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This work reports assessing risks to human health resulting from mercury levels in sardines (Sardinella brasiliensis), which have been highly consumed by the low-income population from Salvador, Brazil. Mercury was determined using the Direct Mercury Analysis (DMA) in fifty-one commercially acquired samples in seventeen neighborhoods. The mercury content on a wet basis ranged from 0.023 to 0.083 µg g-1 for an average value of 0.039 µg g-1. The estimated weekly intake (EWI), target hazard quotient (THQ), and maximum safe consuming quantity (MSCQ) were used in the toxicological assessment, and all these indices denoted that this food does not pose any risks to the human health of the population that consumes it. The development of this work was very significant because most sardines sold in Salvador originate from Todos os Santos Bay, which has a history of mercury contamination.

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This work proposes the synthesis of a new polymer with imprinted ions (IIP) for the pre-concentration of uranium in natural waters using digital imaging as a detection technique. The polymer was synthesized using 2-(5-bromo-2-pyridylazo)-5-diethylaminophenol (Br-PADAP) for complex formation, ethylene glycol dimethacrylate (EGDMA) as a crosslinking reagent, methacrylic acid (AMA) as functional monomer, and 2,2'-azobisisobutyronitrile as a radical initiator. The IIP was characterized by Fourier transform infrared spectroscopy and scanning electron microscopy (FTIR). Uranium determination was performed using digital imaging (ID), and some experimental conditions (sample pH, eluent concentration, and sampling flow rate) were optimized using a two-level full factorial design and Doelhert response surface methodology. Thus, using the optimized conditions, the system allowed the determination of uranium with detection and quantification limits of 2.55 and 8.51 µg L-1, respectively, and a pre-concentration factor of 8.2. All parameters were determined using a 25 mL sample volume. The precision expressed as relative deviation (RSD%) was 3.5% for a solution with a concentration of 50 µg L-1. Given this, the proposed method was used for the determination of uranium in four samples of natural waters collected in the city of Caetité, Bahia, Brazil. The concentrations obtained ranged from 35 to 75.4 µg L-1. The accuracy was evaluated by the addition/recovery test, and the values found ranged between 91 and 109%.

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This work reports the quantification of total mercury in sediments collected in periods with and without rain from the Joanes River, Bahia, Brazil. Determinations were made using Direct Mercury Analysis (DMA), the accuracy of which was confirmed with two certified reference materials. The highest total mercury concentrations were found at the sampling point close to commercial areas and large residential condominiums. On the other hand, the lowest levels were found in the site close to a mangrove region. The geoaccumulation index was applied to the total mercury results, evidencing low contamination in the region studied. The contamination factor showed that of the seven stations investigated, four samples collected in the rainy season showed moderate contamination. The results of the ecological risk assessment were utterly consistent with the contamination factor data. This study showed that the smaller sediment particles concentrate more mercury, corroborating what has been predicted by the adsorption processes.

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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.

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Matrix complexity of fruit juices and their low antimony level requires sensitive, cost-effective instruments, time-consuming and error-prone sample pretreatment methods. Therefore, a flow-batch procedure (HG-FBA-AFS) was developed for the fast and sensitive determination of total inorganic Sb in grape juice samples by hydride generation atomic fluorescence spectrometry. The sample pretreatment, pre-reduction and stibine formation steps run through the mixing chamber. The HCl and NaBH4 concentrations, and carrier gas flowrate were optimized through a Box-Behnken design. The detection limit (LOD) was 20 ng L-1, intra and inter-day precision ranged in 3.0 - 3.5 %, and low errors within (- 2.4 to 6.6 %) for samples containing 1.23 - 4.58 µg L-1 total Sb. Both HG-FBA-AFS and reference method agreed at 95% confidence level. An 87 h-1 sample throughput, and a 1.15 mL total waste per determination attest that HG-FBA-AFS is a fast, and ecofriendly tool for determining Sb in grape juices.

