Evaluation of a carbon paste electrode modified with organofunctionalised SBA-15 silica in the determination of copper

The performance of a carbon paste electrode (CPE) modified with SBA-15 nanostructured silica organofunctionalised with 2-benzothiazolethiol for determination of Cu(II) ions in sugar cane spirit (cachaça) is described, based on differential pulse anodic stripping voltammetry (DPASV) procedure. The Cu(II) oxidation peak was observed at 0.03 V (vs. SCE) in phosphate solution (pH 3.0). The results were obtained using optimised conditions such as 100 mV pulse amplitude, 3 min accumulation time, 25 mV s-1 scan rate in phosphate solution pH 3.0, resulting in a linear dynamic range from 8.0 x 10-7 to 1.0 x 10-5 mol L-1 Cu(II) and a limit of detection 2.0 x10-7 mol L-1. Cu(II) spiked in a cachaça sample was determined with 102.5 % mean recovery at mmol L-1 level. Interference from other metallic cations present in the sample was avoided by the standard addition procedure.

Temperature trends at the Mauna Loa observatory, Hawaii

Observations at the Mauna Loa Observatory, Hawaii, established the systematic increase of anthropogenic CO2 in the atmosphere. For the same reasons that this site provides excellent globally averaged CO2 data, it may provide temperature data with global significance. Here, we examine hourly temperature records, averaged annually for 1977–2006, to determine linear trends as a function of time of day. For night-time data (22:00 to 06:00 LST (local standard time)) there is a near-uniform warming of 0.040 °C yr−1. During the day, the linear trend shows a slight cooling of −0.014 °C yr−1 at 12:00 LST (noon). Overall, at Mauna Loa Observatory, there is a mean warming trend of 0.021 °C yr−1. The dominance of night-time warming results in a relatively large annual decrease in the diurnal temperature range (DTR) of −0.050 °C yr−1 over the period 1977–2006. These trends are consistent with the observed increases in the concentrations of CO2 and its role as a greenhouse gas (demonstrated here by first-order radiative forcing calculations), and indicate the possible relevance of the Mauna Loa temperature measurements to global warming.

Can reanalyses represent extreme precipitation over England and Wales?

A new generation of reanalysis products is currently being produced that provides global gridded atmospheric data spanning more than a century. Such data may be useful for characterising the observed long-term variability of extreme precipitation events, particularly in regions where spatial coverage of surface observations is limited, and in the pre-satellite era. An analysis of extreme precipitation events is performed over England and Wales, investigating the ability of Twentieth Century Reanalysis and ERA-Interim to represent extreme precipitation accumulations as recorded in the England and Wales Precipitation dataset on accumulation time-scales from 1 to 7 days. Significant correlations are found between daily precipitation accumulation observations and both reanalysis products. A hit-rate analysis indicates that the reanalyses have hit rates (as defined by an event above the 98th percentile) of approximately 40–65% for extreme events in both summer (JJA) and winter (DJF). This suggests that both ERA-Interim and Twentieth Century Reanalysis are difficult to use for representing individual extreme precipitation events over England and Wales.

Satellite Rainfall Estimates Over South America - Possible Applicability to the Water Management of Large Watersheds1

This work analyzes high-resolution precipitation data from satellite-derived rainfall estimates over South America, especially over the Amazon Basin. The goal is to examine whether satellite-derived precipitation estimates can be used in hydrology and in the management of larger watersheds of South America. High spatial-temporal resolution precipitation estimates obtained with the CMORPH method serve this purpose while providing an additional hydrometeorological perspective on the convective regime over South America and its predictability. CMORPH rainfall estimates at 8-km spatial resolution for 2003 and 2004 were compared with available rain gauge measurements at daily, monthly, and yearly accumulation time scales. The results show the correlation between satellite-derived and gauge-measured precipitation increases with accumulation period from daily to monthly, especially during the rainy season. Time-longitude diagrams of CMORPH hourly rainfall show the genesis, strength, longevity, and phase speed of convective systems. Hourly rainfall analyses indicate that convection over the Amazon region is often more organized than previously thought, thus inferring that basin scale predictions of rainfall for hydrological and water management purposes have the potential to become more skillful. Flow estimates based on CMORPH and the rain gauge network are compared to long-term observed average flow. The results suggest this satellite-based rainfall estimation technique has considerable utility. Other statistics for monthly accumulations also suggest CMORPH can be an important source of rainfall information at smaller spatial scales where in situ observations are lacking.

