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This work proposes an on-line digestion system employing 70% (w/w) hydrogen peroxide and UV radiation for producing hydroxyl radicals for the determination of chromium in beer samples by electrothermal atomization atomic absorption spectrometry (ETAAS). The digester system consists of a closed wooden box, which is painted black internally, containing a PTFE tube wrapped around a 15 W UV lamp. During the mineralization step, a peristaltic pump is employed to propel the sample solution over the UV lamp. The experimental factors UV irradiation time and hydrogen peroxide volume were optimized using a two-level full factorial design. Degradation curves at different pH conditions demonstrated that the digestion of beer is faster at alkaline pH. The results demonstrated that, in the presence of 70% H2O2 and 15 W UV radiation, 75% of the chromophore species is degraded with an irradiation time of 25 min. The degradation kinetic curves of beer samples under different conditions were also evaluated. The apparent kinetic constant (kapp) found for the process assisted by 70% H2O2 and 15 W UV light was 0.0668 min−1 (R2 = 0.9936). The on-line digestion procedure with a sample flow rate of 2 mL min−1 for 45 min allowed the determination of chromium in beer samples by ETAAS, utilizing the external calibration technique, with the analytical line 357.9 nm, in the presence of magnesium as chemical modifier with limits of detection and quantification of 0.86 and 2.90 μg L−1, respectively. The method accuracy was confirmed by the analysis of the certified reference material of ERM-CA713 wastewater provided by the European Reference Materials. Six beer samples were digested and the chromium was determined. The contents found varied from 4.26 to 33.28 μg L−1. Addition/recoveries tests were also performed to evaluate the accuracy method. The recoveries obtained varied from 93.2 to 96.4%.

This work reports the determination of mercury in fish samples purchased at a public market in Belem City, Brazil. The mercury quantification was performed using the DMA method, which allows limits of detection and quantification of 0.004 and 0.012 ng, respectively. Method accuracy was confirmed using a certified reference material of fish protein from (NRCC) National Research Council, Canada. The analyzed species were: Dourada (Brachyplatystoma rousseauxii), Filhote (Brachyplatystoma filamentosum), Pescada Branca (Cynoscion leiarchus), Piramutaba (Brachyplatystoma vaillanti). The mercury contents expressed as wet sample weight varied from 0.078 to 0.150 μg g-1. Afterward, the health risk assessment indices Estimated Weekly Intake (EWI), Target Hazard Quotient (THQ), and Maximum Safe Consuming Quantity (MSCQ) were applied to the analytical data, and the results obtained were exhaustively interpreted and discussed. All the indices demonstrated that the daily consumption of 25 g of these fishes does not pose a risk to the human health of the local population. However, these conclusions are preliminary and should not be used in public policy matters.

This work presents a critical review of multivariate techniques employed for optimization of methods developed in food analysis. A comparison between the response surface methodologies has been performed, it evidencing advantages and drawbacks of these. Applications of the main chemometric tools (central composite and Box Behnken designs and Doehlert matrix) often utilized for optimization of sample preparation procedures and also instrumental conditions of analytical techniques for determination of organic and inorganic species in food samples are shown. Also, a brief discussion on the use of multiple responses and robustness test in food analysis has been presented.

This paper proposes a closed inline system for decomposition of wine, aiming at the determination of lead using electrothermal atomization atomic absorption spectrometry (ETAAS). The system is built using a 0.8 mm diameter PTFE tube, which is wrapped around an 8 W UV lamp. The sample in the presence of 70% hydrogen peroxide is circulated on an 8 W UV lamp at the flow rate of 1 mL min−1 for 45 min. Under these conditions, the carbon content varied from 10% to 2% for a red wine sample before and after digestion, respectively. The system has allowed the determination of lead in wine samples using the analytical line 283.306 nm in the presence of aluminum as the chemical modifier and pyrolysis and atomization temperatures of 800 and 1800 °C, respectively. Then, lead can be quantified employing the external calibration technique with limits of detection 0.27 and quantification 0.89 µg L−1, and characteristics mass of 18 pg. The precision expressed by relative standard deviation (RSD%) was 2.13%, calculated using six replicates of a digested solution of a wine sample with the lead content of 16.35 µg L−1. For evaluation of the accuracy method, two wine samples were analyzed simultaneously by the method proposed and also by inductively coupled plasma mass spectrometry (ICP-MS). A statistical test demonstrated no significant difference between the means obtained by these two techniques. Also, experiments involving addition/recovery tests confirmed the method's accuracy. The system was employed for digestion and determination of lead in four Brazilian wine samples. The lead content varied from 2.19 to 43.48 µg L−1.

This work review shows a description of non-chromatographic and chromatographic procedures proposed for speciation analysis of antimony employing hydride generation (HG) coupled to atomic fluorescence spectrometry (AFS) in environmental matrices, including details of HG-AFS as the detection technique. Non-chromatographic procedures have been developed based on the determination of total antimony after a pre-reduction step. The main reductant agents used are discussed. Antimony(III) has been quantified in the presence of a masking agent. The most used are citrate and 8-hydroquinoline. Chromatographic procedures have been established utilizing High-Performance Liquid Chromatography (HPLC). Advantages and drawbacks of the main extracting agents and mobile phases employed in these procedures have been discussed. Also, alternatives to improve the method sensitivity during the determination of antimony(V) and its organic compounds by HPLC-HG-AFS are presented. Speciation procedures involving preconcentration steps have allowed methods with high sensitivity. Tables evidencing applications of non-chromatographic and chromatographic procedures in speciation studies of environmental samples are also shown. Advantages of automated and flow systems for antimony speciation studies are also highlighted.

