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Microwave induced plasma optical emission spectrometry (MIP OES) was employed to determine the concentrations of macro and micronutrients (Ba, Ca, Cu, Fe, K, Mg, Mn and Na) in products derived from sugarcane: sugars (refined, crystal, demerara and brown) and derived products (molasses and brown sugar candy) produced in the southern region of Brazil. The sample preparation was performed by acid decomposition with a reflux system under optimized conditions: 1000 mg of sample and 5.0 mL of concentrated nitric acid for 4 hours at 150 °C and addition of 1.0 mL of hydrogen peroxide. At the end we obtained a procedure that provides analytical solutions in accordance with the established parameters of acidity and dissolved solids as per the MIP OES spectrometer manufacturer's recommendations. The accuracy was evaluated by the analyte addition tests (80 to 119%). The limits of detection, in mg kg−1, were 0.03 (Ba); 0.03 (Ca); 0.04 (Cu); 0.08 (Fe); 0.18 (K); 0.03 (Mg); 0.02 (Mn) and 0.26 (Na). The concentrations of the analytes in the different samples varied according to the degree of processing, since higher values appeared for the less processed samples, i.e. brown sugar, molasses and brown sugar candy.

The present study provides information about the total concentration and bioaccessible fraction of metals Al, Ba, Bi, Ca, Cd, Cr, Cu, Fe, K, Mg, Mn, Pb, Ti and Zn in nine different infant cereal samples. An in vitro digestion method was employed to evaluate the bioaccessibility. The determinations were performed by microwave induced plasma optical emission spectrometry (MIP OES). The bioaccessibility varied according to the type of infant cereal sample. The values of bioaccessible fraction (minimum and maximum) for Cu, Fe, Mn, Pb and Zn were 24–68, 1–10, 7–58, 24–100 and 1–7% of the total concentration, respectively. Al and Ti presented bioaccessibility in only two samples: 6% in the multicereal A and 14% in the rice and oat cereal B, respectively. The concentration of Ba, Bi, Cd, and Cr was below the limit of detection for the bioaccessibility method. The obtained concentrations were lower than the daily recommended intake for essential and toxic elements, with exception of Pb in the rice and oat A sample.

This study evaluated the total concentrations of Cd, Cr, Cu, Pb and Zn in sediments samples from the Sao Goncalo channel, Patos-Mirim lagoon complex, RS state, Southern Brazil during 2013 autumn, winter and spring, and 2014 summer. Ultrasound-assisted extraction method was employed to extract metals from the sediment samples. The sample powder was mixed with HNO3 and HF in an ultrasonic bath during 60 minutes at 25 oC. The limits of detection were 0.002; 0.026; 0.83; 0.386 and 0.44 mg kg-1 for Cd, Cr, Cu, Pb and Zn, respectively. The accuracy of the method was confirmed by analysis of two sediment certified reference materials and its precision was determined by the values of relative standard deviation lower than 9.1%. The concentrations obtained ranged from 0.11 to 0.58 mg kg-1 for Cd; 14.7 to 38.4 mg kg-1 for Cr; 3.9 to 102.0 mg kg-1 for Cu; 1.6 to 3.11 mg kg-1 for Pb; and 29.3 to 126 mg kg-1 for Zn. These values did not exceed the probable effect levels (PEL). Simplicity, low cost and high efficiency are some of the qualities of the method, making it adequate for routine analysis.

The present work describes a sample preparation method using acid decomposition in reflux system for the determination of Hg on xanthan gum samples by cold vapor atomic absorption spectrometry (CV AAS). The best conditions of sample preparation method were optimized. This procedure proved to be safe for the quantification of this analyte, because no significant losses of Hg by volatilization, which is due to the efficient reflux system. The limits of detection and quantification were 0.0049 and 0.0163 μg g−1, respectively. The accuracy was evaluated through recovery tests performed with different species of Hg and CRM analysis, obtaining excellent recoveries. The values of Hg were below the LOD(m) for xanthan gum samples A and B. However, the other samples showed concentrations in the range of 0.027–0.325 μg g−1. The method proves suitable for the quantification of Hg, which is important due to the wide applicability of xanthan gum.

