Developing a fluorimetric sequential injection methodology to study adsorption/desorption of glyphosate on soil and sediment samples

This paper describes the development of a sequential injection method to automate the fluorimetric determination of glyphosate based on a first step of oxidation to glycine by hypochlorite at 48 degrees C, followed by reaction with the fluorogenic reagent o-phthaldialdehyde in presence of 2-mercaptoethanol in borate buffer (pH > 9) to produce a fluorescent 1-(2`-hydroxyethylthio)-2-N-alkylisoindole. The proposed method has a linear response for glyphosate concentrations between 0.25 and 25.0 mu mol L(-1), with limits of detection and quantification of 0.08 and 0.25 mu mol L(-1), respectively. The sampling rate of the method is 18 samples per hour, consuming only a fraction of reagents consumed by the chromatographic method based on the same chemistry. The method was applied to study adsorption/desorption properties in a soil and in a sediment sample. Adsorption and desorption isotherms were properly fitted by Freundlich and Langmuir equations, leading to adsorption capacities of 1384 +/- 26 and 295 +/- 30 mg kg(-1) for the soil and sediment samples, respectively. These values are consistent with the literature, with the larger adsorption capacity of the soil being explained by its larger content of clay minerals, while the sediment was predominantly sandy. (C) 2011 Elsevier B.V. All rights reserved.

Sensing of 2,4-dichlorophenoxyacetic acid by surface-enhanced Raman scattering

Surface-enhanced Raman scattering (SERS) spectra of the herbicide 2,4-dichlorophenoxyacetic acid (2,4-D) was obtained by employing a bi-layer gold substrate, assembled by the reduction of Au(III) over gold-seeded nanoparticles immobilized on functionalized glass substrates. The SERS signal was linear with the logarithm of the solution concentrations between 1.0 x 10(-7) mol L(-1) and 1.0 x 10(-3) mol L(-1), indicating that the bi-layer gold substrate affords a significant dynamic range for SERS, providing an excellent analytical response within this concentration range, and revealing the high sensitivity of the gold surface towards such analyte. In addition, using the same gold substrate, a similar calibration curve was obtained for crystal-violet (CV), and it was possible to identify the concentration limit corresponding to the transition from the average SERS to the nonlinear SERS response. (C) 2010 Elsevier B.V. All rights reserved.

Development of an Analytical Methodology for Quantification of Strong Acid in Diesel Oil

Many factors can affect the quality of diesel oil, in particular the degradation processes that are directly related to some organosulfur compounds. During the degradation process, these compounds are oxidized into their corresponding sulfonic acids, generating a strong acid content during the process. p-Toluene sulfonic acid analysis was performed using the linear sweep voltammetry technique with a platinum ultramicroelectrode in aqueous solution containing 3 mol L(-1) potassium chloride. An extraction step was introduced prior to the voltammetric detection in order to avoid the adsorption of organic molecules, which inhibit the electrochemical response. The extraction step promoted the transference of sulfonic acid from the diesel oil to an aqueous phase. The method was accurate and reproducible, with detection and quantification limits of 5 ppm and 15 ppm, respectively. Recovery of sulfonic acid was around 90%.

Nanogravimetric study of the complex voltammetric response in the electro-oxidation of methanol on platinum

Instead of a time-invariant voltammetric profile, many electrochemical systems display a cycle-dependent current-potential response. This phenomenon has been referred to as complex voltammetric response and it has been observed during the electro-oxidation of several molecules such as methanol, ethanol, propanol and hydrogen. There are currently two explanations for the surface mechanism underlying this behavior. In one scenario, the complex voltammogram would result from the specific kinetic pathway taken during the forward sweep. In the other explanation, the phenomenon is discussed in terms of the interplay among the surface roughening and subsequent relaxation, and the ohmic drop coupled to a negative differential resistance. We report in this paper a nanogravimetric investigation of the complex voltammetric response in the electro-oxidation of methanol on platinum electrode in both acidic and alkaline media. Different periodic patterns composed of intercalated small and large hysteresis cycles were observed as a function of the applied voltage and the series resistance between the working electrode and the potentiostat. Independently, nanogravimetric results indicated no detectable difference in the delta-frequency versus voltage profile between small and large hysteresis cycles. These findings were interpreted as experimental evidence of the secondary, if any, role played by the very electrochemical reaction on the emergence of complex voltammetric response. (C) 2009 Elsevier Ltd. All rights reserved.

