Multivariate optimization of ultrasound-assisted liquid-liquid microextraction based on two solvents for cadmium preconcentration prior to determination by flame atomic absorption spectrometry.

A method based on ultrasound-assisted emulsification liquid-liquid microextraction (USAEME) for cadmium determination by flame atomic absorption spectrometry (FAAS) was developed in this work. USAEME is based on the use of the mixture of 1,2-dichloroethane and trichloroethylene as an acceptor phase, 2-(2-bromo-5-pyridylazo)-5(diethylamino)phenol (Br-PADAP) as a chelating reagent, and ethanol as a dispersive solvent. The composition of the extraction and dispersive solvents, the volume of the extraction solvent, pH, and the sonication time were optimized using the multivariate strategy. The limits of detection and quantification calculated under optimum conditions were, respectively, 0.39 and 1.33 µg L-1, and the obtained enrichment factor was 21. The accuracy was tested by the analysis of certified reference materials. The method was applied to cadmium determination in bivalve mollusks, water, and urban wastewater from Pontal Bay, Bahia, Brazil. The proposed method is simple, fast, and efficient, and uses small amounts of organic solvents for the determination of cadmium.

Artificial neural network employment for element determination in Mugil cephalus by ICP OES in Pontal Bay, Brazil.

Fish are important sources of protein, making them very significant in the human diet. Although the consumption of this food is beneficial for health, it is essential that the product does not contain inorganic components above the limits recommended by the current legislation. Therefore, a method for determination of elements in fish (Mugil cephalus) samples was optimized. A simplex centroid mixture design with restriction was applied for optimization of the acid digestion of samples in an open system under reflux in order to evaluate the best ratio between the reagents HNO3, H2O2 and H2O. The results indicated that more intense analyte signals were obtained when a mixture containing 3.6 mL of HNO3 (65% v/v), 0.4 mL of H2O2 (30% v/v) and 6.0 mL of H2O was used. The accuracy of the method was assessed with a CRM of oyster tissue (NIST 1566b). The method presented relative standard deviations (RSDs) of 3.54%; 3.82%; 4.81% and 3.50% for Zn, Fe, Cu and S, respectively. The detection limits were 0.002 mg kg-1 for Cu and Zn and 0.02 mg kg-1 for Fe and S. The proposed method was applied for the determination of Zn, Fe, Cu and S in fish samples. A Kohonen Self-Organizing Map (KSOM) with K-means implementation was applied to better delimit the boundary between groups and the spatial and temporal influence on how concentrations of the chemical elements were perceived. To verify the separation, the Davies-Bouldin and Silhouette indices were used, obtaining 0.5374 and 0.8541, respectively, indicating satisfactory separation.

Evaluation of macro and micronutrient elements content from soft drinks using principal component analysis and Kohonen self-organizing maps.

This study approaches the determination of nine elements from Brazilian carbonated soft drinks of several flavors and manufactures using inductively coupled plasma optical emission spectrometry (ICP OES). The concentrations of the elements varied as follows: (in µg L-1: Cu: 4.00-78.0; Fe: 74.0-506; Mn: 20.0-66.0; Zn: 104-584) and (in mg L-1: Ca: 4.81-16.2; K: 6.73-260; Na: 26.0-175; S: 1.43-5.41; P: 0.186-219). Principal component analysis has shown some tendencies to form two groups according to the drink flavor (orange and cola), but only cola presented a clear and complete separation. Using Kohonen maps, it was observed a tendency to form three flavor groups: (i) cola, (ii) orange and lemon, and (iii) guarana. However, this last tool proved to be more accurate in the groups' formation.

Direct determination of Ca, K, Mg, Na, P, S, Fe and Zn in bivalve mollusks by wavelength dispersive X-ray fluorescence (WDXRF) and laser-induced breakdown spectroscopy (LIBS).

This study aims to develop methods for determination of Ca, K, Mg and Na by laser-induced breakdown spectroscopy (LIBS) and Ca, K, Mg, Na, P, S, Fe and Zn by wavelength dispersive X-ray fluorescence (WDXRF) in pressed pellets bivalve mollusks. LIBS and WDXRF calibration models were built with references values determined by inductively coupled plasma optical emission spectrometry (ICP OES) after acid digestion. The calibration models for LIBS and WDXRF were obtained from 28 samples (14 for calibration and 14 for validation). It was possible to implement a validation between LIBS and WDXRF methods for elements Ca, K, Mg and Na. The proposed calibration model obtained using LIBS and WDXRF data presented a good correlation with reference values obtained by ICP OES.

Determination and Evaluation of Metallothionein and Metals in Mugil cephalus (Mullet) from Pontal Bay, Brazil.

To assess environmental contamination, studies have been increasingly carried out using biomarkers to diagnose the effects of toxic metal exposure, such as metallothionein (MT). In this context, the aims of the present study were to determine Cd, Cu, Ni and Pb concentrations, by ICP-MS, in liver samples from Mugil cephalus from the municipality of Ilhéus, located in North-Southeastern Brazil, in the state of Bahia, which has been increasingly suffering from anthropogenic pressure, and to quantify total MT in liver and gills. Among essential metals, copper (199.2 µg g-1) presented concentrations approximately 7 times higher than allowed by the World Health Organization (30 µg g-1). Liver samples showed higher concentrations than gills. Metallothionein concentrations indicate differential contamination along the study area. The first sampling showed higher induction of MT synthesis overall. Differences between liver and gill MT concentration trends were relatively minor, which may indicate the adequacy of analyzing gills in an environmental monitoring context.