Determination of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) in Brazilian cow milk.

The determination of polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) in raw cow milks have never been reported in Brazil. Since the consumption of food of animal origin, including milk and dairy products, is the major source of human exposure to these compounds, this study aimed to establish the levels and profile of seven PCDDs and ten PCDFs in raw cow milk samples collected in eight Brazilian states which among the major milk producer states. Raw milk samples were collected in 34 different dairy cattle farms during the summer of 2013. All PCDD/Fs congeners were found at least in some of the 34 samples studied. The octa-chlorinated congeners (OCDD and OCDF) were ubiquitous and also present in high concentrations. The mean values of WHO-TEQ1998;2005 were respectively 1.66 and 1.36pgTEQg-1 fat and samples taken in São Paulo showed the highest WHO-TEQ values (2.46 TEQ1998g-1 fat and 2.10pgTEQ2005g-1 fat). Although all samples showed some contamination level, all values were below the limit established by European Union for total PCDD/Fs in cow milk (3pgWHO-TEQ1998g-1 fat). Principal Component Analysis (PCA) showed that OCDD and OCDF were responsible for 73% and 20% of the total data variance, respectively and they presented an independent behavior, probably as a result of distinct origins. The use of TEQ as weights in the PCA, revealed the importance of the penta-chloro congeners and it was possible to identify sample distribution patterns probably associated with the main PeCDD and PeCDF. The importance of local sources to PCDD/Fs concentrations is still to be evaluated and determined.

An alternative derivatization reaction to the determination of doramectin in bovine milk using spectrofluorimetry.

The doramectin (DOR), which belongs to the avermectins group (AVM), has a high antiparasitic activity and so it has been widely used in food-producing animals. The DOR shows low fluorescence quantum efficiency and as a consequence, chemical derivatization reactions are necessary to produce derivatives with improved luminescent properties before its determination by fluorimetry. As the presence of this compound in food represents a risk to human health, an easy, clean and low cost derivatization reaction, which is alternative to those usually employed and that enables its spectrofluorimetric determination in milk samples, was developed. Ethanolic solutions of DOR, containing sodium hydroxide at a final concentration of 0.25 mol L(-1), after 60 min of heating at 50 °C, produced fluorescent signals 1000 times higher than the original ethanolic solution. Using these optimized conditions, a linear response range that extended from 50.00 to 1000 µg L(-1), with a value of (R(2)) equal to 0.9970, was obtained. Average recovery of DOR was 92.5±1.5% (n=3) in bovine milk fortified samples submitted to a liquid-liquid extraction at low temperature and pre concentration process, indicating the usefulness and effectiveness of the proposed method. The proposed spectrofluorimetric method is an alternative to high-performance liquid chromatography (HPLC) based methods, allowing rapid and simple detection of doramectin in milk samples.

Superficial distribution of aromatic compounds and geomicrobiology of sediments from Suruí Mangrove, Guanabara Bay, RJ, Brazil.

The distribution of selected aromatic compounds and microbiology were assessed in superficial sediments from Suruí Mangrove, Guanabara Bay. Samples were collected at 23 stations, and particle size, organic matter, aromatic compounds, microbiology activity, biopolymers, and topography were determined. The concentration of aromatic compounds was distributed in patches over the entire mangrove, and their highest total concentration was determinated in the mangrove's central area. Particle size differed from most mangroves in that Suruí Mangrove has chernies on the edges and in front of the mangrove, and sand across the whole surface, which hampers the relationship between particle size and hydrocarbons. An average @ 10% p/p of organic matter was obtained, and biopolymers presented high concentrations, especially in the central and back areas of the mangrove. The biopolymers were distributed in high concentrations. The presence of fine sediments is an important factor in hydrocarbon accumulation. With high concentration of organic matter and biopolymers, and the topography with chernies and roots protecting the mangrove, calmer areas are created with the deposition of material transported by wave action. Compared to global distributions, concentrations of aromatic compounds in Suruí Mangrove may be classified from moderate to high, showing that the studied area is highly impacted.

Superficial distribution of aromatic compounds and geomicrobiology of sediments from Suruí Mangrove, Guanabara Bay, RJ, Brazil

The distribution of selected aromatic compounds and microbiology were assessed in superficial sediments from Suruí Mangrove, Guanabara Bay. Samples were collected at 23 stations, and particle size, organic matter, aromatic compounds, microbiology activity, biopolymers, and topography were determined. The concentration of aromatic compounds was distributed in patches over the entire mangrove, and their highest total concentration was determinated in the mangrove's central area. Particle size differed from most mangroves in that Suruí Mangrove has chernies on the edges and in front of the mangrove, and sand across the whole surface, which hampers the relationship between particle size and hydrocarbons. An average @ 10 percent p/p of organic matter was obtained, and biopolymers presented high concentrations, especially in the central and back areas of the mangrove. The biopolymers were distributed in high concentrations. The presence of fine sediments is an important factor in hydrocarbon accumulation. With high concentration of organic matter and biopolymers, and the topography with chernies and roots protecting the mangrove, calmer areas are created with the deposition of material transported by wave action. Compared to global distributions, concentrations of aromatic compounds in Suruí Mangrove may be classified from moderate to high, showing that the studied area is highly impacted.