Respostas dinâmicas em sistemas distribuídos e decomposição forçada da superfície livre para um modelo acoplado Oceano-Atmosfera

O objetivo deste trabalho é a introdução e desenvolvimento de uma metodologia analítico-simbólica para a obtenção de respostas dinâmicas e forçadas (soluções homogêneas e não homogêneas) de sistemas distribuídos, em domínios ilimitados e limitados, através do uso da base dinâmica gerada a partir da resposta impulso. Em domínios limitados, a resposta impulso foi formulada pelo método espectral. Foram considerados sistemas com condições de contorno homogêneas e não homogêneas. Para sistemas de natureza estável, a resposta forçada é decomposta na soma de uma resposta particular e de uma resposta livre induzida pelos valores iniciais da resposta particular. As respostas particulares, para entradas oscilatórias no tempo, foram calculadas com o uso da fun»c~ao de Green espacial. A teoria é desenvolvida de maneira geral permitindo que diferentes sis- temas evolutivos de ordem arbitrária possam ser tratados sistematicamente de uma forma compacta e simples. Realizou-se simulações simbólicas para a obtenção de respostas dinâmicas e respostas for»cadas com equações do tipo parabólico e hiperbólico em 1D,2D e 3D. O cálculo das respostas forçadas foi realizado com a determinação das respostas livres transientes em termos dos valores iniciais das respostas permanentes. Foi simulada a decomposição da resposta forçada da superfície livre de um modelo acoplado oceano-atmosfera bidimensional, através da resolução de uma equação de Klein-Gordon 2D com termo não-homogêneo de natureza dinâmica, devido a tensão de cisalhamento na superfície do oceano pela ação do vento.

Processamento e análise de imagens na caracterização da superfície do titânio submetido a um ensaio de cultura de células

This work aims to develop a methodology for analysis of images using overlapping, which assists in identification of microstructural features in areas of titanium, which may be associated with its biological response. That way, surfaces of titanium heat treated for 08 (eight) different ways have been subjected to a test culture of cells. It was a relationship between the grain, texture and shape of grains of surface of titanium (attacked) trying to relate to the process of proliferation and adhesion. We used an open source software for cell counting adhered to the surface of titanium. The juxtaposition of images before and after cell culture was obtained with the aid of micro-hardness of impressions made on the surface of samples. From this image where there is overlap, it is possible to study a possible relationship between cell growth with microstructural characteristics of the surface of titanium. This methodology was efficient to describe a set of procedures that are useful in the analysis of surfaces of titanium subjected to a culture of cells

Estudo de adsorvente obtido de terras diatomáceas para remoção de metais pesados em águas produzidas: processamento, caracterização e dinâmica em leito fixo

The acceleration of industrial growth in recent decades on all continents aroused the interest of the companies to counter the impacts produced on the environment, spurred primarily by major disasters in the petroleum industry. In this context, the water produced is responsible for the largest volume of effluent from the production and extraction of oil and natural gas. This effluent has in its composition some critical components such as inorganic salts, heavy metals (Fe, Cu, Zn, Pb, Cd, ), presence of oil and chemicals added in the various production processes. In response to impact, have been triggered by research alternative adsorbent materials for water treatment and water produced, in order to removing oils and acids and heavy metals. Many surveys of diatomaceous earth (diatomite) in Brazil involve studies on the physico-chemical, mineral deposits, extraction, processing and applications. The official estimated Jazi are around 2.5 million tonnes, the main located in the states of Bahia (44%) and Rio Grande do Norte (37,4%). Moreover, these two states appear as large offshore producers, earning a prominent role in research of adsorbents such as diatomite for treatment of water produced. Its main applications are as an agent of filtration, adsorption of oils and greases, industrial load and thermal insulator. The objective of this work was the processing and characterization of diatomite diatomaceous earth obtained from the municipality of Macaíba-RN (known locally as tabatinga) as a low cost regenerative adsorbent for removal of heavy metals in the application of water produced treatment. In this work we adopted a methodology for batch processing, practiced by small businesses located in producing regions of Brazil. The characterization was made by X-ray diffraction (XRD), scanning electron microscopy (SEM) and specific surface area (BET). Research conducted showed that the improvement process used was effective for small volume production of diatomite concentrated. The diatomite obtained was treated by calcination at temperature of 900 oC for 2 hours, with and without fluxing Na2CO3 (4%), according to optimal results in the literature. Column adsorption experiments were conducted to percolation of the in nature, calcined and calcined fluxing diatomites. Effluent was used as a saline solution containing ions of Cu, Zn, Na, Ca and Mg simulating the composition of produced waters in the state of Rio Grande do Norte, Brazil. The breakthrough curves for simultaneous removal of copper ions and zinc as a result, 84.3% for calcined diatomite and diatomite with 97.3 % for fluxing. The calcined fluxing diatomite was more efficient permeability through the bed and removal of copper and zinc ions. The fresh diatomite had trouble with the permeability through the bed under the conditions tested, compared with the other obtained diatomite. The results are presented as promising for application in the petroleum industry