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The Joanes River is located in the northeast of Brazil, crosses the Camaçari Petrochemical Complex, the largest integrated industrial complex in the Southern Hemisphere, which has over 90 companies in the chemical and petrochemical industry. The present study aims to evaluate spatial distribution, seasonal variation and identify possible sources of trace metal contamination in surface water samples of the Joanes River. Samples were collected in the dry (December 2018) and rainy (August 2019) seasons. Analysis of trace elements (As, Cd, Cr, Cu, Ni, Mn and Pb) were performed by ICP-MS. A total of 60 water samples were obtained. Samples were analyzed using exploratory techniques such as principal component analysis (PCA) and cluster analysis (CA). It was possible to characterize the samples according to the seasonal variation. The formation of two groups was observed. Among these, samples from the rainy season presented the higher levels of metals in relation to the samples of the dry season. Natural and anthropic sources of metal contamination were identified using CA. Similarity was shown in the relationship between the metals As-Pb and Ni-Cd-Cr-Cu in the dry season, and Cd-Ni and Pb-As-Cr-Cu in the rainy season. Dermal absorption (HQderm) and ingestion hazard quotients (HQing) routes exhibited values of less than one for all the elements analyzed for adults and children, in both rainy and dry seasons. This indicated that the pollutants analyzed posed little or no health risk over a lifetime of exposure. According to international guidelines (US EPA), the values of Cu, Pb and Cr were above the limit established.

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As a natural adsorbent, sisal (agave sisalana) fibers were used to extract Cu, Ni, Mn, and Zn from diesel oil samples for posterior determination (i.e., direct analytical measurements on the solid support) of the analytes by energy dispersive X-ray fluorescence spectrometry (EDXRF). In the proposed procedure, 0.2 g of sisal fiber was directly added to 5.0 mL of diesel oil contained in a glass tube. After 5 min of contact time, the mixture was filtered, and the collected fibers were oven-dried for 30 min at 70 °C. After drying, the analytes were quantified directly by EDXRF using the sisal fibers as a solid support. The calibration curves showed linear concentration ranges of 0.09-1.00, 0.12-1.00, 0.09-1.00, 0.06-1.0 µg g-1 for Cu, Ni, Mn, and Zn, respectively. The limits of detection (LOD) for Cu, Ni, Mn, and Zn were 0.03, 0.04, 0.03, and 0.02 µg g-1, respectively. The repeatability, evaluated by performing ten measurements at a concentration of 0.50 µg g-1 for each metal, with the results expressed in terms of the relative standard deviation (RSD), was 3.2, 6.5, 6.8, and 6.1% for Cu, Ni, Mn, and Zn, respectively. The results obtained by the proposed method were compared with the results obtained by a comparative method using inductively coupled plasma optical emission spectrometry, and both results showed good agreement. The proposed method was applied for Ni, Cu, Mn, and Zn determination in diesel oil samples collected from different gas stations.

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In this paper, a flow-batch analysis (FBA) system, hydride generation (HG), and atomic fluorescence spectrometry (AFS) are coupled for the first time to develop a fast and sensitive FBA-HG-AFS method for automated inorganic antimony speciation in waters, whether from the sea, mineral water, tap water, or lakes. Unlike previous automated flow methods that use confluent fluids and complex devices, the main advantage of the proposed FBA-HG-AFS method is an innovative use of a simple laboratory made flow-batch chamber to simultaneously perform mixing, homogenization, reactions, antimony hydride formation, and gas-liquid separation. The FBA-HG-AFS method was optimized using two-level full factorial and Box-Behnken designs, and validated on the basis of real repeated measurements and analysis of variance, yielding a satisfactory working range (100-2000 ng L-1), precision (RSD = 4%), sensitivity, and limit of detection (6 ng L-1) for the water samples analyzed. Accuracy was evaluated by recovery tests and analysis of a standard reference material (SRM 1643e) of trace elements in water (NIST, USA), resulting in recovery rates of from 90 to 114%, and relative error = 0.7%. The high sampling throughput (54 speciations h-1), together with low waste generation, low costs, low reagent and sample consumption make this FBA-HG-AFS method an interesting proposal for fast large-scale analysis in routine laboratoy according to the principles of green analytical chemistry.

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This work proposes an analytical strategy utilizing digital images (DI) for the iron inorganic speciation in white wine. The method was established by the reaction of iron(II) ions with 1,2 ortho-phenanthroline as a chromogenic reagent. Total iron was determined using the same reagent after the addition of hydroxyl ammonium chloride as a reducing agent. In both cases, digital images of the standards/chromogenic reagent and samples were acquired and stored in JPEG format. The region of interest (ROI) was determined with a constant square shape for all images. The ROI was submitted to decomposition in color values according to the RGB additive color model. However, the data obtained by the blue channel was the one used in the construction of the analytical curves because it presented the highest sensitivity. The optimization of the experimental conditions of the procedure was performed by employing multivariate techniques. The precision was evaluated using a wine sample with iron (II) and total iron contents of 0.41 and 0.69 mg L-1, respectively. The results expressed as relative standard deviations were 3.57% for iron (II) and 4.76% for total iron contents. A comparison between the results obtained for total iron by the DI method with the results found using flame atomic absorption spectrometry confirmed the method accuracy. The DI procedure was applied for speciation analysis in six white wine samples and the contents found varied from 0.41 to 1.67 mg L-1 for iron (II) and from 0.69 to 1.71 mg L-1 for total iron. These results are in agreement with those found for speciation analysis of iron in wine samples. Iron (III) contents can be found by the difference between the total iron and iron (II) contents.

