Novel extraction induced by microemulsion breaking: a model study for Hg extraction from Brazilian gasoline.

This paper proposes a novel approach for the extraction of Hg from Brazilian gasoline samples: extraction induced by microemulsion breaking (EIMB). In this approach, a microemulsion is formed by mixing the sample with n-propanol and HCl. Afterwards, the microemulsion is destabilized by the addition of water and the two phases are separated: (i) the top phase, containing the residual gasoline and (ii) the bottom phase, containing the extracted analyte in a medium containing water, n-propanol and the ethanol originally present in the gasoline sample. The bottom phase is then collected and the Hg is measured by cold vapor atomic absorption spectrometry (CV-AAS). This model study used Brazilian gasoline samples spiked with Hg (organometallic compound) to optimize the process. Under the optimum extraction conditions, the microemulsion was prepared by mixing 8.7mL of sample with 1.2mL of n-propanol and 0.1mL of a 10molL-1 HCl solution. Emulsion breaking was induced by adding 300µL of deionized water and the bottom phase was collected for the measurement of Hg. Six samples of Brazilian gasoline were spiked with Hg in the organometallic form and recovery percentages in the range of 88-109% were observed.

Development of a method for total Hg determination in oil samples by cold vapor atomic absorption spectrometry after its extraction induced by emulsion breaking.

This work reports the development of a novel extraction method for total Hg determination in oil samples. After extracting Hg from samples it was quantified in the extracts by cold vapor atomic absorption spectrometry (CV-AAS), employing a laboratory-made gas-liquid separator (GLS) and NaBH4 as reducing agent. The extraction of Hg from samples was carried out by extraction induced by emulsion breaking (EIEB), which is based on the formation and breaking of water-in-oil emulsion between the oil samples and an extractant solution containing an emulsifying agent (surfactant) and nitric acid. Operational parameters of the GLS were evaluated in order to set the best performance of the measurement system. In these studies it was proven that the volume of sample and the concentration of HCl added to the sample extracts had significant influence on Hg response. The best conditions were achieved by adding 0.5 mL of a 0.3 mol L(-1) HCl solution on 1 mL of sample extract. The extraction conditions were also optimized. The highest efficiency was observed when 4 mL of a solution containing 2.5% triton X-100 and 15% v/v HNO3 were employed for the extraction of Hg contained in 20 mL of sample. Emulsion breaking was performed by heating at 80 °C and took approximately 20 min. The limit of quantification of the method was 1.9 µg L(-1) and recovery percentages between 80% and 103% were observed when spiked samples (2 and 10 µg L(-1)) of diesel oil, biodiesel and mineral oil were analyzed.

Determination of mercury and methylmercury in fish and hair samples / Determinação de mercúrio e metilmercúrio em amostras de cabelo e peixes

The cold vapor atomic absorption spectrometry (CVAAS) is one of the most useful analytical technique for mercury and methylmercury determinations in biological materials due to several advantagens such as operation facility, fast analytical response, good sensitivity and low cost. This study also shows the results obtained by our laboratory in the World-Wide Intercomparison Exercise for the Determination of Trace Elements and Methylmercury in Tuna Fish Flesh Homogenate (IAEA-436), during the period of October 2004 and July 2005. The precision and accuracy of the method for total mercury and MeHg determinations were verified by means of the reference material analyses. The results obtained showed good precision and accuracy with relative standard deviation ranged from 2.2 to 10 % and relative error from 0.4 to 12% for MeHg and relative standard deviation ranged from 2.6 to 11.7 % and relative error from 0.9 to 3.1% for Hg. The method presented has been shown to be suitable for determination of background levels of these contaminants in fish and hair samples and can be used in studies related to the health effects of mercury and its species in man.

A Espectrometria de Absorção Atômica com Geração de Vapor Frio (CVAAS) está entre os métodos mais utilizados atualmente para a determinação de mercúrio (Hg) e metilmercúrio (MeHg) em materiais biológicos devido a vantagens, tais como: facilidade de operação, rápida resposta analítica, boa sensibilidade e baixo custo. Neste estudo apresentam-se os resultados obtidos no programa de intercomparação da Agência Internac ional de Energia Atômica (IAEA) o World-Wide Intercomparison Exercise for the Determination of Trace Elements and Methylmercury in Tuna Fish Flesh Homogenate (IAEA-436), realizado no período de outubro de 2004 a julho de 2005. A precisão e a exatidão do método para determinação de Hg e MeHg foram verificadas por meio da análise de materiais de referência com valores certificados para ambos. Os resultados obtidos apresentaram boa precisão e exatidão, com desvio padrão relativo de 2,2 a 10 % e erro relativo, de 0,4 a 12% para MeHg e desvio padrão relativo de 2,6 a 11,7% e erro relativo, de 0,9 a 3,11%, para Hg. O método apresentado mostrou-se adequado para determinação de baixos níveis destes contaminantes em amostras de cabelo e peixe e pode ser usado em estudos relacionados aos efeitos do Hg e suas espécies na saúde do ser humano.

Determinaçäo dos teores de Hg, Pb, Cd, Cu e Zn em moluscos (Crassostrea brasiliana, Perna perna e Mytella falcata) / Determination of Pb, Cd, Hg, Cu and Zn levels in molluscs (Crassostrea brasiliana, Perna perna and Mytella falcata)

Os moluscos bivalves quando ingeridos podem oferecer risco à saúde pública por serem organismos filtradores e bioacumuladores de resíduos químicos e biológicos. O objetivo deste trabalho foi determinar os teores de Hg, Pb,Cd, Cu e Zn nos bivalves C.brasiliana, P.perna e M.falcata coletados em vários bancos naturais do litoral da Baixada Santista. No período de setembro de 1996 a fevereiro de 1997, foram coletadas e analisadas 70 amostras provenientes de doze bancos naturais. As determinaçöes analíticas de Hg no tecido mole dos bivalves foram realizadas por espectrometria de absorçäo atômica com gerador de vapor frio, enquanto que o Pb, Cd, Zn e Cu foram analisados por ICP OES. Os resultados revelaram que as amostras apresentaram níveis de concentraçäo permitidas pelas normas legais vigentes com relaçäo aos teores de Pb, Cd, Hg e Cu analisados. Todas as amostras de mexilhäo e sururu analisadas apresentaram teores de zinco abaixo do valor estabelecido pela legislaçäo brasileira, que é de 50,0 mg/kg, exceto todas as amostras de ostras C. brasiliana. (AU)

Bivalves as filter-feeders and bioaccumulators of chemical and biological residues canoffer risk to public health when consumed by the population. This study aims at determining Pb, Cd, Hg,Cu and Zn levels in bivalves C. brasiliana, P. perna and Mytella falcata collected in several naturalsandbanks in the coastal Baixada Santista, São Paulo. Seventy samples from twelve natural sandbankswere collected and analyzed from September 1996 to February 1997. Mercury concentration in soft tissuesof bivalves was determined by continuos flow injection ­ flameless atomic absorption spectrometry. Pb,Cd, Zn and Cu were determined by Inductively Coupled Plasma Optical Emission Spectrometry (ICP OES).The results showed that Pb, Cd, Hg and Cu levels in samples were according to Brazilian legislation. Theconcentration of Zn for all samples of oyster C. brasiliana was higher than those indicated by legal limitsfor foods in Brazil, that is 50 mg/kg; for other samples the Zn levels were below the levels established forBrazilian legislation. (AU)