Peat as a natural solid-phase for copper preconcentration and determination in a multicommuted flow system coupled to flame atomic absorption spectrometry

The physical and chemical characteristics of peat were assessed through measurement of pH, percentage of organic matter, cationic exchange capacity (CEC), elemental analysis, infrared spectroscopy and quantitative analysis of metals by ICP OES. Despite the material showed to be very acid in view of the percentage of organic matter, its CEC was significant, showing potential for retention of metal ions. This characteristic was exploited by coupling a peat mini-column to a flow system based on the multicommutation approach for the in-line copper concentration prior to flame atomic absorption spectrometric determination. Cu(II) ions were adsorbed at pH 4.5 and eluted with 0.50 mol L(-1) HNO(3). The influence of chemical and hydrodynamic parameters, such as sample pH, buffer concentration, eluent type and concentration, sample flow-rate and preconcentration time were investigated. Under the optimized conditions, a linear response was observed between 16 and 100 mu g L(-1), with a detection limit estimated as 3 mu g L(-1) at the 99.7% confidence level and an enrichment factor of 16. The relative standard deviation was estimated as 3.3% (n = 20). The mini-column was used for at least 100 sampling cycles without significant variation in the analytical response. Recoveries from copper spiked to lake water or groundwater as well as concentrates used in hemodialysis were in the 97.3-111 % range. The results obtained for copper determination in these samples agreed with those achieved by graphite furnace atomic absorption spectrometry (GFAAS) at the 95% confidence level. (C) 2009 Elsevier B.V. All rights reserved.

A multicommuted flow-system for spectrophotometric determination of tannin exploiting the Cu(I)/BCA complex formation

A flow system exploiting the multicommutation approach is proposed for spectrophotometric determination of tannin in beverages. The procedure is based on the reduction of Cu(II) in the presence of 4,4`-dicarboxy-2,2`-biquinoline, yielding a complex with maximum absorption at 558 nm. Calibration graph was linear (r=0.999) for tannic acid concentrations up to 5.00 mu mol L-1. The detection limit and coefficient of variation were estimated as 10 nmol L-1 (99.7% confidence level) and 1% (1.78 mu mol L-1 tannic acid, n=10), respectively. The sampling rate was 50 determinations per hour. The proposed procedure is more sensitive and selective than the official Folin-Denis method, also minimizing drastically waste generation. Recoveries within 91.8 and 115% were estimated for total tannin determination in tea and wine samples. (C) 2007 Elsevier B.V. All rights reserved.

Simultaneous analysis of five antidepressant drugs using direct injection of biofluids in a capillary restricted-access media-liquid chromatography-tandem mass spectrometry system

Direct analysis, with minimal sample pretreatment, of antidepressant drugs, fluoxetine, imipramine, desipramine, amitriptyline, and nortriptyline in biofluids was developed with a total run time of 8 min. The setup consists of two HPLC pumps, injection valve, capillary RAM-ADS-C18 pre-column and a capillary analytical C 18 column connected by means of a six-port valve in backflush mode. Detection was performed with ESI-MS/MS and only 1 mu m of sample was injected. Validation was adequately carried out using FLU-d(5) as internal standard. Calibration curves were constructed under a linear range of 1-250 ng mL(-1) in plasma, being the limit of quantification (LOQ), determined as 1 ng mL(-1), for all the analytes. With the described approach it was possible to reach a quantified mass sensitivity of 0.3 pg for each analyte (equivalent to 1.1-1.3 fmol), translating to a lower sample consumption (in the order of 103 less sample than using conventional methods). (C) 2008 Elsevier B.V. All rights reserved.

Determination of Minoxidil by Bleaching the Permanganate Carrier Solution in a Flow-Based Spectrophotometric System

The determination of minoxidil (MX) with potassium permanganate as a carrier in a flow injection method is described. The detection at 550nm was linear from 1.0x10-5 to 5.0x10-4mol L-1. The limit of detection (3 sigma/slope) was 8.92x10-6mol L-1, with an analytical frequency of 32h-1. The proposed method was applied to commercial samples, with recoveries from 104.7 to 106.4%. Comparison with the HPLC procedure reveled relative errors from 0.48 to 1.4%, and the results agreed within a 95% confidence level.