Benthic response to upwelling events off the SE Brazilian coast

The main aim of the present study was to evaluate and compare temporal responses of the benthos in 2 continental shelf areas (Cabo Frio and Ubatuba) off the SE Brazilian coast. In Cabo Frio (23 degrees S, 42 degrees W), the western boundary coastal upwelling of the South Atlantic Central Water (SACW) enhances primary productivity, potentially increasing food supply to the benthic communities via sinking of particulate organic carbon (POC). In contrast, POC fluxes in Ubatuba (23 degrees S, 45 degrees W) are expected to be comparatively lower because SACW remains subsurface. We analyzed the temporal and spatial input of phytodetritus (concentration of chlorophyll a in sediments) and the benthic microbial biomass (estimated by ATP-based carbon content in sediments). Median surface chlorophyll concentration was computed for all daily available SeaWiFS images (from 2001 and 2002) to follow chlorophyll a inputs. All parameters used to investigate benthic responses in the study areas showed consistently higher values in Cabo Frio than in Ubatuba. The results showed that benthic response to upwelling may last months, fueling the microbial communities in the Cabo Frio region.

Response of minimally processed carambola to chemical treatments and low-oxygen atmospheres

Fresh-cut carambola (Averrhoa carambola L.) has limited marketability due to cut-surface browning. The effect of chemical treatments (ascorbic acid, citric acid and Ca-EDTA), controlled atmosphere (0.4-20.3% O-2) and the association of these processes was investigated. Post-cutting dip and low-oxygen atmospheres did not prevent discoloration or improve sensory and physicochemical parameters. However, ascorbic acid (0.5% and 1%) dips reduced polyphenol oxidase (PPO) activity during storage at 4.5 degrees C, with 1% ascorbic acid inducing the lowest activity. Although cut-surface browning of 'Maha' slices was not relevant, carambola slices treated with 1% ascorbic acid in association with 0.4% oxygen did not present significant browning or loss of visual quality for up to 12 days, 3 days longer than low oxygen alone (0.4% O-2), thus, their quality can be significantly improved by combining both treatments. (c) 2007 Elsevier B.V. All rights reserved.

Análise e projeto de superfícies seletivas de frequência com elementos pré-fractais para aplicações em comunicações indoor

In this thesis, a frequency selective surface (FSS) consists of a two-dimensional periodic structure mounted on a dielectric substrate, which is capable of selecting signals in one or more frequency bands of interest. In search of better performance, more compact dimensions, low cost manufacturing, among other characteristics, these periodic structures have been continually optimized over time. Due to its spectral characteristics, which are similar to band-stop or band-pass filters, the FSSs have been studied and used in several applications for more than four decades. The design of an FSS with a periodic structure composed by pre-fractal elements facilitates the tuning of these spatial filters and the adjustment of its electromagnetic parameters, enabling a compact design which generally has a stable frequency response and superior performance relative to its euclidean counterpart. The unique properties of geometric fractals have shown to be useful, mainly in the production of antennas and frequency selective surfaces, enabling innovative solutions and commercial applications in microwave range. In recent applications, the FSSs modify the indoor propagation environments (emerging concept called wireless building ). In this context, the use of pre-fractal elements has also shown promising results, allowing a more effective filtering of more than one frequency band with a single-layer structure. This thesis approaches the design of FSSs using pre-fractal elements based on Vicsek, Peano and teragons geometries, which act as band-stop spatial filters. The transmission properties of the periodic surfaces are analyzed to design compact and efficient devices with stable frequency responses, applicable to microwave frequency range and suitable for use in indoor communications. The results are discussed in terms of the electromagnetic effect resulting from the variation of parameters such as: fractal iteration number (or fractal level), scale factor, fractal dimension and periodicity of FSS, according the pre-fractal element applied on the surface. The analysis of the fractal dimension s influence on the resonant properties of a FSS is a new contribution in relation to researches about microwave devices that use fractal geometry. Due to its own characteristics and the geometric shape of the Peano pre-fractal elements, the reconfiguration possibility of these structures is also investigated and discussed. This thesis also approaches, the construction of efficient selective filters with new configurations of teragons pre-fractal patches, proposed to control the WLAN coverage in indoor environments by rejecting the signals in the bands of 2.4~2.5 GHz (IEEE 802.11 b) and 5.0~6.0 GHz (IEEE 802.11a). The FSSs are initially analyzed through simulations performed by commercial software s: Ansoft DesignerTM and HFSSTM. The fractal design methodology is validated by experimental characterization of the built prototypes, using alternatively, different measurement setups, with commercial horn antennas and microstrip monopoles fabricated for low cost measurements

