Evaluation of a carbon paste electrode modified with organofunctionalised SBA-15 nanostructured silica in the simultaneous determination of divalent lead, copper and mercury ions

The performance of a carbon paste electrode (CPE) modified with SBA-15 nanostructured silica organofunctionalised with 2-benzothiazolethiol in the simultaneous determination of Pb(II), Cu(II) and Hg(II) ions in natural water and sugar cane spirit (cachaca) is described. Pb(II), Cu(II) and Hg(II) were pre-concentrated on the surface of the modified electrode by complexing with 2-benzothiazolethiol and reduced at a negative potential (-0.80 V). Then the reduced products were oxidised by DPASV procedure. The fact that three stripping peaks appeared on the voltammograms at the potentials of -0.48 V (Pb2+), -0.03 V (Cu2+) and +0.36 V (Hg2+) in relation to the SCE, demonstrates the possibility of simultaneous determination of Pb2+, Cu2+ and Hg2+. The best results were obtained under the following optimised conditions: 100 mV pulse amplitude, 3 min accumulation time, 25 mV s(-1) scan rate in phosphate solution pH 3.0. Using such parameters, calibration graphs were linear in the concentration ranges of 3.00-70.0 x 10(-7) mol L-1 (Pb2+), 8.00-100.0 X 10(-7) mol L-1 (Cu2+) and 2.00-10.0 x 10(-6) mol L-1 (Hg2+). Detection limits of 4.0 x 10(-8) mol L-1 (Pb2+), 2.0 x 10(-7) mol L-1 (Cu2+) and 4.0 x 10(-7) mol L-1 (Hg2+) were obtained at the signal noise ratio (SNR) of 3. The results indicate that this electrode is sensitive and effective for simultaneous determination of Pb2+, Cu2+ and Hg2+ in the analysed samples. (C) 2008 Published by Elsevier B.V.

Ex Situ Scanning Electrochemical Microscopy (SECM) Investigation of Bismuth- and Bismuth/Lead Alloy Film-Modified Gold Electrodes in Alkaline Medium

Scanning electrochemical microscopy (SECM) in feedback mode was employed to characterise the reactivity and microscopic peculiarities of bismuth and bismuth/lead alloys plated onto gold disk substrates in 0.1 molL(-1) NaOH solutions. Methyl viologen was used as redox mediator, while a platinum microelectrode was employed as the SECM tip. The metal films were electrodeposited ex situ from NaOH solutions containing either bismuth ions only or both bismuth and lead ions. Approach curves and SECM images indicated that the metal films were conductive and locally reactive with oxygen to provide Bi(3+) and Pb(2+) ions. The occurrence of the latter chemical reactions was verified by local anodic stripping voltammetry (ASV) at the substrate solution interface by using a mercury-coated platinum SECM tip. The latter types of measurements allowed also verifying that lead was not uniformly distributed onto the bismuth film electrode substrate. These findings were confirmed by scanning electron microscopy images. The surface heterogeneity produced during the metal deposition process, however, did not affect the analytical performance of the bismuth coated gold electrode in anodic stripping voltammetry for the determination of lead in alkaline media, even in aerated aqueous solutions. Under the latter conditions, stripping peak currents proportional to lead concentration with a satisfactory reproducibility (within 5% RSD) were obtained.

Surface Properties of Calcinated Titanium Dioxide Probed by Solvatochromic Indicators: Relevance to Catalytic Applications

Titanium dioxide was obtained by hydrolysis of the corresponding ethoxide, followed by washing, drying, and calcination at 80, 160, 240, 320, 400, and 700 C, respectively. The following surface properties of the solids obtained were determined as a function of the calcinations temperature: T(Calcn); area by the BET method; BrOnsted acidity by titration with sodium hydroxide; empirical polarity, ET(30); Lewis acidity, alpha(Surf); Lewis basicity, beta(Surf); and dipolarity/polarizability pi*(Sturf), by use of solvatochromic indicators. Except for le surf whose value increased slightly, heating the samples resulted in a decrease of all of the above-mentioned surface properties, due to the decrease of surface hydroxyl groups. This conclusion has been corroborated by FTIR. Values of E(T)(30), alpha(Surf), and pi*(Surf) are higher than those of water and alcohols; the BrOnsted and Lewis acidities of the samples correlate linearly. The advantages of using solvatochromic indicators to probe the surface properties and relevance of the results to the applications of TiO(2) are discussed.