An analytical method for the determination of Al, Ca, Cd, Cr, Cu, Fe, Hg, K, Mg, Na and Zn in breast of conventional, country and Christmas chicken and turkey samples using microwave induced plasma optical emission spectrometry (MIP-OES) technique was developed. Samples were decomposed in a digester block with a reflux system under conditions optimized using a central composite design as it follows: 2 g of sample, in 7.5 mL of HNO3 during 180 min at 160 °C. The accuracy was evaluated by the analysis of standard reference material SRM 1546 meat homogenate (94 to 108%) and also by addition and recovery tests (80 to 121%). The highest concentrations, in mg kg-1, of Al (2.77), Ca (88.3), Cu (1.99), Fe (3.65), K (3236), Mg (292.62) and Na (312.03) were found in the breast of conventional chicken sample. Zinc presented high value in the breast of turkey sample (10.6 mg kg-1). However, the found concentrations were lower than the daily consumption limit established by supervisory agencies and reference limits from Brazilian legislation. Cadmium, Cr and Hg presented values below limit of quantification. In this way, it is evident that chicken breast should be consumed in a complementary way in a healthy diet.

This study presents information about the total concentration and bioaccessible fraction of barium (Ba), calcium (Ca), cadmium (Cd), copper (Cu), iron (Fe), mercury (Hg), potassium (K), lithium (Li), magnesium (Mg), manganese (Mn), molybdenum (Mo), lead (Pb) and zinc (Zn) in different cultivars of tomato (Gaucho, Paulista, Italiano and Cherry) and their derivatives (sauce and tomato extract). The determinations were performed by microwave induced plasma optical emission spectrometry (MIP OES). The bioaccessible fraction of the elements was evaluated through in vitro digestion process and the concentrations varied between 25 and 100 % ​for Cu, Fe, Mn and Zn, depending on the type of tomato sample and its derivatives. The total concentrations for all the elements studied were below the recommendation of dietary guidelines. For Ba, only the Italiano sample presented 22 % of bioaccessibility. For Pb, the highest percentage of bioaccessible fraction was found in sauces and tomato extracts. The elements Cd, Hg, Li and Mo presented concentrations lower than the limit of detection for the bioaccessibility method.

This study presents a comparative evaluation of three different methods for sample preparation in rice for As, Cd, Pb, and Se determination by graphite furnace atomic absorption spectrometry (GF AAS). Raw and cooked white rice, parboiled rice, and brown rice samples were studied with the following procedures: i) HNO3 decomposition in open system with cold finger, ii) HNO3 decomposition in ultrasonic bath, and iii) alkali solubilization with TMAH. The sample preparation using reflux system was optimized and the best conditions were: 750 mg of sample, 10 mL of HNO3, 120 °C (heating), and 90 min in the digester block. In rice samples, medium concentrations of 12.0 ± 4.0 and 177.0 ± 64.0 ng g− 1 for Cd and Pb were found, respectively, while for As and Se, the concentrations were below the limit of detection of the studied methods. After cooking, samples presented a maximum decrease of 61% in Cd concentration. The method validations were assured by analysis of certified reference material (NIST 1568a), and results were in accordance with the certified values. The recovery test was carried out and results ranged between 80 and 115% for all analytes in the rice samples, before and after cooking. All evaluated procedures presented accurate and precise results; however, the decomposition with reflux system proved to be more effective, simple and secure. Such characteristics are necessary for the application in routine analysis with medium detection limits of 77.2; 1.0; 35.5 and 192.1 ng g− 1 for As, Cd, Pb and Se, respectively.