PARALLEL ALGORITHMS FOR MAXIMAL CLIQUES IN CIRCLE GRAPHS AND UNRESTRICTED DEPTH SEARCH

We present parallel algorithms on the BSP/CGM model, with p processors, to count and generate all the maximal cliques of a circle graph with n vertices and m edges. To count the number of all the maximal cliques, without actually generating them, our algorithm requires O(log p) communication rounds with O(nm/p) local computation time. We also present an algorithm to generate the first maximal clique in O(log p) communication rounds with O(nm/p) local computation, and to generate each one of the subsequent maximal cliques this algorithm requires O(log p) communication rounds with O(m/p) local computation. The maximal cliques generation algorithm is based on generating all maximal paths in a directed acyclic graph, and we present an algorithm for this problem that uses O(log p) communication rounds with O(m/p) local computation for each maximal path. We also show that the presented algorithms can be extended to the CREW PRAM model.

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.

Automated two-dimensional separation flow system with electrochemical preconcentration, stripping, capillary electrophoresis and contactless conductivity detection for trace metal ion analysis

This paper describes the automation of a fully electrochemical system for preconcentration, cleanup, separation and detection, comprising the hyphenation of a thin layer electrochemical flow cell with CE coupled with contactless conductivity detection (CE-C(4)D). Traces of heavy metal ions were extracted from the pulsed-flowing sample and accumulated on a glassy carbon working electrode by electroreduction for some minutes. Anodic stripping of the accumulated metals was synchronized with hydrodynamic injection into the capillary. The effect of the angle of the slant polished tip of the CE capillary and its orientation against the working electrode in the electrochemical preconcentration (EPC) flow cell and of the accumulation time were studied, aiming at maximum CE-C(4)D signal enhancement. After 6 min of EPC, enhancement factors close to 50 times were obtained for thallium, lead, cadmium and copper ions, and about 16 for zinc ions. Limits of detection below 25 nmol/L were estimated for all target analytes but zinc. A second separation dimension was added to the CE separation capabilities by staircase scanning of the potentiostatic deposition and/or stripping potentials of metal ions, as implemented with the EPC-CE-C(4)D flow system. A matrix exchange between the deposition and stripping steps, highly valuable for sample cleanup, can be straightforwardly programmed with the multi-pumping flow management system. The automated simultaneous determination of the traces of five accumulable heavy metals together with four non-accumulated alkaline and alkaline earth metals in a single run was demonstrated, to highlight the potentiality of the system.

Volunteered Geographic Information For Water Management: A Prototype Architecture

Driven by Web 2.0 technology and the almost ubiquitous presence of mobile devices, Volunteered Geographic Information (VGI) is knowing an unprecedented growth. These notable technological advancements have opened fruitful perspectives also in the field of water management and protection, raising the demand for a reconsideration of policies which also takes into account the emerging trend of VGI. This research investigates the opportunity of leveraging such technology to involve citizens equipped with common mobile devices (e.g. tablets and smartphones) in a campaign of report of water-related phenomena. The work is carried out in collaboration with ADBPO - Autorità di bacino del fiume Po (Po river basin Authority), i.e. the entity responsible for the environmental planning and protection of the basin of river Po. This is the longest Italian river, spreading over eight among the twenty Italian Regions and characterized by complex environmental issues. To enrich ADBPO official database with user-generated contents, a FOSS (Free and Open Source Software) architecture was designed which allows not only user field-data collection, but also data Web publication through standard protocols. Open Data Kit suite allows users to collect georeferenced multimedia information using mobile devices equipped with location sensors (e.g. the GPS). Users can report a number of environmental emergencies, problems or simple points of interest related to the Po river basin, taking pictures of them and providing other contextual information. Field-registered data is sent to a server and stored into a PostgreSQL database with PostGIS spatial extension. GeoServer provides then data dissemination on the Web, while specific OpenLayers-based viewers were built to optimize data access on both desktop computers and mobile devices. Besides proving the suitability of FOSS in the frame of VGI, the system represents a successful prototype for the exploitation of user local, real-time information aimed at managing and protecting water resources.