This review presents fundamentals and a critical evaluation of the multivariate optimization techniques employed by the analytical chemistry. Characteristics of the surface response methodologies (SRM) are shown and compared. Additionally, a bibliographic survey was performed in the web of science database using as keywords names of the chemometric tools utilized for experimental designs. Papers classified in the analytical chemistry area demonstrated that the two-level full factorial design had often been used for preliminary assessment of factors. For determination of critical conditions using quadratic models, the central composite design (CCD) is the technique most utilized by the analytical chemists. Remarks about standardized effects and the Pareto chart, description of the several multiple response functions employed in experimental designs, efficiencies of the SRM's and robustness tests are also discussed.

This work proposes an on-line preconcentration system using ion-imprinted polymer (IIP) for determination of bismuth in seawater employing atomic fluorescence spectrometry (AFS). The polymer was synthesized using 2- (5-bromo-2-pyridylazo) -5-diethylaminophenol (Br-PADAP) for complex formation, ethylene glycol dimethacrylate (EGDMA), cross-linking reagent and methacrylic acid (AMA) reagents, used as the functional monomer, 2,2-azobisisobutyronitrile was used as the radical initiator. The polymer was characterized employing the Fourier transform infrared spectroscopy (FTIR) and scanning electron microscopy (SEM). The determination of bismuth was performed employing hydride generation atomic fluorescence spectrometry (HG AFS) and the experimental conditions were optimized using a Box Behnken design involving the factors sample pH, eluent concentration and sodium tetrahydroborate concentration. So, using the optimized conditions the system allows the determination of bismuth with limits of detection and quantification of 26 and 88 ng L−1, a preconcentration factor of 19.8. All these parameters were determined using a sample volume of 25 mL. The precision expressed as relative standard deviation (RSD%) was 3.7% for a bismuth(III) solution of concentration 0.25 µg L−1. The system proposed was applied for the determination of bismuth in four seawater samples collected in Salvador City, Bahia State, Brazil. The concentrations obtained varied from 0.38 to 0.45 μg L−1. The accuracy was evaluated by addition/recovery test, and the recoveries found varied from 92% to 101%.

This study describes the preparation of a novel ion-imprinted polymer (IIP) to apply pre-concentration of cadmium ions in water samples of the Pontal Bay in Ilheus, Brazil. First, cadmium ion was complexed with 2-(2-thiazolylazo)-p-cresol (TAC). Subsequently, there was the polymerization using ethylene glycol dimethacrylate and methacrylic acid monomers along with the radical azobisisobutyronitrile initiator. The mold ions were removed using 2:1 (v v-1) nitric acid. The thermal stability of the polymer was evaluated by thermogravimetry and the characterization was performed by Fourier transform infrared spectroscopy. The maximum adsorption capacity for IIP (qmax = 84.75 mg g-1) could be described by the Langmuir isotherm. The variables: sample flow rate, pH and eluent (nitric acid) were optimized using Box-Behnken design with determination by flame atomic absorption spectrometry (FAAS). The enrichment factor, as well as the limits of detection and quantification (LOQ), were found to be 44, 0.14 and 0.46 µg L-1, respectively. Selectivity was evaluated by using solutions containing CdII, CuII, NiII, PbII, CoII, SO42-, and Cl- ions. The concentration of cadmium ions in the samples varied between < LOQ to 1.25 µg L-1.

In the present work is described a new on-line solid-phase extraction system using a novel ion imprinted polymer as adsorbent for the preconcentration and determination of mercury(II) in natural water samples by Cold Vapor Atomic Fluorescence Spectrometry (CV AFS). The ion imprinted polymer was prepared by the improved bulk polymerization technique, occurring in only 3 h, based on mercury(II)-dithizone chelate, using methacrylic acid as monomer, ethylene glycol dimethacrylate as cross-linking reagent, 2,2′‑azobisisobutyronitrile as radical initiator, and dimethyl sulfoxide and acetonitrile as porogen solvents. The obtained polymer was characterized by Fourier Transform Infrared Spectroscopy (FTIR), Scanning Electron Microscopy (SEM), Thermogravimetry (TG), Derivative Thermogravimetry (DTG) and X-ray Diffraction (XRD). The on-line system was mounted by the easy coupling the mini-column packed with the Hg2+-IIP sorbent to the cold vapor system of the spectrometer. The optimum experimental conditions for the on-line preconcentration system were established employing multivariate methodology (two-level full factorial design and Doehlert matrix). Under the optimized conditions, limits of detection and quantification of 0.02 and 0.06 μg L−1, and preconcentration factor of 29 were obtained for the determination of mercury using the developed on-line system, considering a sample volume of 50 mL. Precision expressed as a relative standard deviation (RSD%) was of 5.2% (n = 7) for a standard solution with mercury(II) concentration of 0.5 μg L−1. Then, the on-line system was applied for the selective preconcentration and determination of mercury (II) in four natural water samples, and addition/recovery tests were performed to evaluate the accuracy of the method. All analyzed samples presented Hg2+ concentrations below the limit of quantification of the proposed method and the recovery values found were in range from 90 to 105%.