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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.

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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%.

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This work proposes a method for the determination of free and total sulfur(IV) compounds in coconut water samples, using the high-resolution continuum source molecular absorption spectrometry. It is based on the measurement of the absorbance signal of the SO2 gas generate, which is resultant of the addition of hydrochloric acid solution on the sample containing the sulfating agent. The sulfite bound to the organic compounds is released by the addition of sodium hydroxide solution, before the generation of the SO2 gas. The optimization step was performed using multivariate methodology involving volume, concentration and flow rate of hydrochloric acid. This method was established by the sum of the absorbances obtained in the three lines of molecular absorption of the SO2 gas. This strategy allowed a procedure for the determination of sulfite with limits of detection and quantification of 0.36 and 1.21mgL-1 (for a sample volume of 10mL) and precision expressed as relative standard deviation of 5.4% and 6.4% for a coconut water sample containing 38.13 and 54.58mgL-1 of free and total sulfite, respectively. The method was applied for analyzing five coconut water samples from Salvador city, Brazil. The average contents varied from 13.0 to 55.4mgL-1 for free sulfite and from 24.7 to 66.9mgL-1 for total sulfur(IV) compounds. The samples were also analyzed employing the Ripper´s procedure, which is a reference method for the quantification of this additive. A statistical test at 95% confidence level demonstrated that there is no significant difference between the results obtained by the two methods.

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This work presents the optimization of a sample preparation procedure using microwave-assisted digestion for the determination of nickel and vanadium in crude oil employing inductively coupled plasma optical emission spectrometry (ICP OES). The optimization step was performed utilizing a two-level full factorial design involving the following factors: concentrated nitric acid and hydrogen peroxide volumes, and microwave-assisted digestion temperature. Nickel and vanadium concentrations were used as responses. Additionally, a multiple response based on the normalization of the concentrations by the highest values was built to establish a compromise condition between the two analytes. A Doehlert matrix optimized the instrumental conditions of the ICP OE spectrometer. In this design, the plasma robustness was used as chemometric response. The experiments were performed using a digested oil sample solution doped with magnesium(II) ions, as well as a standard magnesium solution. The optimized method allows for the determination of nickel and vanadium with quantification limits of 0.79 and 0.20µgg-1, respectively, for a digested sample mass of 0.1g. The precision (expressed as relative standard deviations) was determined using five replicates of two oil samples and the results obtained were 1.63% and 3.67% for nickel and 0.42% and 4.64% for vanadium. Bismuth and yttrium were also tested as internal standards, and the results demonstrate that yttrium allows for a better precision for the method. The accuracy was confirmed by the analysis of the certified reference material trace element in fuel oil (CRM NIST 1634c). The proposed method was applied for the determination of nickel and vanadium in five crude oil samples from Brazilian Basins. The metal concentrations found varied from 7.30 to 33.21µgg-1 for nickel and from 0.63 to 19.42µgg-1 for vanadium.

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The present study evaluated the origin and distribution of polycyclic aromatic hydrocarbons (PAHs) and the organic matter (OM) in the surface sediment of the São Paulo River estuary, Todos os Santos Bay (TSB), Brazil. The samples were collected in the rainy (CP1) and the dry (CP2) seasons. We analyzed the 16 PAHs from the United States Environmental Protection Agency (US EPA) priority pollutant list, total organic carbon (TOC), total nitrogen (N), and stable carbon isotope (δ13C). The total concentration of PAHs ranged from 11.45±1.28 to 1825.35±107.96ngg-1, while TOC ranged from 3.8 to 27.7gkg-1. CP1 showed the highest concentrations for all parameters. The δ13C ratio indicated terrigenous OM (-23.81 to -26.63‰). The TOC/N ratio (C/N) indicated transitional OM (12.32 to 24.39), in addition to the continental origin. The diagnostic ratios of PAHs origin revealed only pyrolytic source, although close to areas with a history of petroleum contamination.

