Fully electrochemical hyphenated flow system for preconcentration, cleanup, stripping, capillary electrophoresis with stacking and contactless conductivity detection of trace heavy metals

Successful coupling of electrochemical preconcentration (EPC) to capillary electrophoresis (CE) with contactless conductivity detection (C(4)D) is reported for the first time. The EPC-CE interface comprises a dual glassy carbon electrode (GCE) block, a spacer and an upper block with flow inlet and outlet, pseudo-reference electrode and a fitting for the CE silica column, consisting of an orifice perpendicular to the surface of a glassy carbon electrode with a bushing inside to ensure a tight press fit. The end of the capillary in contact with the GCE is slant polished, thus defining a reproducible distance from the electrode surface to the column bore. First results with EPC-CE-C(4)D are very promising, as revealed by enrichment factors of two orders of magnitude for Tl, Cu, Pb and Cd ion peak area signals. Detection limits for 10 min deposition time fall around 20 nmol L(-1) with linear calibration curves over a wide range. Besides preconcentration, easy matrix exchange between accumulation and stripping/injection favors procedures like sample cleanup and optimization of pH, ionic strength and complexing power. This was demonstrated for highly saline samples by using a low conductivity buffer for stripping/injection to improve separation and promote field-enhanced sample stacking during electromigration along the capillary. (C) 2010 Elsevier B.V. All rights reserved.

A renewable copper electrode as an amperometric flow detector for nitrate determination in mineral water and soft drink samples

A novel approach was developed for nitrate analysis in a FIA configuration with amperometric detection (E=-0.48 V). Sensitive and reproducible current measurements were achieved by using a copper electrode activated with a controlled potential protocol. The response of the FIA amperometric method was linear over the range from 0.1 to 2.5 mmol L(-1) nitrate with a detection limit of 4.2 mu mol L(-1) (S/N = 3). The repeatability of measurements was determined as 4.7% (n=9) at the best conditions (flow rate: 3.0 mL min(-1), sample volume: 150 mu L and nitrate concentration: 0.5 mmol L(-1)) with a sampling rate of 60 samples h(-1). The method was employed for the determination of nitrate in mineral water and soft drink samples and the results were in agreement with those obtained by using a recommended procedure. Studies towards a selective monitoring of nitrite were also performed in samples containing nitrate by carrying out measurements at a less negative potential (-0.20 V). (C) 2009 Elsevier B.V. All rights reserved.

Sequential injection analysis (SIA) and response surface methodology: A versatile small volume approach for optimization of photo-Fenton processes

Optimization of photo-Fenton degradation of copper phthalocyanine blue was achieved by response surface methodology (RSM) constructed with the aid of a sequential injection analysis (SIA) system coupled to a homemade photo-reactor. Highest degradation percentage was obtained at the following conditions [H(2)O(2)]/[phthalocyanine] = 7, [H(2)O(2)]/[FeSO(4)] = 10, pH = 2.5, and stopped flow time in the photo reactor = 30 s. The SIA system was designed to prepare a monosegment containing the reagents and sample, to pump it toward the photo-reactor for the specified time and send the products to a flow-through spectrophotometer for monitoring the color reduction of the dye. Changes in parameters such as reagent molar ratios. residence time and pH were made by modifications in the software commanding the SI system, without the need for physical reconfiguration of reagents around the selection valve. The proposed procedure and system fed the statistical program with degradation data for fast construction of response surface plots. After optimization, 97% of the dye was degraded. (C) 2009 Elsevier B.V. All rights reserved.

Applying sequential injection analysis (SIA) and response surface methodology for optimization of Fenton-based processes

This work presents the use of sequential injection analysis (SIA) and the response surface methodology as a tool for optimization of Fenton-based processes. Alizarin red S dye (C.I. 58005) was used as a model compound for the anthraquinones family. whose pigments have a large use in coatings industry. The following factors were considered: [H(2)O(2)]:[Alizarin] and [H(2)O(2)]:[FeSO(4)] ratios and pH. The SIA system was designed to add reagents to the reactor and to perform on-line sampling of the reaction medium, sending the samples to a flow-through spectrophotometer for monitoring the color reduction of the dye. The proposed system fed the statistical program with degradation data for fast construction of response surface plots. After optimization, 99.7% of the dye was degraded and the TOC content was reduced to 35% of the original value. Low reagents consumption and high sampling throughput were the remarkable features of the SIA system. (C) 2008 Published by Elsevier B.V.