Electrodeposition and characterization of thin selenium films modified with lead ad-atoms

The deposition and characterization of Se films doped with Pb underpotentially deposited (UPD) ad-atoms was studied in this work. The employed experimental techniques were cyclic voltammetry, chronoamperometry, electrochemical impedance spectroscopy, UV-vis spectroscopy and atomic force microscopy. The initial deposition of Se film by chronoamperometry yielded a thin film composed of approximately 700 layers. The Pb UPD on Se was achieved by chronoamperometry in a potential value previously determined in voltammetric experiments. This deposition yielded a deposition charge of approximately 7.5% of the total one. The film resistance altered from 320 Omega cm(2) for Se to 65 Omega cm(2) for the Se/Pb one. Flat band potential values and number of acceptors and donors were also calculated for both films and the values obtained were + 0.95 and -0.51 V for Se and Se/Pb, respectively. The Se coating presented 1.2 x 10(17) cm(3) acceptors while the Se/Pb one presented 3.2 x 10(17) cm(3) donors. The band gap values for both films were 2.4 eV and 1.9 eV, correspondingly. (C) 2008 Elsevier B.V. All rights reserved.

Hydrogen peroxide and supercritical carbon dioxide: a new bleaching stage for Eucalyptus kraft-O(2) pulps

Kraft pulp is currently bleached largely by the elemental chlorine free (ECF) technology with oxygen, chlorine dioxide, and hydrogen as active agents. This technology brought about significant environmental improvements in relation to standard processes based on chlorine gas and hypochlorite, but there is still need for further improvements. This study presents a novel environmentally friendly bleaching stage - the so-called `hydrogen peroxide in supercritical carbon dioxide`, P((SC-CO2)) - that can be adapted to current ECF bleaching processes, with preference in cases where hydrogen peroxide is already used. In this study, the P((SC-CO2)) stage was evaluated as a replacement to the last peroxide stage of the D(EP)DP bleaching sequence and to the first peroxide stage of the D(EP)DP sequence, for an oxygen delignified eucalypt kraft-O(2) pulp. The P((SC-CO2)) stage was run with 0.5% hydrogen peroxide, at 15% consistency, 70 degrees C, and 73 bar. The reaction time was 30 min. The performances of regular P stages and the new P((SC-CO2)) stage were compared. Promising results were observed with the DEP((SC-CO2))DP sequence; the P((SC-CO2)) decreased kappa number from 2.7 to 2.1, and the hexenuronic acid groups from 17.0 to 12.4 mmol kg(-1). The P((SC-CO2)) stage showed poor performance when applied in the D(EP)DP((SC-CO2)) sequence. It is concluded that the process presents potential but requires further optimization to improve selectivity and efficiency.

Carbon dioxide reforming of ethanol over Ni/Y(2)O(3)-ZrO(2) catalysts

Supported nickel catalysts of composition Ni/Y(2)O(3)-ZrO(2) were synthesized in one step by the polymerization method and compared with a nickel catalyst prepared by wet impregnation. Stronger interactions were observed in the formed catalysts between NiO species and the oxygen vacancies of the Y(2)O(3)-ZrO(2) in the catalysts made by polymerization, and these were attributed to less agglomeration of the NiO during the synthesis of the catalysts in one step. The dry reforming of ethanol was catalyzed with a maximum CO(2) conversion of 61% on the 5NiYZ catalyst at 800 degrees C, representing a better response than for the catalyst of the same composition prepared by wet impregnation. (C) 2009 Published by Elsevier B.V.

Lead Wiping Class

Students are pictured with a professor around a workbench during a lead wiping class at the New York Trade School. Photograph is black and white.