A distribuição de compostos aromáticos selecionados e a microbiologia foram avaliados em sedimentos superficiais do Manguezal de Suruí, Baía de Guanabara. Amostras foram coletadas em 23 pontos e determinados a granulometria, matéria orgânica, compostos aromáticos, atividade microbiológica, biopolímeros e a topografia. A concentração dos compostos aromáticos foi distribuída em manchas por todo o manguezal e sua concentração total mais elevada foi encontrada na área central do manguezal. A granulometria diferiu da maioria dos manguezais, uma vez que no Manguezal de Suruí existem chernies nas bordas e na frente dos manguezais e areia através da superfície inteira, impedindo o relacionamento entre granulometria e os hidrocarbonetos. Uma média de 10 por cento p/p da matéria orgânica foi obtida e os biopolímeros apresentaram concentrações elevadas, especialmente na área central e fundo do Manguezal. Os biopolímeros se distribuíram em altas concentrações. A presença de finos sedimentos é fator importante na acumulação de hidrocarbonetos. Na concentração elevada de matéria orgânica e de biopolímeros, topografia com chernies e as raízes que protegem os manguezais, áreas mais calmas são criadas, com depósito do material transportado pela ação das ondas. Comparadas às distribuições globais, as concentrações das substâncias aromáticas neste manguezal podem ser classificadas de moderadas a elevadas, demonstrando que a área estudada está altamente impactada.

Optimization of an improved analytical method for the determination of 1-nitropyrene in milligram diesel soot samples by high-performance liquid chromatography-mass spectrometry.

A method for determination of nitrated polycyclic aromatic hydrocarbons (NPAHs) in diesel soot by high-performance liquid chromatography-mass spectrometry with atmospheric pressure chemical ionization (APCI) and detection by ion-trap following ultrasonic extraction is described. The determination of 1-nitropyrene that it is the predominant NPAH in diesel soot was emphasized. Vaporization and drying temperatures of the APCI interface, electronic parameters of the MS detector and the analytical conditions in reversed-phase HPLC were optimized. The patterns of fragmentation of representative NPAHs were evaluated by single and multiple fragmentation steps and negative ionization led to the largest signals. The transition (247-->217) was employed for quantitative analysis of 1-nitropyrene. Calibration curves were linear between 1 and 15 microgL(-1) with correlation coefficients better than 0.999. Typical detection limit (DL) of 0.2 microgL(-1) was obtained. Samples of diesel soot and of the reference material (SRM-2975, NIST, USA) were extracted with methylene chloride. Recoveries were estimated by analysis of SRM 2975 and were between 82 and 105%. DL for 1-nitropyrene was better than 1.5 mg kg(-1), but the inclusion of an evaporation step in the sample processing procedure lowered the DL. The application of the method to diesel soot samples from bench motors showed levels

Determination of Cu, Fe, Mn and Zn by flame atomic absorption spectrometry in multivitamin/multimineral dosage forms or tablets after an acidic extraction.

This work presents the development of a methodology for the determination of Cu, Fe, Mn and Zn in samples of multivitamin/multimineral tablets, by flame atomic absorption spectrometry (FAAS), after extraction of the analytes with diluted hydrochloric acid solution. Several parameters that could influence the extraction process such as acid extraction solution concentration and nature, mixing mode (ultrasonic or magnetic stirring), extraction time and sample composition were evaluated. The obtained results showed that Fe, Mn and Zn were easily extracted with 1 mol/L HCl solution after 5 min of mixing with either ultrasonic or magnetic stirring for all studied samples. On the other hand, Cu extraction appeared to be more complex since it could only be extracted at the same conditions for silicate-free samples. For samples containing silicates the time of contact between solid sample and extraction solution presented remarkable influence, being necessary up to 12 h to achieve quantitative recovery with 1 mol/L HCl solution. The developed methodology was applied in the determination of Cu, Fe, Mn and Zn in seven commercially available multivitamin/multimineral tablets. The results obtained with the developed method were compared with those obtained after total digestion of samples using a closed-vessel microwave oven device.