Development of a spectrophotometric Sequential Injection Analysis (SIA) procedure for determination of ammonium: A Response Surface Methodology (RSM) approach

This paper describes the optimization and use of a Sequential Injection Analysis (SIA) procedure for ammonium determination in waters. Response Surface Methodology (RSM) was used as a tool for optimization of a procedure based on the modified Berthelot reaction. The SIA system was designed to (i) prepare the reaction media by injecting an air-segmented zone containing the reagents in a mixing chamber, (ii) to aspirate the mixture back to the holding coil after homogenization, (iii) drive it to a thermostated reaction coil, where the flow is stopped for a previously established time, and (iv) to pump the mixture toward the detector flow cell for the spectrophotometric measurements. Using a 100 mu mol L(-1) ammonium solution, the following factors were considered for optimization: reaction temperature (25 - 45 degrees C), reaction time (30 - 90 s), hypochlorite concentration (20 - 40 mmol L(-1)) nitroprusside concentration (10 - 40 mmol L(-1)) and salicylate concentration (0.1 - 0.3 mol L(-1)). The proposed system fed the statistical program with absorbance data for fast construction of response surface plots. After optimization of the method, figures of merit were evaluated, as well as the ammonium concentration in some water samples. No evidence of statistical difference was observed in the results obtained by the proposed method in comparison to those obtained by a reference method based on the phenol reaction. (C) 2010 Elsevier B.V. All rights reserved.

Temperature (over) compensation in an oscillatory surface reaction

Biological rhythms are regulated by homeostatic mechanisms that assure that physiological clocks function reliably independent of temperature changes in the environment. Temperature compensation, the independence of the oscillatory period on temperature, is known to play a central role in many biological rhythms, but it is rather rare in chemical oscillators. We study the influence of temperature on the oscillatory dynamics during the catalytic oxidation of formic acid on a polycrystalline platinum electrode. The experiments are performed at five temperatures from 5 to 25 degrees C, and the oscillations are studied under galvanostatic control. Under oscillatory conditions, only non-Arrhenius behavior is observed. Overcompensation with temperature coefficient (q(10), defined as the ratio between the rate constants at temperature T + 10 degrees C and at T) < I is found in most cases, except that temperature compensation with q(10) approximate to I predominates at high applied currents. The behavior of the period and the amplitude result from a complex interplay between temperature and applied current or, equivalently, the distance from thermodynamic equilibrium. High, positive apparent activation energies were obtained under voltammetric, nonoscillatory conditions, which implies that the non-Arrhenius behavior observed under oscillatory conditions results from the interplay among reaction steps rather than, from a weak temperature dependence of the individual steps.

A surface-enhanced infrared absorption spectroscopic (SEIRAS) study of the oscillatory electro-oxidation of methanol on platinum

The oscillatory electro-oxidation of methanol was studied by means of in situ infrared (IR) spectroscopy in the attenuated total reflection (ATR) configuration using a platinum film on a Si prism as working electrode. The surface-enhanced infrared absorption (SEIRA) effect considerably improves the spectroscopic resolution, allowing at following the coverage of some adsorbing species during the galvanostatic oscillations. Carbon monoxide was the main adsorbed specie observed in the induction period and within the oscillatory regime. The system was investigated at two distinct time-scales and its dynamics characterized accordingly. During the induction period the main transformation observed as the system move through the phase space towards the oscillatory region was the decrease of the coverage of adsorbed carbon, coupled to the increase of the electrode potential. Similar transition characterizes the evolution within the oscillatory region, but at a considerably slower rate. Experiments with higher time resolution revealed that the electrode potential oscillates in-phase with the frequency of the linearly adsorbed CO vibration and that the amount of adsorbed CO oscillates with small amplitude. Adsorbed formate was found to play, if any, a very small role. Results are discussed and compared with other systems. (C) 2010 Elsevier B.V. All rights reserved.