Lead Wiping Students at Work

A lead wiping class at the New York Trade School is shown. Many students can be seen around workbenches. Black and white photograph that is damaged by scratches and is yellowing.

Avaliação da genotoxicidade induzida por emissões de veículos automotores - Ctenomys minutus como organismo bioindicador

Existe um número crescente de componentes químicos lançados ao meio ambiente, muitos dos quais são capazes de induzir efeitos danosos adversos à saúde de animais e humanos, representando uma causa importante de preocupação por seus possíveis efeitos a longo prazo. O impacto ecológico e os riscos a saúde dos organismos associados com a exposição a poluentes ambientais são extremamente difíceis de se avaliar devido a muitos desses componentes serem parte de misturas complexas. Os gases produzidos pelos motores dos veículos à combustão contém diversos poluentes sabidamente genotóxicos, como óxidos de nitrogênio (NOX), monóxido de carbono (CO), óxidos de enxofre (SOx), hidrocarbonetos (HC) e seus derivados, bem como particulados, e metais (cádmio, cromo, cobre, níquel, vanádio, zinco e chumbo). Todos esses compostos isolados ou associados a outros elementos são tóxicos ou de efeito danoso aos organismos, de forma não totalmente esclarecida. Este estudo teve como objetivo verificar o possível efeito genotóxico das emissões dos automóveis em roedor nativo Ctenomys minutus cronicamente exposto, através do Ensaio Cometa (EC), comparando os resultados com o Teste de Micronúcleos (MN), ambos em sangue periférico. Levando em consideração alguns fatores que pudessem influenciar os resultados dos testes de genotoxicidade, este trabalho ainda teve como objetivos: identificar a presença de alguns agentes envolvidos na poluição gerada pelos veículos; verificar possíveis diferenças sazonais, como temperatura e ventos; e se existe influência da idade e sexo dos roedores. Os C. minutus (Octodontidae-Rodentia), foram capturados em dois campos diferentes, ambos ao lado da estrada RS/030, na cidade de Osório, Estado do Rio Grande do Sul (RS): (a) Amaral, e (b) Weber. Animais para controle externo foram capturados no Campo Maribo à cerca de 3 km de distância de outra estrada (RS/389-Osório/RS), conseqüentemente afastada das emissões dos veículos. No final do período desse estudo, foram capturados 123 animais (73 fêmeas e 50 machos).

A comment on "Rational learning lead to nash equilibrium" by professors Ehud Kalai and Ehud Lehrer

Kalai and Lebrer (93a, b) have recently show that for the case of infinitely repeated games, a coordination assumption on beliefs and optimal strategies ensures convergence to Nash equilibrium. In this paper, we show that for the case of repeated games with long (but finite) horizon, their condition does not imply approximate Nash equilibrium play. Recently Kalai and Lehrer (93a, b) proved that a coordination assumption on beliefs and optimal strategies, ensures that pIayers of an infinitely repeated game eventually pIay 'E-close" to an E-Nash equilibrium. Their coordination assumption requires that if players believes that certain set of outcomes have positive probability then it must be the case that this set of outcomes have, in fact, positive probability. This coordination assumption is called absolute continuity. For the case of finitely repeated games, the absolute continuity assumption is a quite innocuous assumption that just ensures that pIayers' can revise their priors by Bayes' Law. However, for the case of infinitely repeated games, the absolute continuity assumption is a stronger requirement because it also refers to events that can never be observed in finite time.