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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.

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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.

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A method was established to simultaneously determine cadmium, iron and tin in canned-food samples using high-resolution continuum source graphite furnace atomic absorption spectrometry (HR-CS GF AAS). The quantification step has been performed using the primary line (228.802nm) for cadmium and the adjacent secondary lines (228.725nm and 228.668nm) for iron and tin, respectively. The selected chemical modifier was an acid solution that contained a mixture of 0.1% (w/v) Pd and 0.05% (w/v) Mg. The absorbance signals were measured based on the peak area using 3 pixels for cadmium and 5 pixels for iron and tin. Under these conditions, cadmium, iron and tin have been determined in canned-food samples using the external calibration technique based on aqueous standards, where the limits of quantification were 2.10ngg(-1) for cadmium, 1.95mgkg(-1) for iron and 3.00mgkg(-1) for tin, and the characteristic masses were 1.0pg for cadmium, 0.9ng for iron and 1.1ng for tin. The precision was evaluated using two solutions of each metal ion, and the results, which were expressed as the relative standard deviation (RSD%), were 3.4-6.8%. The method accuracy for cadmium and iron was confirmed by analyzing a certified reference material of apple leaves (NIST 1515), which was supplied by NIST. However, for tin, the accuracy was confirmed by comparing the results of the proposed method and another analytical technique (inductively coupled plasma optical emission spectrometry). The proposed procedure was applied to determine cadmium, iron and tin in canned samples of peeled tomato and sardine. Eleven samples were analyzed, and the analyte concentrations were 3.57-62.9ngg(-1), 2.68-31.48mgkg(-1) and 4.06-122.0mgkg(-1) for cadmium, iron and tin, respectively. In all analyzed samples, the cadmium and tin contents were lower than the permissible maximum levels for these metals in canned foods in the Brazilian legislation.

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The present work proposed an analytical method for the direct determination of chromium in infant formulas employing the high-resolution continuum source electrothermal atomic absorption spectrometry combined with the solid sample analysis (SS-HR-CS ET AAS). Sample masses up to 2.0mg were directly weighted on a solid sampling platform and introduced into the graphite tube. In order to minimize the formation of carbonaceous residues and to improve the contact of the modifier solution with the solid sample, a volume of 10 µL of a solution containing 6% (v/v) H2O2, 20% (v/v) ethanol and 1% (v/v) HNO3 was added. The pyrolysis and atomization temperatures established were 1600 and 2400 °C, respectively, using magnesium as chemical modifier. The calibration technique was evaluated by comparing the slopes of calibration curves established using aqueous and solid standards. This test revealed that chromium can be determined employing the external calibration technique using aqueous standards. Under these conditions, the method developed allows the direct determination of chromium with limit of quantification of 11.5 ng g(-1), precision expressed as relative standard deviation (RSD) in the range of 4.0-17.9% (n=3) and a characteristic mass of 1.2 pg of chromium. The accuracy was confirmed by analysis of a certified reference material of tomato leaves furnished by National Institute of Standards and Technology. The method proposed was applied for the determination of chromium in five different infant formula samples. The chromium content found varied in the range of 33.9-58.1 ng g(-1) (n=3). These samples were also analyzed employing ICP-MS. A statistical test demonstrated that there is no significant difference between the results found by two methods. The chromium concentrations achieved are lower than the maximum limit permissible for chromium in foods by Brazilian Legislation.

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An assisted liquid-liquid extraction of copper, iron, nickel and zinc from vegetable oil samples with subsequent determination by high-resolution continuum source flame atomic absorption spectrometry (HR-CS FAAS) was optimized by applying a full factorial design in two levels and the response surface methodology, Box-Behnken. The effects of the acid concentration and the amplitude, cycle and time of sonication on the extraction of the analytes, as well as their interactions, were assessed. In the selected condition (sonication amplitude = 66%, sonication time = 79 s, sonication cycle = 74%), using 0.5 mol L(-1) HCl as the extractant, the limits of quantification were 0.14, 0.20, 0.21 and 0.04 µg g(-1) for Cu, Fe, Ni and Zn, respectively, with R.S.D. ranging from 1.4% to 3.6%. The proposed method was applied for the determination of the analytes in soybean, canola and sunflower oils.

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