municipality, nearly in the center of São Paulo State, Brazil. Hydrochemical analyses of groundwater were realized under different periods of time, with the aim of evaluating the possibility of release of several constituents to the liquid phase, which may be a source of pollution of the surface hydrological resources and of the deeper Guarani aquifer. This is because the site is located at the recharge area of Guarani aquifer and some tributaries from Corumbataí river may also be suffering contamination, implying on the impoverishment of the water quality that are very important resources in the region, as they are extensively used for drinking purposes, among others.© 2011 WIT Press.