Ensaios sobre a estrutura a termo da taxa de juros

Esta tese é composta de três artigos que analisam a estrutura a termo das taxas de juros usando diferentes bases de dados e modelos. O capítulo 1 propõe um modelo paramétrico de taxas de juros que permite a segmentação e choques locais na estrutura a termo. Adotando dados do tesouro americano, duas versões desse modelo segmentado são implementadas. Baseado em uma sequência de 142 experimentos de previsão, os modelos propostos são comparados à benchmarks e concluí-se que eles performam melhor nos resultados das previsões fora da amostra, especialmente para as maturidades curtas e para o horizonte de previsão de 12 meses. O capítulo 2 acrescenta restrições de não arbitragem ao estimar um modelo polinomial gaussiano dinâmico de estrutura a termo para o mercado de taxas de juros brasileiro. Esse artigo propõe uma importante aproximação para a série temporal dos fatores de risco da estrutura a termo, que permite a extração do prêmio de risco das taxas de juros sem a necessidade de otimização de um modelo dinâmico completo. Essa metodologia tem a vantagem de ser facilmente implementada e obtém uma boa aproximação para o prêmio de risco da estrutura a termo, que pode ser usada em diferentes aplicações. O capítulo 3 modela a dinâmica conjunta das taxas nominais e reais usando um modelo afim de não arbitagem com variáveis macroeconômicas para a estrutura a termo, afim de decompor a diferença entre as taxas nominais e reais em prêmio de risco de inflação e expectativa de inflação no mercado americano. Uma versão sem variáveis macroeconômicas e uma versão com essas variáveis são implementadas e os prêmios de risco de inflação obtidos são pequenos e estáveis no período analisado, porém possuem diferenças na comparação dos dois modelos analisados.

Voltammetric determination of total iron in fuel ethanol using a 1,10 fenantroline/nafion carbon paste-modified electrode

This work presents a methodology for iron determination in fuel ethanol using a modified carbon paste electrode with 1.10 fenantroline/nafion. The electrochemical parameters were optimized for the proposed system and the voltammetric technique of square wave was employed for iron determination. An accumulation time of 5 minutes, such as a 100 mV of pulse magnitude (E(sw)) and frequency (f) of 25 Hz were used as optimized experimental conditions. The modified carbon paste electrode presented linear dependence of amperometric signal with iron concentration in a work range from 6.0x10(-6) until 2.0x10(-5) mol L(-1) of iron, exhibiting a linear correlation coefficient of 0.9884, a detection limit of 2.4 x10(-6) mol L(-1) (n = 3) and amperometric sensibility of 4.5x10(5) mu A/mol L(-1). Analytical curve method was used for iron determination at a commercial fuel sample. Flame atomic absorption spectroscopy was employed as comparative technique.

