RESUMO

This paper proposes the use of a multisyringe flow injection analysis (MSFIA) system for inorganic antimony speciation analysis, trimethyl antimony(V) and determination of total antimony in soil samples using hydride generation atomic fluorescence spectrometry (HG-AFS). Total antimony has been determined after reduction of antimony(V) to antimony(III) using potassium iodide and ascorbic acid. For determination of total inorganic antimony the sample is percolated in a mini-column containing the Dowex 50W-X8 resin for retention of the organic species of antimony. Antimony(III) is quantified in presence of 8-hydroxyquinoline as masking agent for antimony(V) after an extraction step of the organic antimony species using the also same mini-column. The trimethyl antimony(V) content is found by difference between total antimony and total inorganic antimony. By other hand, antimony(V) is quantified by difference between total inorganic antimony and antimony(III). The analytical determinations were performed using sodium tetrahydroborate as reducing agent. The optimization step was performed using two-level full factorial design and Doehlert matrix involving the factors: hydrochloric acid and sodium tetrahydroborate concentrations and sample flow rate. The optimized experimental conditions allow the antimony determination utilizing the external calibration technique with limits of detection and quantification of 0.9 and 3.1ngg-1, respectively, and a precision expressed as relative standard deviation of 3.2% for an antimony solution of 5.0µgL-1. The method accuracy was confirmed by analysis of the soil certified reference material furnished from Sigma-Aldrich RTC. Additionally, addition/recovery tests were performed employing synthetic solutions prepared using trimethyl antimony(V), antimony(III), antimony(V) and five soil samples. The antimony extraction step was performed in a closed system using hydrochloric acid, ultrasonic radiation and controlled temperature. The method proposed was applied for analysis of thirteen soil samples collected in different sites of the Balearic Islands, Spain, and the results obtained varied from 19 to 46ngg-1 for trimethyl antimony(V) and from 113 to 215ngg-1 for total inorganic antimony. The concentrations obtained to antimony(V) were always higher than for antimony(III) in all the analyzed samples.

RESUMO

This paper proposed a multisyringe flow injection analysis (MSFIA) system for antimony, arsenic and selenium determination in peanut samples by hydride generation atomic fluorescence spectrometry (HG-AFS). The optimization step of the hydride generation was performed using a two-level full factorial design involving the parameters: hydrochloric acid, sodium tetrahydroborate and potassium iodide concentrations. So, using the chemical conditions optimized, this method allows the determination of these elements employing the external calibration technique using aqueous standards with limits of detection and quantification of 0.04 and 0.14µgL(-1) for antimony, 0.04 and 0.14µgL(-1) for arsenic and 0.14 and 0.37µgL(-1) for selenium, respectively. Additionally, the effect of vanadium, chromium, cobalt, nickel, zinc, copper, iron and molybdenum on the generation of chemical vapour was also studied. The precision expressed as relative standard deviation varied from 1.2 to 3.6% for antimony, 1.8-3.9% for arsenic and 1.8-2% for selenium. The accuracy for arsenic and selenium was confirmed using the certified peach leaves reference material SRM 1547 produced by National Institute of Standard and Technology. The proposed method showed 45 injection throughput (h(-1)) using 1.6mL sample volume for each element, 0.8mL NaBH4 0.5% (w/v) containing NaOH 0.05% (w/v), 0.8mL HCl 5M and 0.4mL KI 14% (w/v) containing L-ascorbic acid 2.5% (w/v). The method was applied to the determination of antimony, arsenic and selenium in peanut samples, which were firstly lyophilized and afterward digested using microwave assisted radiation. Six samples were analyzed and the contents of the elements found were: 28.7-41.3µgkg(-1) for arsenic, 86.4-480.1µgkg(-1) for selenium and 32.6-52.4µgkg(-1) for antimony. Addition/recovery tests were also performed to confirm the method accuracy for the three elements.