Radiation balance at the surface in the city of So Paulo, Brazil: diurnal and seasonal variations

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Response of wheat to foliar application of zinc

Wheat is grown in Brazil, mostly in no-till, a system in which the zinc can become potentially deficient, due to excessive application of acidity corrective and phosphate fertilizers in surface and, or at shallow depths. This study aimed to evaluate the effect of foliar application of zinc in agronomic characteristics and yield of wheat. The experimental design was randomized blocks with five replications. Treatments consisted of four doses of zinc (0, 54, 108 and 216g ha(-1) Zn), divided into two foliar applications, the first at tillering (18 days after plant emergence) and the second at the boot stage (65 days after emergence). Foliar application of zinc increased the number of fertile tillers and yield of wheat, however, have little effect on the agronomic characteristics of no-tilled crop with high nutrient content in soil.

Análise topológica experimental por perfilometria cíclica indutiva de superficies de paredes estruturais

To enhance the maintenance practices, Oil and Gas Pipelines are inspected from the inside by automated systems called PIG (Pipeline Inspection Gauge). The inspection and mapping of defects, as dents and holes, in the internal wall of these pipelines are increasingly put into service toward an overall Structural Integrity Policy. The residual life of these structures must be determined such that minimize its probability of failure. For this reason, the investigation on the detection limits of some basic topological features constituted by peaks or valleys disposed along a smooth surface is of great value for determining the sensitivity of the measurements of defects from some combinations of circumferential, axial and radial extent. In this investigation, it was analyzed an inductive profilometric sensor to scan three races, radius r1, r2, r3, in a circular surface of low carbon steel, equipped with eight consecutive defects simulated by bulges and holes by orbit, equally spaced at p/4 rad. A test rig and a methodology for testing in laboratory were developed to evaluate the sensor response and identify their dead zones and jumps due to fluctuations as a function of topological features and scanning velocity, four speeds different. The results are presented, analyzed and suggestions are made toward a new conception of sensor topologies, more sensible to detect these type of damage morphologies

Interaction of small amounts of bovine serum albumin with phospholipid monolayers investigated by surface pressure and atomic force microscopy

The influence of small amounts of bovine serum albumin (BSA) (nM concentration) on the lateral organization of phospholipid monolayers at the air-water interface and transferred onto solid substrates as one-layer Langmuir-Blodgett (LB) films was investigated. The kinetics of adsorption of BSA onto the phospholipid monolayers was monitored with surface pressure isotherms in a Langmuir trough, for the zwitterionic dipalmitoylphosphatidyl ethanolamine (N,N-dimethyl-PE) and the anionic dimyristoylphosphatidic acid (DMPA). A monolayer of N,N-dimethyl-PE or DMPA incorporating BSA was transferred onto a solid substrate using the Langmuir-Blodgett technique. Atomic force microscopy (AFM) images of one-layer LB films displayed protein-phospholipid domains, whose morphology was characterized using dynamic scaling theories to calculate roughness exponents. For DMPA-BSA films the surface is characteristic of self-affine fractals, which may be described with the Kardar-Parisi-Zhang (KPZ) equation. on the other hand, for N,N-dimethyl-PE-BSA films, the results indicate a relatively flat surface within the globule. The height profile and the number and size of globules varied with the type of phospholipid. The overall results, from kinetics of adsorption on Langmuir monolayers and surface morphology in LB films, could be interpreted in terms of the higher affinity of BSA to the anionic DMPA than to the zwitterionic N,N-dimethyl-PE. Furthermore, the effects from such small amounts of BSA in the monolayer point to a cooperative response of DMPA and N,N-dimethyl-PE monolayers to the protein. (c) 2005 Elsevier B.V. All rights reserved.

Spray layer-by-layer films based on phospholipid vesicles aiming sensing application via e-tongue system

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