Hydrodynamic Simulations Of Vacuum-Driven Storage Tanks

As a result of urbanization, stormwater runoff flow rates and volumes are significantly increased due to increasing impervious land cover and the decreased availability of depression storage. Storage tanks are the basic devices to efficiently control the flow rate in drainage systems during wet weather. Presented in the paper conception of vacuum-driven detention tanks allows to increase the storage capacity by usage of space above the free surface water elevation at the inlet channel. Partial vacuum storage makes possible to gain cost savings by reduction of both the horizontal area of the detention tank and necessary depth of foundations. Simulation model of vacuum-driven storage tank has been developed to estimate potential profits of its application in urban drainage system. Although SWMM5 has no direct options for vacuum tanks an existing functions (i.e. control rules) have been used to reflect its operation phases. Rainfall data used in simulations were recorded at raingage in Czestochowa during years 2010÷2012 with time interval of 10minutes. Simulation results gives overview to practical operation and maintenance cost (energy demand) of vacuum driven storage tanks depending of the ratio: vacuum-driven volume to total storage capacity. The following conclusion can be drawn from this investigations: vacuum-driven storage tanks are characterized by uncomplicated construction and control systems, thus can be applied in newly developed as well as in the existing urban drainage systems. the application of vacuum in underground detention facilities makes possible to increase of the storage capacity of existing reservoirs by usage the space above the maximum depth. Possible increase of storage capacity can achieve even a few dozen percent at relatively low investment costs. vacuum driven storage tanks can be included in existing simulation software (i.e. SWMM) using options intended for pumping stations (including control and action rules ).

Cash flow and discount rate risk decomposition and ICAPM for the US and brazilian stock markets

Esse trabalho é uma aplicação do modelo intertemporal de apreçamento de ativos desenvolvido por Campbell (1993) e Campbell e Vuolteenaho (2004) para as carteiras de Fama-French 2x3 brasileiras no period de janeiro de 2003 a abril de 2012 e para as carteiras de Fama-French 5x5 americanas em diferentes períodos. As varíaveis sugeridas por Campbell e Vuolteenaho (2004) para prever os excessos de retorno do mercado acionário americano no period de 1929 a 2001 mostraram-se também bons preditores de excesso de retorno para o mercado brasileiro no período recente, com exceção da inclinação da estrutura a termo das taxas de juros. Entretanto, mostramos que um aumento no small stock value spread indica maior excesso de retorno no futuro, comportamento que não é coerente com a explicação para o prêmio de valor sugerida pelo modelo intertemporal. Ainda, utilizando os resíduos do VAR preditivo para definir o risco de choques de fluxo de caixa e de choques nas taxas de desconto das carteiras de teste, verificamos que o modelo intertemporal resultante não explica adequadamente os retornos observados. Para o mercado norte-americano, concluímos que a abilidade das variáveis propostas para explicar os excessos de retorno do mercado varia no tempo. O sucesso de Campbell e Vuolteenaho (2004) em explicar o prêmio de valor para o mercado norte-americano na amostra de 1963 a 2001 é resultado da especificação do VAR na amostra completa, pois mostramos que nenhuma das varíaveis é um preditor de retorno estatisticamente significante nessa sub-amostra.

O papel das transferências intergovernamentais na equalização fiscal dos municípios brasileiros

