A simple and sensitive spectrophotometric method is proposed for the simultaneous determination of protocatechuic acid and protocatechuic aldehyde. The method is based on the difference in the kinetic rates of the reactions of analytes with [Ag(NH3)2]+ in the presence of polyvinylpyrrolidone to produce silver nanoparticles. The data obtained were processed by chemometric methods using principal component analysis artificial neural network and partial least squares. Excellent linearity was obtained in the concentration ranges of 1.23-58.56 µg mL-1 and 0.08-30.39 µg mL-1 for PAC and PAH, respectively. The limits of detection for PAC and PAH were 0.039 and 0.025 µg mL-1, respectively.

Silver ion imprinted polymer (IIP) was synthesized in the presence of Ag(I)-N,N’‑bis(salicylidene)ethylenediamine (salen) complex using 4-vinylpyridine as the functional monomer, ethylene glycol dimethacrylate (EGDMA) as the crosslinker, and 2,2-azobis(isobutyronitrile) (AIBN) as the initiator. The Ag(I)-imprinted polymer (IIP) particles were characterized by SEM (scanning electron microscope), FTIR (Fourier transform infrared spectroscopy) and BET/BJH (Brunauer-Emmett-Teller/Barrett-Joyner-Halenda) analysis. The imprinted Ag(I) ions were completely removed by leaching the IIP with thiourea (0.5 mol L-1). The polymer was employed as a selective sorbent for extraction and separation of the trace amounts of the Ag(I) ions. The preconcentrated ion was determined via the flame atomic absorption spectrometry (FAAS) or it was reduced to silver nanoparticles and quantified by spectrophotometry based on its localized surface plasmon resonance peak (LSPRP). The figures of merit of both methods were compared. Under the optimized conditions, a sample volume of 80 mL resulted in an enhancement factor of 312. The detection limit (3Sb/m) and the relative standard deviation (n = 10) at 10 µg L-1 level for FAAS were found to be 0.06 µg L-1, 2.9%, whereas for the LSPRP method they were 0.5 µg L-1 and 10.3%, respectively. The methods were successfully applied to the determination of silver in radiology film, hair, nails, and water samples.

O cádmio de uma amostra aquosa foi quantitativamente adsorvido em uma microcoluna empacotada com cadion imobilizado em nanopartículas de TiO2 recobertas por dodecilsulfato de sódio. O cádmio retido foi eluido com uma solução de ácido clorídrico 2,5 mol L-1 e medido por espectroscopia de absorção atômica com vapor frio (CVAAS). As influências de diferentes variáveis, como pH, taxas de fluxo da amostra e do eluente, quantidade do sorvente e volume da amostra, na recuperação do cádmio foram investigadas. Sob condições ótimas, um volume de 200 mL de amostra resultou em um fator de pré-concentração de 100. A precisão (RSD%, n = 8) em 0,05 µg L-1 de cádmio foi 3,6% e o limite de detecção, baseado em três vezes o desvio padrão do branco (3Sb), foi de 1,3 ng L-1. O método foi aplicado com sucesso à determinacão de cádmio em amostras de arroz, peixe, leite e água.

Cadmium was quantitatively adsorbed from aqueous sample onto a microcolumn packed with cadion immobilized on sodium dodecyl sulfate-coated TiO2 nanoparticles. The retained cadmium was eluted with 2.5 mol L-1 hydrochloric acid solution and measured by cold vapor atomic absorption spectrometry (CVAAS). The influences of different variables such as pH, sample and eluent flow rates, amount of the sorbent and volume of the sample on the recovery of cadmium were investigated. Under the optimum conditions, a sample volume of 200 mL resulted in a preconcentration factor of 100. The precision (RSD%, n = 8) at the 0.05 µg L-1 level of cadmium was 3.6% and the limit of detection based on three times the standard deviation of blank solution (3Sb) was 1.3 ng L-1. The method was successfully applied to the determination of cadmium in rice, fish, milk, and water samples.

A dispersive liquid-liquid microextraction based on solidification of floating organic drop for simultaneous extraction of trace amounts of nickel, cobalt and copper followed by their determination with electrothermal atomic absorption spectrometry was developed. 300 µL of acetone and 1-undecanol was injected into an aqueous sample containing diethyldithiocarbamate complexes of metal ions. For a sample volume of 10 mL, enrichment factors of 277, 270 and 300 and detection limits of 1.2, 1.1 and 1 ng L-1 for nickel, cobalt and copper were obtained, respectively. The method was applied to the extraction and determination of these metals in different water samples.

