Polycyclic aromatic hydrocarbons in bays of the Rio de Janeiro state coast, SE - Brazil: Effects on catfishes.

The Brazilian coast of the Rio de Janeiro State has bays of great economic, ecological and social importance. However, these ecosystems have been suffering intense anthropogenic influence, mainly due to the contamination by polycyclic aromatic hydrocarbons (PAHs) from urban-industrial activities. Moreover, PAHs are organic pollutants of high toxicity and carcinogenicity causing global concern to human and environmental health. This study evaluated on catfish (Genidens genidens) a set of key parameters (sex, morphometric traits, condition factor (K), PAH metabolites in gallbladder, frequency of micronucleus (MN) and erythrocytic nuclear abnormalities (ENA) in blood. In addition we also evaluated histopathological hepatic effects, Ethoxyresorufin-O-deethylase (EROD) activity and Benzo(a)pyrene diol epoxide (BPDE)-DNA adducts) in liver samples, in order to indicate the fish health status and environmental pollution levels of three main Bays (Guanabara, Sepetiba and Ilha Grande) of the Rio de Janeiro State, in the Southeast of Brazil. In general, the worst physical and metabolic conditions in catfishes were evidenced in Guanabara Bay, possibly indicating the highest level of contamination by PAHs. Contrary evidence was observed in Ilha Grande Bay, showing lower biological changes in G. genidens. However in Sepetiba Bay, the influence of PAHs contamination showed the highest hepatic lesions in catfishes, prevailing foci of cellular alterations, megalocytic hepatosis and hydropic vacuolations. The employability of a set of biomarkers on catfish was efficient for screening pollution for PAHs in tropical environments. This reinforces the need for effective actions of monitoring and conservation strategies of bays of the Rio de Janeiro State (Brazil), in order to ensure quality and health to both human and environment.

A novel strategy based on in-syringe dispersive liquid-liquid microextraction for the determination of nickel in chocolate samples.

In this work, a novel approach was developed to perform dispersive liquid-liquid microextraction using a rapid pressure variation to disperse the extraction solvent in an aqueous medium. A glass syringe was used to produce an environment subject to a rapid pressure difference. The element used as a model was nickel and the approach was called pressure variation in-syringe dispersive liquid-liquid microextraction (PV-IS-DLLME). The extraction solvent used was 1-butyl-3-methylimidazolium hexafluorophosphate, and ammonium pyrrolidine dithiocarbamate was the complexing reagent. The variables pH, solvent volume, amount of complexing agent, extraction time and syringe volume were studied by a factorial 25-1 fractional design. All variables were significant. However, the two least significant, amount of complexing agent (50.0 µL) and syringe volume (20.0 mL) were fixed at their optimum levels, according to the generated Pareto chart. A Doehlert matrix was studied for the variables volume of solvent, pH and extraction time to obtain optimal levels of these factors, and the contour plots showed the following critical values: 120.0 µL, 2.0 and 60.0 s respectively. The developed method presented limits of detection and quantification of 0.1 and 0.3 mg kg-1, an enrichment factor of 17 and a precision of 4.8% (100.0 µg L-1). The developed method was applied to the analysis of samples of powdered chocolate and certified reference material.

Development of a non-destructive method for determining protein nitrogen in a yellow fever vaccine by near infrared spectroscopy and multivariate calibration.

Near infrared spectroscopy (NIR) with diffuse reflectance associated to multivariate calibration has as main advantage the replacement of the physical separation of interferents by the mathematical separation of their signals, rapidly with no need for reagent consumption, chemical waste production or sample manipulation. Seeking to optimize quality control analyses, this spectroscopic analytical method was shown to be a viable alternative to the classical Kjeldahl method for the determination of protein nitrogen in yellow fever vaccine. The most suitable multivariate calibration was achieved by the partial least squares method (PLS) with multiplicative signal correction (MSC) treatment and data mean centering (MC), using a minimum number of latent variables (LV) equal to 1, with the lower value of the square root of the mean squared prediction error (0.00330) associated with the highest percentage value (91%) of samples. Accuracy ranged 95 to 105% recovery in the 4000-5184 cm-1 region.

Spectrophotometric determination of rosuvastatin in pharmaceutical formulations using quinalizarin

ABSTRACT This work presents the development of a methodology based on the formation of a charge transfer complex between quinalizarin and rosuvastatin, allowing for the spectrophotometric determination of rosuvastatin at 579 nm. The factors involved in the sensitivity of the technique were studied (nature and proportion of the solvent, reaction time, pH of aqueous phase and quinalizarin concentration). The proposed spectrophotometric procedures were validated with respect to linearity, ranges, precision, accuracy, detection and quantification limits. Calibration curves of the formed color products showed good linear relationships over the concentration range of 6-15 mg L-1. The proposed method has been successfully applied, which can be confirmed by interference test (comparison between the standard curves and addition of analyte), method precision (RSD 2.3% to 6 mg L-1), and by accuracy (statistically equivalent results between the proposed method and a chromatographic method of reference).

Multivariate technique for optimization of digestion procedure by focussed microwave system for determination of Mn, Zn and Fe in food samples using FAAS.

This article describes the development by response surface methodology (RSM) of a procedure for iron, zinc and manganese determination by flame atomic absorption spectrometry (FAAS) in food samples after digestion employing a focussed microwave system. A Doehlert matrix was used to find optimal conditions for the procedure through response surface study. Three variables (irradiation power and time and composition of oxidant solution-HNO(3)+H(2)O(2)) were regarded as factors in the optimization study. The working conditions were established as a compromise between optimum values found for each analyte taking into consideration the robustness of the procedure. These values were 12min, 260W and 42% (v/v) for irradiation time, irradiation power and percent of H(2)O(2) in solution, respectively. The accuracy of the optimized procedure was evaluated by analysis of certified reference materials and by comparison with a well-established closed vessel microwave dissolution methodology.