Analytical Assessment of a Home Made Capillary Electrophoresis Equipment with Linear Charge Coupled Device for Visible Light Absorption Detection in the Determination of Food Dyes

The performance of modular home made capillary electrophoresis equipment with spectrophotometric detection, at a visible region by means of a miniaturized linear charge coupled device, was evaluated for the determination of four food dyes. This system presents a simple but efficient home made cell detection scheme. A computer program that converts the spectral data after each run into the electropherograms was developed to evaluate the analytical parameters. The dyes selected for analytical evaluation of the system were Brilliant Blue FCF, Fast Green FCF, Sunset Yellow FCF, and Amaranth. Separation was carried out in a 29cm length and 75 mu m I.D fused silica capillary, using 10mmolL-1 borate buffer at pH 9, with separation voltage of 7.5kV. The detection limits for the dyes were between 0.3 and 1.5mgL-1 and the method presented adequate linearity over the ranges studied, with correlation coefficients greater than 0.99. The method was applied for determination and quantification of these dyes in fruit juices and candies.

Variation of System Performance with Design and Climate for Combisystems in Sweden

In Sweden, 90% of the solar heating systems are solar domestic hot water and heating systems (SDHW&H), so called combisystems. These generally supply most of the domestic hot water needs during the summer and have enough capacity to supply some energy to the heating system during spring and autumn. This paper describes a standard Swedish combisystem and how the output from it varies with heating load, climate within Sweden, and how it can be increased with improved system design. A base case is defined using the standard combi- system, a modern Swedish single family house and the climate of Stockholm. Using the simulation program Trnsys, parametric studies have been performed on the base case and improved system designs. The solar fraction could be increased from 17.1% for the base case to 22.6% for the best system design, given the same system size, collector type and load. A short analysis of the costs of changed system design is given, showing that payback times for additional investment are from 5-8 years. Measurements on system components in the laboratory have been used to verify the simulation models used. More work is being carried out in order to find even better system designs, and further improvements in system performance are expected.

TCA Evaluation : Lab Measurements, Modelling and System Simulations

The study reported here is part of a large project for evaluation of the Thermo-Chemical Accumulator (TCA), a technology under development by the Swedish company ClimateWell AB. The studies concentrate on the use of the technology for comfort cooling. This report concentrates on measurements in the laboratory, modelling and system simulation. The TCA is a three-phase absorption heat pump that stores energy in the form of crystallised salt, in this case Lithium Chloride (LiCl) with water being the other substance. The process requires vacuum conditions as with standard absorption chillers using LiBr/water. Measurements were carried out in the laboratories at the Solar Energy Research Center SERC, at Högskolan Dalarna as well as at ClimateWell AB. The measurements at SERC were performed on a prototype version 7:1 and showed that this prototype had several problems resulting in poor and unreliable performance. The main results were that: there was significant corrosion leading to non-condensable gases that in turn caused very poor performance; unwanted crystallisation caused blockages as well as inconsistent behaviour; poor wetting of the heat exchangers resulted in relatively high temperature drops there. A measured thermal COP for cooling of 0.46 was found, which is significantly lower than the theoretical value. These findings resulted in a thorough redesign for the new prototype, called ClimateWell 10 (CW10), which was tested briefly by the authors at ClimateWell. The data collected here was not large, but enough to show that the machine worked consistently with no noticeable vacuum problems. It was also sufficient for identifying the main parameters in a simulation model developed for the TRNSYS simulation environment, but not enough to verify the model properly. This model was shown to be able to simulate the dynamic as well as static performance of the CW10, and was then used in a series of system simulations. A single system model was developed as the basis of the system simulations, consisting of a CW10 machine, 30 m2 flat plate solar collectors with backup boiler and an office with a design cooling load in Stockholm of 50 W/m2, resulting in a 7.5 kW design load for the 150 m2 floor area. Two base cases were defined based on this: one for Stockholm using a dry cooler with design cooling rate of 30 kW; one for Madrid with a cooling tower with design cooling rate of 34 kW. A number of parametric studies were performed based on these two base cases. These showed that the temperature lift is a limiting factor for cooling for higher ambient temperatures and for charging with fixed temperature source such as district heating. The simulated evacuated tube collector performs only marginally better than a good flat plate collector if considering the gross area, the margin being greater for larger solar fractions. For 30 m2 collector a solar faction of 49% and 67% were achieved for the Stockholm and Madrid base cases respectively. The average annual efficiency of the collector in Stockholm (12%) was much lower than that in Madrid (19%). The thermal COP was simulated to be approximately 0.70, but has not been possible to verify with measured data. The annual electrical COP was shown to be very dependent on the cooling load as a large proportion of electrical use is for components that are permanently on. For the cooling loads studied, the annual electrical COP ranged from 2.2 for a 2000 kWh cooling load to 18.0 for a 21000 kWh cooling load. There is however a potential to reduce the electricity consumption in the machine, which would improve these figures significantly. It was shown that a cooling tower is necessary for the Madrid climate, whereas a dry cooler is sufficient for Stockholm although a cooling tower does improve performance. The simulation study was very shallow and has shown a number of areas that are important to study in more depth. One such area is advanced control strategy, which is necessary to mitigate the weakness of the technology (low temperature lift for cooling) and to optimally use its strength (storage).

