Search

A rapid liquid chromatographic (LC) method was developed for simultaneous determination of 7 pyrethroid insecticides in beans. Residues were extracted from beans with acetone, followed by partition with ethyl acetate/cyclohexane (1+1) and clean up by gel-permeation chromatography. LC separation was performed on a LiChrospher 100 RP-18 column using acetonitrile/water (8+2) as mobile phase. The pesticides were detected by molecular absorption spectrophotometry at 212 nm. Recoveries of 7 pyrethroids fortified at 0.010; 0.10; 1.0 mg kg-1 levels were within the range 71-105 %. Advantageous features of this method are: the quantification limits, which were between 0.004 and 0.011 mg kg-1, and the simplicity in the sample treatment, which requires less clean-up if compared with the GC-ECD determination. No residues of pyrethroids were detected in 48 bean samples commercialized in São Paulo City during 2008.

The year of 2010 marks the 20th anniversary of the development of Sequential Injection Analysis (SIA) by Ruzicka and Marshall. Considered the second generation of the flow injection methods, this article briefly describes the history, the basic principles of the technique and reviews all papers developed by Brazilian scientists aiming the divulgation of this automation technique in Analytical Chemistry.

Secondary alcohol concentrations in sugar cane spirits from different origins were determined by gas chromatography. A great variation in the concentration of the secondary alcohols was found in these spirits. Of the 33 brands analyzed, 8 of them were found to be out of conformity with the legislation. Sec butanol, for which the maximum allowed concentration level is 100 mg.L-1 in absolute ethanol, was found within a concentration range between 5 mg.L-1, the limit of quantitation (LQ) and 408 mg.L-1 in absolute ethanol. Sugar cane samples from Salinas, MG, were the only ones that exhibited self similarity because of the low concentrations of n-butanol and n-amylic alcohol (< limit of detection LD).

The sensitivity and accuracy of sequential injection methods are dependent on efficient overlapping of reagent and sample zones as they are propelled toward the detector cell. The formation of the reduced phosphomolybdic acid is used to demonstrate that the overlapping efficiency in a fixed reaction coil relies on a suitable choice of reagent to sample volume ratio. Additionally, under poor mixing conditions or highly concentrated samples, the reaction extension is strongly dependent on the reagent concentration. The zone-sampling concept is exploited to determine phosphate in cola-based soft drinks after in-line dilution in an auxiliary coil.

Proton binding properties of humic and fulvic acids were studied by potentiometric titration. Carboxylic groups were the predominant ionizable sites in comparison to phenolic and amine groups. Total acidity of fulvic acid was 12 x 10-3 mol g-1, a number significantly higher than that obtained for humic acid (5.2 x 10-3 mol g-1). Copper ion binding was evaluated at pH 4, 5 and 6 by potentiometric titration with an ion selective electrode for Cu(II). Differential stability constants and complexation capacities were systematically higher for humic acid, despite its lower number of ionizable sites in comparison with fulvic acid.

The contamination of natural environments by trace metals has several adverse effects on human health, which is mainly due to the high toxicity, persistence and reactivity of these species in the environment. To understand the bioavailability of trace metals, it is necessary to know the speciation in equilibrium and the dynamic behavior of the system. In this context, the present work aims to present a bibliographic review about the potentialities of the Stripping Chronopotentiometry (SCP) and Stripping Chronopotentiometry at Scanned Deposition Potential (SSCP) in the study of dynamic trace metal speciation. These techniques have low detection limits and do not suffer interference due to the adsorption of organic matter on the surface of the working electrode. Coupling these techniques with the Absence of Gradients and Nernstian Equilibrium Stripping (AGNES) enables simultaneous determination of free ions, complexation equilibrium constants and diffusion coefficients of the complexes, thus providing information on the dynamic and heterogeneity of the metal complexes in the presence of macromolecules or particles. In this paper we will present the theory of dynamic speciation of trace metals, a detailed description of how to use the techniques to obtain this information, and examples of application in model systems and natural samples.

A sequential injection method with square wave anodic stripping voltammetry (SI-SWASV) using screen printed and crystalline gold electrode was developed for determination of As(III). The carrier solution used for electrode conditioning and stripping medium was composed of 0.050 mol L-1 HCl, whereas the supporting electrode for samples (deposition medium) was 0.50 mol L-1 HCl. The limits of detection and quantification were 20 and 70 nmol L-1 (1.5 and 5.2 µg L-1), respectively. This limit of quantification is almost two times lower than the maximum concentration of As(III) allowed in waters by World Health Organization (10 µg L-1). The sampling throughput was 20 analyses per hour using a sample volume of 1500 µL, pumped through the flow cell at the flow rate of 15 µL s-1. Screen printed gold electrodes were not suitable for work with 0.50 mol L-1 HCl because the results were strongly dependent on the lot of sensors. Crystalline gold electrodes provided reproducible results and the method was applied for determination of As(III) in river water samples. The accuracy was evaluated by recovery studies and analyses by Graphite Furnace Atomic Absorption Spectrometry, providing recoveries between 95 and 108%.

Sediment samples from Tietê river were submitted to chemical and sequential extractions of heavy metals (Cd, Cr, Cu, Ni, Pb and Zn). It was followed a single extraction by using 0.1 mol L-1 hydrochloric acid and a sequential procedure to evaluate possible chemical associations described as exchangeable, carbonate, reducible oxides, sulfide, organic matter and residual fractions. High concentrations of heavy metals were determined at Pirapora reservoir, which is closer to the Metropolitan Area of São Paulo while for Barra Bonita reservoir, the results showed low concentrations for such elements. Acid volatile sulfides, grain size distribution and carbon contents were also determined.