Determinação de pesticidas organofosforados em água usando microextração em fase sólida e CGAR-EM

Solid-phase microextraction (SPME) has been applied to direct extraction of 11 organophosphorus pesticides in water using a 100 mm fiber polydimethylsiloxane. The method was evaluated with respect time of exposure, detection limits (LODs), linearity and precision. The detection limits (S/N = 3) depend of each pesticide and varie about ng/L levels. The linearity was satisfactory with coefficients of correlation usually greater than 0.993. The precision of the method was determined by extraction from 4.0 mg/L aqueous standard with coefficients of variation between 5.7 to 17.2%.

Método potenciométrico para determinação de cobre em cachaça

'Cachaça' is the Brazilian name for the spirit obtained from sugarcane. According to Brazilian regulations, it may be sold raw or with addition of sugar and may contain up to 5 mg/L of copper. Copper in "cachaça" was determined by titration with EDTA, using a homemade copper membrane electrode for end-point detection. It was found a pooled standard deviation of 0,057 mg/L and there was no significant difference between the results obtained by the potentiometric method and by flame atomic absorption spectrometry with standard addition. Among the 21 'cachaça' samples from 16 different brands analyzed, three overpassed the legal copper limit. For its characteristics of accuracy, precision, and speed, the potentiometric method may be employed advantageously in routine analysis, specially when low cost is a major concern.

Avaliando as aproximações usadas no ensino de Físico-Química

The approaches are part of the everyday of the Physical Chemistry. In many didactic books in the area of Chemistry, the approaches are validated starting from qualitative and not quantitative approaches. We elaborated some examples that allow evaluating the quantitative impact of the approaches, being considered the mistake tolerated for the approximate calculation. The estimate of the error in the approaches should serve as guide to establish the validity of the calculation, which use them. Thus, the shortcut that represents a calculation approached to substitute accurate calculations; it can be used without it loses of quality in the results, besides indicating, as they are valid the adopted criterions.

Relação entre as massas úmida, seca e de cinza em materiais biológicos - uma ferramenta para amostragens em campo e análise de amostras

Little is known about the amount of water and ash in brazilian foodstuffs and plants. The relationships between fresh, dry and ash weight were determined in 40 different biological samples. It could be an important tool when one studies biological material containing low concentration of the chemical elements. This study address to determine these relationships and to provide the amount of biological material that one needs to collect. It aims to supply information that could be used to improve the detection limit, precision and accuracy of the analytical methodology utilized.

Construção de uma cela de fluxo para medidas por espectrofotometria em fase sólida

A simple and low cost flow cell is proposed for measurements by solid-phase spectrophotometry employing a conventional spectrophotometer. The flow cell geometry allows the employment of a large amount of the solid support without causing both excessive attenuation of the radiation beam and increasing of the back-pressure. The adaptation of the flow cell in the optical path of the spectrophotometer in order to increase the precision is discussed. The flow cell characteristics were demonstrated by measurements of Co(II), employing 1-(2-tiazolylazo)-2-naphthol (TAN) immobilized on C18 bonded silica as solid support. The apparent molar absorptivity and coefficient of variation were estimated as 1.86 x 10(5) L mol-1 cm-1 and 1.4 % (n=15). A sample throughput of 40 determinations per hour and a detection limit of 15 mug L-1 (99.7 % confidence level) were achieved.

Avaliação dos métodos analíticos para a determinação de metabólitos do benzeno como potenciais biomarcadores de exposição humana ao benzeno no ar

Increasing attention is being paid to the use of biomarkers for determining the exposure of humans to air toxics. Biomarkers include the nonreacted toxic substance, their metabolites, or the reaction products of these toxics with naturally substances in the body. Significant progress has been made in the measurement of biomarkers during the past several years. Much of this progress has been because of the development of advanced analytical techniques for identification and quantification of the chemical species in complex matrix, such as biological fluids. The assessment of the potential cancer risk associated with exposure to benzene at occupational and non-occupational ambient is necessary because of the toxicological implications of this air pollutant. Thus, in this review, the analytical methodologies used to determine the benzene metabolites, in special, urinary muconic acid and S-phenylmercapturic acid, are described and several problems affecting the precision of these procedures are discussed. Finally, in view of the difficulty pointed out for selecting the more adequate biomarker, further studies to evaluate the human exposure levels to benzene should be done.

Especiação de cobre e chumbo em sedimento do Rio Tubarão (SC) pelo método Tessier

The sequential extraction procedure proposed by Tessier and total digestion were applied for the analysis of sediment samples from Tubarão River. The recoveries were between 93.5 and 102.5% for Cu and 99.2 and 111% for Pb. The precision was tipically better than 6% for Cu and 3% for Pb. Comparison of the values obtained for the total digest with the sum of the extracted fractions showed that there were no significant losses in the extraction steps so that the method can be used for the monitoring availability and mobility of these analytes. According to ten points of sampling, was possible to determined the average of labiles phases (fractions 1 and 4) for Pb and Cu: 33.70% and 18.18%, respectively; and the inert phases (fraction 5- residual): 66.30% for Pb and 81.82% for Cu.