Testing linear cointegration against smooth-transition cointegration

This paper studies a smooth-transition (ST) type cointegration. The proposed ST cointegration allows for regime switching structure in a cointegrated system. It nests the linear cointegration developed by Engle and Granger (1987) and the threshold cointegration studied by Balke and Fomby (1997). We develop F-type tests to examine linear cointegration against ST cointegration in ST-type cointegrating regression models with or without time trends. The null asymptotic distributions of the tests are derived with stationary transition variables in ST cointegrating regression models. And it is shown that our tests have nonstandard limiting distributions expressed in terms of standard Brownian motion when regressors are pure random walks, while have standard asymptotic distributions when regressors contain random walks with nonzero drift. Finite-sample distributions of those tests are studied by Monto Carlo simulations. The small-sample performance of the tests states that our F-type tests have a better power when the system contains ST cointegration than when the system is linearly cointegrated. An empirical example for the purchasing power parity (PPP) data (monthly US dollar, Italy lira and dollar-lira exchange rate from 1973:01 to 1989:10) is illustrated by applying the testing procedures in this paper. It is found that there is no linear cointegration in the system, but there exits the ST-type cointegration in the PPP data.

Effects of a quantum measurement on the electric conductivity : Application to graphene

We generalize the standard linear-response (Kubo) theory to obtain the conductivity of a system that is subject to a quantum measurement of the current. Our approach can be used to specifically elucidate how back-action inherent to quantum measurements affects electronic transport. To illustrate the utility of our general formalism, we calculate the frequency-dependent conductivity of graphene and discuss the effect of measurement-induced decoherence on its value in the dc limit. We are able to resolve an ambiguity related to the parametric dependence of the minimal conductivity.

System Integration of PV/T Collectors in Solar Cooling Systems

The demand for cooling and air-conditioning of building is increasingly ever growing. This increase is mostly due to population and economic growth in developing countries, and also desire for a higher quality of thermal comfort. Increase in the use of conventional cooling systems results in larger carbon footprint and more greenhouse gases considering their higher electricity consumption, and it occasionally creates peaks in electricity demand from power supply grid. Solar energy as a renewable energy source is an alternative to drive the cooling machines since the cooling load is generally high when solar radiation is high. This thesis examines the performance of PV/T solar collector manufactured by Solarus company in a solar cooling system for an office building in Dubai, New Delhi, Los Angeles and Cape Town. The study is carried out by analyzing climate data and the requirements for thermal comfort in office buildings. Cooling systems strongly depend on weather conditions and local climate. Cooling load of buildings depend on many parameters such as ambient temperature, indoor comfort temperature, solar gain to the building and internal gains including; number of occupant and electrical devices. The simulations were carried out by selecting a suitable thermally driven chiller and modeling it with PV/T solar collector in Polysun software. Fractional primary energy saving and solar fraction were introduced as key figures of the project to evaluate the performance of cooling system. Several parametric studies and simulations were determined according to PV/T aperture area and hot water storage tank volume. The fractional primary energy saving analysis revealed that thermally driven chillers, particularly adsorption chillers are not suitable to be utilizing in small size of solar cooling systems in hot and tropic climates such as Dubai and New Delhi. Adsorption chillers require more thermal energy to meet the cooling load in hot and dry climates. The adsorption chillers operate in their full capacity and in higher coefficient of performance when they run in a moderate climate since they can properly reject the exhaust heat. The simulation results also indicated that PV/T solar collector have higher efficiency in warmer climates, however it requires a larger size of PV/T collectors to supply the thermally driven chillers for providing cooling in hot climates. Therefore using an electrical chiller as backup gives much better results in terms of primary energy savings, since PV/T electrical production also can be used for backup electrical chiller in a net metering mechanism.