Luxury brands and online consumer-generated content: dealing with the new lead of customers in brand perception

User-generated content – conteúdo gerado por usuários – cresceu consideravelmente na Internet nos cinco últimos anos, levando a grandes mudanças nas práticas de marketing. A força do e-word-of mouth, está aumentando e tem uma influência muito forte na percepção da marca pelos consumidores (Allsop, Basset & Hoskins, 2007). Todos os novos instrumentos fornecidos pela Internet permitiram a criação de comunidades de marca online, impactando o compromisso e a lealdade dos consumidores para com a marca (De Valk, Van Bruggen, Wierenga 2009). Todas essas interações criadas entre os consumidores e a marca são relativamente novas e incomuns para as empresas que devem adaptar suas práticas de marketing a essas mudanças. Dadas as especificidades que aplicam as marcas de luxo nas suas políticas de marketing (Kapferer and Bastien, 2009), a questão da adaptação das suas estratégias ao fenômeno de user-generated content é particularmente complicada. As marcas de luxo costumam ter habitualmente uma relação muito reservada com os seus consumidores, baseada em princípios de exclusividade e raridade (Kapferer, 1997). Esta dissertação busca proporcionar algumas pistas de entendimento sobre como as marcas de cosméticos de luxo podem adaptar suas estratégias de marketing em relação à expansão do conteúdo gerado por usuários na Internet. Esta pesquisa qualitativa sugere meios de controlar o conteúdo gerado por usuários, como o incentivar positivamente com certas práticas de marketing e como tirar proveito dele. A seguinte análise mostra que o conteúdo gerado por usuários tem duas facetas: pode atuar como um mídia digital para as empresas de luxo e como uma fonte de informação, inspiração e criação para o desenho dos novos produtos. Sendo um meio de comunicação, as empresas de cosméticos de luxo podem contar com a nova potência do “e-word-of-mouth” a fim de promover sua imagem de marca e seus produtos através do conteúdo gerado por usuários. Sendo uma fonte de inspiração, o conteúdo gerado por usuários pode conduzir a ótimos processos de co-criação e cooperação entre as marcas de cosméticos de luxo e seus consumidores com o objetivo de projetar produtos perfeitamente ajustados ao pedido dos consumidores.

Comparison and analysis of corporate social responsibility (CSR) reports of the top five companies ranked on the 2013 CSR RepTrak

In the 1970s, Corporate Social Responsibility (CSR) was discussed by Nobel laureate Milton Friedman in his article “The Social Responsibility of Business Is to Increase Its Profits.” (Friedman, 1970). His view on CSR was contemptuous as he referred to it as “hypocritical window-dressing” a reflection of the view of Corporate America on CSR back then. For a long time short-term maximization of shareholder value was the only maxim for top management across industries and companies. Over the last decade, CSR has become a more important and relevant factor of a company’s reputation, shifting the discussion from whether CSR is necessary to how best CSR commitments should be done (Smith, 2003). Inevitably, companies do have an environmental, social and economic impact, thereby imposing social costs on current and future generations. In 2013, 50 of the world biggest companies have been responsible for 73 percent of the total carbon dioxide (CO2) emission (Global 500 Climate Change Report 2013). Post et al. (2002) refer to these social costs as a company’s need to retain its “license to operate”. In the late 1990s, CSR reporting was nearly unknown, which drastically changed during the last decade. Allen White, co-founder of the Global Reporting Initiative (GRI), said that CSR reporting”… has evolved from the extraordinary to the exceptional to the expected” (Confino, 2013). In confirmation of this, virtually all of the world’s largest 250 companies report on CSR (93%) and reporting by now appears to be business standard (KPMG, 2013). CSR reports are a medium for transparency which may lead to an improved company reputation (Noked, 2013; Thorne et al, 2008; Wilburn and Wilburn, 2013). In addition, it may be used as part of an ongoing shareholder relations campaign, which may prevent shareholders from submitting Environmental and Social (E&S)1 proposals (Noked, 2013), based on an Ernst & Young report 1 The top five E&S proposal topic areas in 2013 were: 1. Political spending/ lobbying; 2. Environmental sustainability; 3. Corporate diversity/ EEO; 4.Labor/ human rights and 5. Animal testing/ animal welfare. Three groups of environmental sustainability proposal topics of sub-category number two (environmental sustainability) 6 2013, representing the largest category of shareholder proposals submitted. PricewaterhouseCoopers (PwC) even goes as far as to claim that CSR reports are “…becoming critical to a company’s credibility, transparency and endurance.” (PwC, 2013).