Espectrometria de absorção atômica com atomização eletrotérmica em filamento de tungstênio: uma re-visão crítica

In this review it is presented some aspects of electrothermal atomic absorption spectrometry with tungsten coil (ETAW-AAS) since its beginning until the present days as well as the perspectives for this technique. Some aspects concerning its development and theoretical concepts are discussed. The analytical figures of merit such as limit of detection (LD), characteristic mass (m0), relative standard deviation (RSD), accuracy and precision are evaluated, compared and discussed considering published works. It is also evaluated its advantages, applications, limitations and instrumental development. The use of diode laser as radiation source and its perspectives to ETAW are also discussed.

Aplicação da espectroscopia de ressonância magnética nuclear para estudos de difusão molecular em líquidos: a técnica DOSY

Diffusion coefficients provide uniquely detailed and easily interpreted information on molecular organization and phase structure. They are quite sensitive to structural changes, and to binding and association phenomena, in particular for liquid colloidal or macromolecular systems. This paper describes the principles of diffusion measurements in liquids by pulsed magnetic field gradient spin-echo (PFG-SE) NMR spectroscopy. The important PFG-SE technique known as DOSY is presented and discussed. This is a noninvasive technique that can provide individual multicomponent translational diffusion coefficients with good precision in a few minutes, without the need for radioactive isotopic labelling.

Um banho termostático de baixo custo (temperatura ambiente até 0ºC)

Thermal baths to decrease ambient temperature are an indispensable tool for most research and teaching laboratories, especially those in tropical or equatorial regions. A simple and inexpensive thermal bath has been developed based on a scratched compressor. It has three possible setups for cooling: sample immersed into the bath, sample flowing through the bath, and cooling liquid flowing in a jacket around the sample. It has been tested for 40 months. The temperature ranges from room temperature to 0 °C, when using water. The repeatability is better than 3% and the precision varies from 0.5% to 2%.

Sistema de alimentação gás-líquido para medidas de atividade catalítica

This note has as objective to present the advantages of the use of syringe-type pumps for the feeding of liquid reactants, together with mass flow controllers for gases, instead of the saturators, as it is generally accomplished. Among the advantages, the system with syringe pumps presents a greater flexibility in flow control as well as in composition compared with the system that uses saturator. In addition, the flow of the liquid reactants is known with precision in the syringe pump system.

Emprego de padrão único para a construção de curvas analíticas em sistema de análise por injeção em fluxo associado à espectrofotometria em fase sólida

In this work two procedures were proposed for analytical curves construction using a single standard solution employing a flow injection system with solid phase spectrophotometric detection (FI-SPS). A flow cell contends the chromogenic reagent 1-(2-tiazolylazo)-2-naphtol was positioned on the optical path. The first procedure was based on controlled concentration of analyte on solid phase and the relations between absorbance and the total volume of injected allowed the calculation of analyte concentration. The second procedure was developed employing controlled dispersion/retention in flow system where analyte concentration was obtained by exploiting the relation between transient signals of samples and single standard solution at equivalent reading time. The procedures were successfully applied for zinc determination in synthetic solutions with good precision and accuracy at 95% confidence level.

Determinação potenciométrica em fluxo de cloreto de cetilpiridinio em desinfectantes bucais

The work describes a new procedure for cetylpyridinium chloride determination in oral disinfectants, based on a flow-injection system with potentiometric detection. The determination was based on the measurement of picrate concentration decrease as result of ion-pair reaction with the analyte present in the injected sample. In the optimised set-up the sample injection volume was kept at 400 µL and merged downstream with the reagent solution containing 1,0 x10-5 mol/L of picrate adjusted to pH 5.0 with citrate/citric acid buffer. The flow rate was fixed at 8 mL/min and the reactor length at 40 cm. The proposed procedure enables the determination of cetylpyridinium in the analytical range of 5,0x10-6 - 7,5x10-5 mol/L at a sampling rate of 60/h. The results for real samples had a precision better than 3% and were comparable to the labelled values.

A escolha da faixa espectral no uso combinado de métodos espectroscópicos e quimiométricos

A method is presented for the choice of spectral regions when absorption measurements are coupled to chemometric tools to perform quantitative analyses. The method is based on the spectral distribution of the relative standard deviation of concentration (s c/c). It has been applied to the development of PLS-FTNIR calibration models for the determination of density and MON of gasoline, and ethanol content and density of ethanol fuel. The new method was also compared with the correlation (R²) method and has proved to generate PLS calibration models that present better accuracy and precision than those based on R².

Validação de modelos de calibração multivariada: uma aplicação na determinação de pureza polimórfica de carbamazepina por espectroscopia no infravermelho próximo

The application of analytical procedures based on multivariate calibration models has been limited in several areas due to requirements of validation and certification of the model. Procedures for validation are presented based on the determination of figures of merit, such as precision (mean, repeatability, intermediate), accuracy, sensitivity, analytical sensitivity, selectivity, signal-to-noise ratio and confidence intervals for PLS models. An example is discussed of a model for polymorphic purity control of carbamazepine by NIR diffuse reflectance spectroscopy. The results show that multivariate calibration models can be validated to fulfill the requirements imposed by industry and standardization agencies.