Scintigraphic validation of AC Biosusceptometry to study the gastric motor activity and the intragastric distribution of food in humans

Abnormal intragastric distribution of food (IDF) and a phasic contractility in the proximal stomach have been related to dyspeptic symptoms. Thus, the behaviour of the stomach and the proximal region, in particular, continues to attract attention and demand for reliable and comfortable techniques. The aims of this study were to employ AC Biosus-ceptometry (ACB) and scintigraphy to evaluate IDF and gastric motor activity in humans. Fifteen healthy volunteers ingested 60 mL of yogurt containing 2 mCi of Tc-99m and 4 g of ferrite. Each volunteer had gastric motility and IDF evaluated twice on separate days; on one occasion by ACB and another by scintigraphy. Digital signal processing was performed in MatLab (Mathworks Inc., Natick, MA, USA). Results were expressed as mean +/- SD. Similar results of distal accumulation time (P < 0.001) were obtained for scintigraphy (6.93 +/- 3.25 min) and for ACB (7.04 +/- 3.65 min). Fast Fourier Transform revealed two dominant frequencies (P > 0.9). Besides the well-know frequency of 3 cpm, our results showed identical frequencies in proximal stomach recordings (P < 0.001) for scintigraphic (1.01 +/- 0.01 cpm) and ACB (0.98 +/- 0.06 cpm). In summary, our data showed that scintigraphy and ACB are promising techniques to evaluate several aspects of gastric motility. Moreover, ACB is non-invasive, radiation-free and deserves the same importance as conventional methods for this kind of analysis.

Lower bounds on blow up solutions of the three-dimensional Navier-Stokes equations in homogeneous Sobolev spaces

Suppose that u(t) is a solution of the three-dimensional Navier-Stokes equations, either on the whole space or with periodic boundary conditions, that has a singularity at time T. In this paper we show that the norm of u(T - t) in the homogeneous Sobolev space (H)over dot(s) must be bounded below by c(s)t(-(2s-1)/4) for 1/2 < s < 5/2 (s not equal 3/2), where c(s) is an absolute constant depending only on s; and by c(s)parallel to u(0)parallel to((5-2s)/5)(L2)t(-2s/5) for s > 5/2. (The result for 1/2 < s < 3/2 follows from well-known lower bounds on blowup in Lp spaces.) We show in particular that the local existence time in (H)over dot(s)(R-3) depends only on the (H)over dot(s)-norm for 1/2 < s < 5/2, s not equal 3/2. (C) 2012 American Institute of Physics. [http://dx.doi.org/10.1063/1.4762841]

Eletroanálise de corantes alimentícios: determinação de índigo carmim e tartrazina

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

Determination of brilliant blue FCF in the presence and absence of erythrosine and quinoline yellow food colours by cathodic stripping voltammetry

A study of the voltammetric behaviour of the food colours brilliant blue FCF (C.I. 42090), erythrosine (C. I. 45430) and quinolin e yellow (C. I. 47005) in the pH range 2-10 have been carried out by cathodic stripping voltammetry. At pH 4.5 (acetate buffer) with an accumulation potential of 0 V and accumulation time of 30 s, the voltammograms presented well-defined reduction peaks at potential - 0.76 V for brilliant blue FCF, - 0.85 V for quinoline yellow and - 0.54 V for erythrosine. Linear calibration graphs were obtained from 8 to 80 mug l(-1) brilliant blue, from 4 to 43 mug l(-1) quinoline yellow and from 10 to 70 mug l(-1) erythrosine. The method has been successfully applied to identify and quantify binary mixtures of these dyes and applied for determining brilliant blue FCF in commercial food products.

Cathodic stripping voltammetric determination of cefaclor in pharmaceutical formulations

A sensitive method is described for the determination of cefaclor by cathodic stripping voltammetry at the hanging mercury drop electrode. cefaclor is accumulated at the electrode surface as a mercury salt, which is reduced at -0.67 V. The optimum accumulation potential and accumulation time were +0.15 V and up to 180 s, respectively. Linear calibration graphs were obtained between 3.9 mu g.L-1 to 39 mu g.L-1 and the limit of determination was evaluated to be 1.9 mu g.L-1. The method was applied successfully to the determination of cefaclor in pharmaceutical formulations.