A extração por ponto nuvem (CPE) é proposta como um procedimento de separação e pré-concentração para a determinação de cádmio em amostras de água por espectrometria de absorção atômica com chama associada a sistema de injeção em fluxo (FI-FAAS). O íon cádmio em solução aquosa foi convertido a [CdI4]2- e sua carga foi neutralizada pela formação do par iônico com o cátion metiltrioctilamônio na presença de TritonX-114 como surfactante não iônico. A separação de fases foi obtida pelo aquecimento da mistura a 80 ºC por 10 min. A fase rica em surfactante foi diluída com 300 µL de etanol e 100 µL foram analisados por FI-FAAS. Os parâmetros que influenciam a formação do par iônico e extração foram otimizados. Sob condições ótimas, a pré-concentração de 35 mL de amostra na presença de 0,04% (v/v) de Triton X-114 possibilitou um limite de detecção de 0,3 µg L-1 de Cd(II). A curva analítica de calibração foi linear até 250 µg L-1 de cádmio e o desvio padrão relativo foi inferior a 4% para uma solução contendo 100 µg L-1 de Cd. O procedimento gerou recuperações no intervalo de 95-102%. O procedimento foi aplicado com sucesso para a determinação de cádmio em água de torneira, água de mar e em material de referência certificado de concentrado de cobre.

Cloud point extraction (CPE) is proposed as a separation and preconcentration procedure for determination of cadmium in water samples by flow injection flame atomic absorption spectrometry (FI-FAAS). The cadmium ion in aqueous solution was converted to [CdI4]2- and its charge was neutralized through ion-pair formation with methyltrioctylammonium cation in the presence of Triton X-114 as a non ionic surfactant. Phase separation was achieved by heating the mixture to 80 ºC for 10 min. The surfactant-rich phase was diluted with 300 µL of ethanol and 100 µL of it was analysed by FI-FAAS. The parameters affecting the ion-pair formation and extraction steps were optimized. Under optimum condition, preconcentration of 35 mL of sample in the presence of 0.04% (v/v) of Triton X- 114 led to a detection limit of 0.3 µg L-1 of Cd(II). Analytical calibration curve was linear up to 250 µg L-1 of cadmium and relative standard deviation was lower than 4% at 100 µg L-1 level. The procedure affords recoveries in the range of 95-102%. The procedure was successfully applied to the determination of Cd in tap water, sea water and certified reference copper concentrate.

Um sistema de injeção em fluxo sensível e simples foi desenvolvido para separação, préconcentração e determinação de tálio. A pré-concentração é baseada na sorção do analito em uma microcoluna de dibenzo-18-coroa-6 (DB18C6) imobilizada em alumina revestida com surfactante e subseqüente eluição com solução de ácido nítrico (500 µL, 2 mol L-1). A concentração de tálio no eluente foi determinada por espectrometria de absorção atômica com atomização eletrotérmica. Os fatores que influenciaram a sorção e dessorção de íon tálio foram investigados. Para um volume da amostra de 5 mL, a calibração foi linear no intervalo de 0,1 a 20 µg L-1 (r = 0,9996) com um limite de detecção de 0,05 µg L-1. A capacidade máxima de sorção foi de 1432 µg de tálio por grama do sorbente. A precisão do método para 1 µg L-1 foi 5,7% RSD (n = 11). O método foi aplicado para determinação de tálio em água, cabelo, unha e em materiais de referência certificados. A exatidão foi avaliada empregando experimentos de adição e recuperação ou por comparação dos resultados com materiais de referência certificados.

A simple and sensitive flow injection system was developed for separation, preconcentration and determination of thallium. Preconcentration is based on the analyte sorption on a microcolumn of dibenzo-18-crown-6 (DB18C6) immobilized on surfactant coated alumina with subsequent elution using a nitric acid solution (500 µL, 2 mol L-1). The concentration of thallium in the eluent was determined using electrothermal atomic absorption spectrometry. Factors influencing the sorption and desorption of thallium ion were investigated. Using a sample volume of 5 mL, the calibration was linear from 0.1 to 20 µg L-1 range (r = 0.9996) with a detection limit of 0.05 µg L-1. The maximum sorption capacity was 1432 µg of thallium per gram of sorbent. The precision of the method at 1 µg L-1 was 5.7% RSD (n = 11). The method was applied for determination of thallium in water, hair, nail, and standard reference samples. The accuracy was assessed using addition-recovery experiment or by comparison of the results with certified reference materials.