Com a descentralização que caracterizou a federação brasileira nas últimas décadas, os municípios receberam maiores atribuições e responsabilidades, implementando políticas públicas e provendo serviços básicos à população. Contudo, uma vez que as receitas próprias municipais são capazes de custear apenas parcialmente estas atividades, torna-se necessário um volume elevado de transferências que fluem dos níveis centrais aos municípios. Além do mais, o Brasil é um país de território vasto e heterogêneo, em que municípios com distintas capacidades de autofinanciamento, bem como diferentes demandas por serviços públicos, convivem no mesmo regime federativo. Diante deste quadro, torna-se fundamental estudar a distribuição dos recursos das transferências, verificando se os municípios que mais necessitam de suporte financeiro têm sido os efetivamente beneficiados. À este processo de reduzir as disparidades horizontais provenientes de diferenças nas bases tributárias e demandas locais dá-se o nome de equalização fiscal. A equalização fiscal permite que municípes de diferentes jurisdições recebam o mesmo nível de serviços públicos para dada carga tributária assumida por eles (net fiscal benefit), ou seja, a equalização promove a equidade na provisão dos serviços públicos, além de evitar a criação de ineficiência alocativa derivada de migrações motivadas por benefícios fiscais. Para criar a equalização fiscal as transferências devem beneficiar aqueles municípios com menor capacidade de autofinanciamento e maiores necessidades fiscais atreladas à custos e demandas pelos serviços públicos. Neste sentido, este trabalho busca avaliar o efeito das transferências intergovernamentais na equalização fiscal dos municípios, considerando as principais proxies de capacidade fiscal – potencial de geração de receita própria – e necessidade fiscal – volume de recursos demandados em virtude das características da região e da população do município. A análise é realizada para cada grupo de transferências, desde aquelas com finalidade essencialmente redistributiva como o FPM até aquelas predominantemente devolutivas, como a cota-parte de ICMS. Os resultados mostram que algumas transferências como o FPM contribuem pouco para a equalização fiscal, apesar do objetivo de natureza redistributiva implícito neste repasse, assim como algumas transferências condicionais, como o FUNDEB, apesar de não almejarem especificamente corrigir as disparidades horizontais na capacidade dos municípios realizarem suas funções, podem significar um efeito positivo para a equalização fiscal no nível municipal da federação. Outro resultado importante que desponta na análise é o efeito da transferência do Bolsa-família na equalização, pois esta transferência consegue atenuar as distorções realizadas pelas demais transferências distribuídas aos municípios. O Bolsa-família, apesar de não ser uma transferência intergovernamental, foi incorporada na análise por representar um expressivo volume de recursos, por concorrer com recursos de outras transferências e ainda ter efeito potencial semelhante ao das demais transferências intergovernamentais no âmbito da equalização fiscal, uma vez que libera recursos no orçamento do governo local que, do contrário, poderiam estar comprometidos com a política local de assistência social. Outro resultado é a observação de que as transferências voluntárias afetam menos a equalização, ou seja, não contribuem para a consecução deste objetivo nem prejudicam a redução das disparidades horizontais, sendo relativamente neutras ou menos intervenientes em relação às demandas e capacidade de arrecadação dos municípios, provavelmente por não seguirem critérios, nem econômicos, como o ICMS, nem redistributivos, como o FPM, e sim critérios políticos, como apontado pela literatura de ciência política.

Geração de sulcos em meio coesivo e caracterização hidrossedimentométrica de sua evolução

Na pesquisa em erosão, nas últimas décadas, está se formando um consenso de que é importante entender os processos básicos que regem o fenômeno. Uma alternativas para tentar compreender melhor as etapas do processo erosivo é separá-lo na fase de sulco (fluxo concentrado) e de entressulco. Dentro desse enfoque foi construído no Laboratório de Processos Erosivos e Deposicionais (LaPED) do IPH/UFRGS um canal de declividade para estudar o processo de incisão e o desenvolvimento dos sulcos de erosão. A estrutura experimental projetada e construída permite que seja controlada a vazão através de um medidor eletromagnético e que seja alterada a declividade do canal através de um sistema hidráulico associado a um nível digital. O solo colocado no canal foi um Latossolo Vermelho distrófico típico, as declividades de trabalho foram 3,0; 6,0 e 9,0% e a seqüência de vazões aplicadas foi 10,0; 18,5; 25,5; 38,5 e 51,0L.min-1. A estrutura experimental montada se mostrou de fácil operação e eficiente para permitir o avanço no entendimento dos processos de desagregação e de transporte de partículas sólidas pela ação do escoamento superficial, além de possibilitar a geração de sulco(s) de erosão na superfície do solo. O escoamento passou da condição de difuso para concentrado a partir do momento em que a velocidade superficial do fluxo alcançou 0,26m.s-1, a altura de lâmina atingiu 0,0102m, a velocidade de cisalhamento superou os 0,059m.s-1, a tensão de cisalhamento chegou a 3,50Pa e que a potência do escoamento atingiu pelo menos 0,22N.s-1. O processo de incisão iniciou-se com o canal experimental colocado em baixa declividade e em regime de escoamento sub-crítico e de transição. A velocidade de cisalhamento, no momento da incisão, foi, praticamente, o dobro daquela encontrada na literatura para solos siltosos e arenosos. Entretanto, para as três declividades a fase de sulco definido ocorreu somente em regime de escoamento turbulento. A tensão de cisalhamento foi o parâmetro que melhor descreveu a evolução da perda de solo. A potência do escoamento foi o parâmetro hidráulico que mostrou maior eficiência para separar as fases evolutivas dos sulcos. O desenvolvimento do(s) sulco(s) teve o seu início em uma condição de escoamento difuso (ausência de sulcos) e com a potência do escoamento oscilando entre 0,057 e 0,198N.s-1. O avanço do(s) sulco(s) começou com uma zona de transição (fase de incisão e de aprofundamento) onde a potência do escoamento varia entre 0,220 e 0,278N.s-1 e, logo em seguida, teve início a fase de sulco definido, com a potência do escoamento entre 0,314 e 0,544N.s-1. Na fase de escoamento concentrado foi preponderante o papel do processo de erosão regressiva para aumentar tanto o tamanho como o peso das partículas sólidas em transporte pelo escoamento superficial e assim fazer com que predominasse o transporte via fundo sobre o transporte via suspensão. As cargas de sedimento geradas nos solos de diferentes classes texturais foram separadas em grupos distintos em função da potência unitária do escoamento.