RESUMO

Most of the procedures for antimony determination require time-consuming sample preparation (e.g. liquid-liquid extraction with organic solvents), which are harmful to the environment. Because of the high antimony toxicity, a rapid, sensitive and greener procedure for its determination becomes necessary. The goal of this work was to develop an analytical procedure exploiting for the first time the cloud point extraction on a lab-in-syringe flow system aiming at the spectrophotometric determination of antimony. The procedure was based on formation of an ion-pair between the antimony-iodide complex and H(+) followed by extraction with Triton X-114. The factorial design showed that the concentrations of ascorbic acid, H2SO4 and Triton X-114, as well as second and third order interactions were significant at the 95% confidence level. A Box-Behnken design was applied to obtain the response surfaces and to identify the critical values. System is robust at the 95% confidence level. A linear response was observed from 5 to 50 µg L(-1), described by the equation A=0.137+0.050C(Sb) (r=0.998). The detection limit (99.7% confidence level), the coefficient of variation (n=5; 15 µg L(-1)) and the sampling rate was estimated at 1.8 µg L(-1), 1.6% and 16 h(-1), respectively. The procedure allows quantification of antimony in the concentrations established by environmental legislation (6 µg L(-1)) and it was successfully applied to the determination of antimony in freshwater samples and antileishmanial drugs, yielding results in agreement with those obtained by HGFAAS at the 95% confidence level.

RESUMO

A dedicated pressure-driven mesofluidic platform incorporating on-chip sample clean-up and analyte preconcentration is herein reported for expedient determination of trace level concentrations of waterborne inorganic mercury. Capitalizing upon the Lab-on-a-Valve (LOV) concept, the mesofluidic device integrates on-chip micro-solid phase extraction (µSPE) in automatic disposable mode followed by chemical vapor generation and gas-liquid separation prior to in-line atomic fluorescence spectrometric detection. In contrast to prevailing chelating sorbents for Hg(II), bare poly(divinylbenzene-N-vinylpyrrolidone) copolymer sorptive beads were resorted to efficient uptake of Hg(II) in hydrochloric acid milieu (pH=2.3) without the need for metal derivatization nor pH adjustment of prior acidified water samples for preservation to near-neutral conditions. Experimental variables influencing the sorptive uptake and retrieval of target species and the evolvement of elemental mercury within the miniaturized integrated reaction chamber/gas-liquid separator were investigated in detail. Using merely <10 mg of sorbent, the limits of detection and quantification at the 3s(blank) and 10s(blank) levels, respectively, for a sample volume of 3 mL were 12 and 42 ng L(-1) Hg(II) with a dynamic range extending up to 5.0 µg L(-1). The proposed mesofluidic platform copes with the requirements of regulatory bodies (US-EPA, WHO, EU-Commission) for drinking water quality and surface waters that endorse maximum allowed concentrations of mercury spanning from 0.07 to 6.0 µg L(-1). Demonstrated with the analysis of aqueous samples of varying matrix complexity, the LOV approach afforded reliable results with relative recoveries of 86-107% and intermediate precision down to 9% in the renewable µSPE format.

Assuntos

RESUMO

In this paper is proposed a simultaneous pre-concentration procedure using cloud point extraction for the determination of copper and zinc in food samples employing sequential multi-element flame atomic absorption spectrometry (FS-FAAS). The reagent used is 1-(2-pyridylazo)-2-naphthol (PAN) and the micellar phase is obtained using the non-ionic surfactant octylphenoxypolyethoxyethanol (Triton X-114) and centrifugation. The optimization step was performed using Box-Behnken design for three factors: solution pH, reagent concentration and buffer concentration. A multiple response function was established in order to get an experimental condition for simultaneous extraction of copper and zinc. Under the optimized experimental conditions, the method allows the determination of copper with a limit of detection (3sigma(b)/S, LOD) of 0.1 microg L(-1), precision expressed as relative standard deviation (R.S.D.) of 2.1 and 1.3% (N=10), for copper concentrations of 10 and 50 microg L(-1), respectively. Zinc is determined with a LOD of 0.15 microg L(-1) and precision as R.S.D. of 2.7 and 1.7% for concentrations of 10 and 50 microg L(-1), respectively. The enhancement factors obtained were 36 and 32 for copper and zinc, respectively. The accuracy was assessed by analysis of certified reference materials, namely, SRM 1567a - Wheat Flour and SRM 8433 - Corn Bran from National Institute of Standards & Technology and BCR 189-wholemeal flour from Institute of Reference Materials and Measurements. The method was applied to the determination of copper and zinc in oats, powdered chocolate, corn flour and wheat flour samples. The copper content in the samples analyzed varied from 1.14 to 3.28 microg g(-1) and zinc from 8.7 to 22.9 microg g(-1).

Assuntos