Reference concentrations for trace elements in urine for the Brazilian population based on q-ICP-MS with a simple dilute-and-shoot procedure

Biomonitoring of trace elements is of critical importance in human health assessment. However, trace element concentrations in biological fluids are affected by environmental and physiological parameters, and therefore considerable variations can occur between specific population subgroups. Brazil is a large country with large environmental diversity and with a limited knowledge of the reference values (baseline data) for trace elements in biological fluids. Atomic absorption spectrometry (AAS) and inductively coupled plasma emission spectrometry (ICP-OES) are still the dominant analytical techniques used for biomonitoring trace element analysis in clinical specimens. However, the use of ICP-MS is becoming more usual in clinical laboratory analysis. Then, we evaluated here a simple dilute-and-shoot method for sequential determination of Al, Ba, Be, Cd, Co, Cu, Cs, Mn, Ni, Pb, Pt, Sb, Se, Sn, Tl and U in urine by quadrupole inductively coupled plasma mass spectrometry (q-ICP-MS). Urine samples (500 µL) were accurately pipetted into conical tubes (15 mL) and diluted to 10 mL with a solution containing 0.5 % (v/v) HNO3 + 0.005% (v/v) Triton X-100. Diluted urine samples also contain rhodium, iridium and yttrium added as internal standards. After that, samples were directly analyzed by ICP-MS against matrix-matching calibration. Method detection limit (3s, n = 20) were in the ng L-1 range for all analytes. The method was applied to the analysis of 412 ordinary urine samples from Brazilian healthy and non-exposed subjects to establish reference values. Data validation was provided by the analysis of the standard reference material (SRM) 2670a toxic elements in urine (freeze-dried) (high and low levels) from the National Institute of Standards and Technology (NIST) and reference urine samples from the trace elements intercomparison program operated by the Institut National de Sante' Publique du Quebec, Canada.O biomonitoramento de elementos químicos é de extrema importância na avaliação da saúde humana. Entretanto, as concentrações dos elementos químicos nos fluidos biológicos são afetadas por parâmetros ambientais e fisiológicos e, consequentemente, consideráveis variações podem ocorrer entre subgrupos de populações específicas. O Brasil é um país com ampla diversidade ambiental e existe limitado conhecimento de valores de referência para elementos químicos em fluidos biológicos. A espectrometria de absorção atômica (AAS) e a espectrometria de emissão ótica com plasma acoplado indutivamente (ICP-OES) ainda são as técnicas analíticas mais comumente empregadas no biomonitoramento de elementos químicos em amostras clínicas. Entretanto, o uso da espectrometria de massas com plasma acoplado indutivamente (ICP-MS) está se tornando a cada dia mais comum nos laboratórios clínicos. Neste estudo, foi avaliado um método rápido envolvendo simples diluição da amostra para determinação de Al, Ba, Be, Cd, Co, Cu, Cs, Mn, Ni, Pb, Pt, Sb, Se, Sn, Tl e U em urina por ICP-MS. Amostras de urina (500 μL) foram pipetadas em frascos cônicos de 15 mL e diluídas para 10 mL com uma solução contendo 0,5 % (v/v) HNO3 + 0,005% (v/v) Triton X-100. Ródio, irídio e ítrio foram adicionados como padrões internos. Em seguida, as amostras foram diretamente analisadas por ICP-MS com calibração por ajuste de matriz. Os limites de detecção do método (3s, n = 20) foram da ordem de ng L-1 para todos os analitos em estudo. O método foi aplicado para a análise de 412 amostras de urina de brasileiros saudáveis e não expostos ambientalmente ou ocupacionalmente a metais para o estabelecimento de valores de referência na população brasileira. A validação dos resultados foi acompanhada pela análise de material de referência certificada de urina (SRM) 2670a proveniente do National Institute of Standards and Technology (NIST) e de materiais de referência provenientes do Institut National de Sante' Publique Du Quebec, no Canadá.Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq

Determination of Cd and Pb in fuel ethanol by filter furnace electrothermal atomic absorption spectrometry

A method was developed for quantification of Cd and Pb in ethanol fuel by filter furnace atomic absorption spectrometry. Filter furnace was used to eliminate the need for chemical modification, to stabilize volatile analytes and to allow the application of short pyrolysis step. The determinations in samples were carried out against calibration solutions prepared in ethanol. Recovery tests were made in seven commercial ethanol fuel samples with values between 90 and 120%. Limits of detection were 0.1 µg L-1 for Cd and 0.3 µg L-1 for Pb. Certified water samples (APS 1071, APS 1033, NIST 1643d, NIST 1640) were also used to evaluate accuracy and recoveries from 86.8% to115% were obtained

Calibration techniques and modifiers for the determination of Cd, Pb and Tl in biodiesel as microemulsion by graphite furnace atomic absorption spectrometry

Different calibration approaches and modifiers were tested for Cd, Pb and Tl determination in biodiesel by graphite furnace atomic absorption spectrometry (GF AAS). Microemulsions were prepared by mixing 2 g of biodiesel, 1 mL of a 10% (v/v) nitric acid aqueous solution and n-propanol to a 10 mL final volume. Pyrolysis temperatures of 600 °C for Cd and Tl with Pd as permanent modifier, and 800 °C for Pb with Ru as permanent modifier were used. Atomization temperatures were also optimized. Calibration solution prepared in aqueous medium did not correct non-spectral interferences, but matrix matching calibration using base oil led to accurate results with recoveries from 80 to 116%. The RSD values were lower than 8% for Cd and Pb and the LOD values were 0.5 ng g-1 for Cd, 6 ng g-1 for Pb and 1 ng g-1 for Tl. The obtained results using the analyte additions method or by matrix matching calibration were in agreement, confirming the accuracy of the proposed procedure. Organometallic standards were not required and different samples were analyzed

Dispersive liquid–liquid microextraction using ammonium O,O-diethyl dithiophosphate (DDTP) as chelating agent and graphite furnace atomic absorption spectrometry for the determination of silver in biological samples

A new method for the determination of silver in biological samples is presented in this work. The method involves application of dispersive liquid–liquid microextraction (DLLME) employing ammonium O,O-diethyl dithiophosphate (DDTP) as the chelating agent for extraction and preconcentration of silver prior to quantification using graphite furnace atomic absorption spectrometry (GFAAS). Chloroform and acetone were selected as the extracting and dispersing solvent, respectively, at optimized volumes of 80 mL and 500 mL, respectively. The concentration of DDTP and the extraction time were optimized as 0.01% (m/v) and 10 min, respectively. Pyrolysis (1100 C) and atomization (1800 C) temperatures were optimized using a L'vov platform treated with 400 mg of tungsten as a permanent chemical modifier. The method was proven virtually free from interference from major constituents of biological samples. A detection limit of 2 ng g 1 was obtained with relative standard deviations better than 13% and an enhancement factor of 70 was achieved. The determined concentrations for Ag in certified reference biological samples were in good agreement with the certified values at a 95% statistical confidence limit. The reported method using DLLME and GFAAS presented good analytical performance for Ag determination when compared to other methods available in the literature