Aproveitamento de subprodutos da industrialização do escargot

The waste in the industries of escargot processing is very big. This is composed basically of escargot meat out of the commercialization patterns and the visceras. In this context, there is a need to take advantage to the use of these sub-products. A possibility should be drying them and transforming them in a certain form to be reused. Than, the present work has the objective of studying the reutilization of the sub-products of the escargot industrialization for by means of drying process. The samples were transformed in pastes, through a domestic processor for approximately 1 minute and compacted in trays of aluminum without perforations with three different heights (5 mm, 10 mm and 15 mm). The drying was accomplished in a tray dryer with air circulation and transverse flow at a speed of 0,2 m/s and three temperature levels (70°C, 80°C and 90ºC). A drying kinetics study was accomplished for the obtained curves and for the heat and mass transfer coefficients using experimental procedures based in an experimental planning of 22 factorial type. Microbiological and physiochemical analysis were also accomplished for the in nature and the dehydrated sub-products. In the drying process, it was observed the great importance of the external resistances to the mass transfer and heat in the period of constant tax influenced by the temperature. The evaporation taxes indicated a mixed control of the mass transfer for the case of the thickest layers. As already expected, the drying constant behavior was influenced by the temperature and thickness of the medium, increasing and decreasing. The statistical analysis of the results, in agreement with the factorial planning 22, showed that the fissures, the shrinking of the transfer area and the formation of a crust on the surface might have contributed to the differences between the practical results and the linear model proposed. The temperature and the thickness influenced significantly in the answers of the studied variables: evaporation tax and drying constant. They were obtained significant statistical models and predictive ones for evaporation tax for the meat as well as for the visceras

Estimativas das componentes da radiação solar incidente em superfícies inclinadas baseadas na radiação global horizontal

Statistics equations and validations with groups of annual and monthly data were evaluated for global, direct and diffuse solar radiation components incident on the tilted surface to 12.85, 22.85 and 32.85 degrees with the face North, in climate and geographical conditions of Botucatu, SP. It was employed the fractions of three components of extraterrestrial radiation in correlation with the coefficient clearness index horizontal plane, in a database of April/1998 to December/2007, whose measures at different periods in three inclinations, however concomitant to the horizontal plane. Increasing the angle of the surface led to increased scattering of the daily values of clearness index for inclined and horizontal surfaces. In annual groups, the lower performances were observed in the estimation of inclined daily diffuse radiation, with maximum Root Mean Square Error to 3.89 MJ m(-2) d(-1) (43.65%) and adjustments around 62%. In estimates of global and direct components of solar radiation on inclined planes, both annual and monthly equations can be applied, with performance dependents to climatic conditions.

Electrochemical evaluation of the a carbon-paste electrode modified with spinel manganese(IV) oxide under flow conditions for amperometric determination of lithium

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

Numerical solution of the eXtended Pom-Pom model for viscoelastic free surface flows

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