Projetos de controladores para sistemas de potência utilizando LMI'S

A presente dissertação tem como objetivo estudar e aprimorar métodos de projetos de controladores para sistemas de potência, sendo que esse trabalho trata da estabilidade dinâmica de sistemas de potência e, portanto, do projeto de controladores amortecedores de oscilações eletromecânicas para esses sistemas. A escolha dos métodos aqui estudados foi orientada pelos requisitos que um estabilizador de sistemas de potência (ESP) deve ter, que são robustez, descentralização e coordenação. Sendo que alguns deles tiveram suas características aprimoradas para atender a esses requisitos. A abordagem dos métodos estudados foi restringida à análise no domínio tempo, pois a abordagem temporal facilita a modelagem das incertezas paramétricas, para atender ao requisito da robustez, e também permite a formulação do controle descentralizado de maneira simples. Além disso, a abordagem temporal permite a formulação do problema de projeto utilizando desigualdades matriciais lineares (LMI’s), as quais possuem como vantagem o fato do conjunto solução ser sempre convexo e a existência de algoritmos eficientes para o cálculo de sua solução. De fato, existem diversos pacotes computacionais desenvolvidos no mercado para o cálculo da solução de um problema de inequações matriciais lineares. Por esse motivo, os métodos de projeto para controladores de saída buscam sempre colocar o problema na forma de LMI’s, tendo em vista que ela garante a obtenção de solução, caso essa solução exista.

Sobre o sistema de amortização linear crescente

Aiming to reach a compromise solution to the issues of default risk and the payment capacity of takers of housing loans, Jorge Oscar de Mello Flôres submited to the Banco Nacional de Habitação, which was then in charge of the Brazilian System of Housing Financing, what he named as the Linearly Increasing System of Amortization. (LISA). Following a critical analysis of the LISA, it is proposed the alternative named as the Generalyzed System of Mixed Amortization (GSMA).

Estudo comparativo do desempenho de controladores robustos aplicados a um sistema de tanques acoplados.

Currently the uncertain system has attracted much academic community from the standpoint of scientific research and also practical applications. A series of mathematical approaches emerge in order to troubleshoot the uncertainties of real physical systems. In this context, the work presented here focuses on the application of control theory in a nonlinear dynamical system with parametric variations in order and robustness. We used as the practical application of this work, a system of tanks Quanser associates, in a configuration, whose mathematical model is represented by a second order system with input and output (SISO). The control system is performed by PID controllers, designed by various techniques, aiming to achieve robust performance and stability when subjected to parameter variations. Other controllers are designed with the intention of comparing the performance and robust stability of such systems. The results are obtained and compared from simulations in Matlab-simulink.

Analysis of the four wave mixing effect (FWM) in a dispersion decreasing fiber (DDF) for a WDM system

We did a numerical investigation of the propagation of short light pulses in the region of 1.55 mu m and the conversion efficiency (CE) for the four wave mixing generation (FWM) of ordinary and dispersion decreasing fibers for use in wavelength division multiplexing (WDM) systems, Our simulations studies three different profiles, linear, hyperbolic. and constant, One conclude that for all the profiles there is decrease of the conversion efficiency with the increase in the channel separation. The hyperbolic profile present a higher efficiency of around 1000 above in magnitude compared with the others profiles at 0.2 nm of channel separation. We calculate the conversion efficiency versus the fiber length for the three profiles. The conversion efficiency for the hyperbolic profile is higher when compared to the constant and linear profiles. The other interesting point of the hyperbolic profile is that the increase of the CE in the beginning of the fiber does not show my oscillation in the CE value (log eta), which was observed for the constant and linear profiles. For all the profiles there is an increase of the conversion efficiency with the increase of the pump power. The compression factor C-i for the generated FWM signal at omega(3) was measured along the DDF's and the constant profile fibers. One can conclude that with the use of decreasing dispersion profile (DDF) fibers one can have a control of the (CE) conversion efficiency and the compression factor of the four wave mixing (FWM) generation in WDM systems. (c) 2005 Elsevier B.V. All rights reserved.

H-infinity control design for time-delay linear systems: a rational transfer function based approach

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