In this work, three vapor generation methods (photochemical vapor generation, cold vapor generation with NaBH4 or with SnCl2) coupled with atomic absorption spectrometry were compared for the analysis of mercury (Hg) in pure glycerin and residual glycerin from biodiesel production. For these methods, a simple sample treatment step was employed through a dilution with formic acid or water and all parameters used were optimized. The limits of detection for the methods PVG-CV AAS, CV AAS with NaBH4, and CV AAS with SnCl2, were 0.12, 0.11, and 0.04 μg L–1, respectively. Because no adequate certified reference material was available, the accuracy was evaluated by assessing the recoveries of Hg2+ spikes in all samples (84%–108.3%). When methods were compared, the PVG-CV AAS presented adequate sensitivity and simplicity, and provided a direct approach to the generation of Hg vapor from glycerin samples while promoting green chemistry. In addition, PVG-CV AAS provided limits of detection that are comparable to co...

The acid decomposition method was applied for the sample preparation of processed fruit juice. The decomposition of 15mL of juice sample using HNO3 and H2O2 was performed in a digester block with reflux system and heated at 200°C for 150min. The limits of detection were 0.03; 0.24; 0.8; 0.008; 0.026 and 0.056mgL-1 for Cr, Cu, K, Mg, Na and Zn, respectively and for Pb was 0.99μgL-1. The accuracy was evaluated by spiked experiments (80 to 119%). Four processed fruit juice samples commercialized in Brazil (strawberry, mango, peach, and orange) were analyzed and indicated the absence of Cr, Zn and Cu in the samples, except for Cu in strawberry juice. Pb was found in the mango juice sample (17.8±0.9μgL-1) and the concentration is below the maximum values recommended by Brazilian legislation for juices of citric fruits (0.3mgkg-1).

In this work, the photochemical vapor generation (PVG) coupled with atomic absorption spectrometry and a pre-concentration step with an Au column was used for the determination of Hg in biological samples and ethanol fuel. PVG with pre-concentration showed an up to 250-fold higher sensitivity compared to the approach without pre-concentration. The accuracy of analysis of biological samples was evaluated using certified reference materials (fish tissues), while for ethanol fuel samples, recovery tests were employed (91%). Analytical curves were linear (R > 0.99) in the studied range of 2.5 to 10 µg L-1 for conventional PVG and 0.2 to 0.5 µg L-1 for PVG with the pre-concentration step. For the last, the limits of detection reached for biological samples and ethanol fuel were 0.02 and 0.01 µg L-1, respectively. The systems presented are simple, sensitive and safe for the control of low Hg concentrations in different samples. However, only the system using pre-concentration with an Au column was capable of obtaining the reproduced signals of Hg in low concentrations of the order of 0.2 µg L-1.

In this work the feasibility of mercury determination in naphtha and petroleum condensate by photochemical vapor generation was investigated. The samples were pumped through the photochemical reactor as microemulsions and the volatile compounds formed were conducted to a quartz cell for the atomic absorption measurements. All the parameters of the system (sample preparation, organic precursor, sample flow rate, carrier gas flow rate and evaluation of the signal measurement mode) were investigated. The microemulsions were prepared mixing the samples with propan-1-ol and a small amount of water. The addition of low molecular weight organic acid was investigated and it was found not necessary once the propan-1-ol itself was efficient for promoting the generation of the volatile compounds of mercury. Calibration curves obtained with organic and inorganic standards showed correlation coefficients higher than 0.99 and characteristic mass of 2.0 and 2.4 ng of mercury for organic and inorganic standards, respectively, was obtained. There was no significant difference between the sensitivity of inorganic or organic standards for the calibration. Relative standard deviations ranged from 1 to 5% for three consecutive measurements. The limit of detection of 0.6 μg L− 1, calculated for the amount of sample used in the microemulsion (1.0 mL), was obtained. A sample throughput was 2 samples per hour, considering triplicate analysis. Different naphtha and petroleum condensate samples were analyzed. No mercury was found in the naphtha samples, considering the limit of detection. In the petroleum condensate samples the concentrations ranged from 76 to 105 μg L− 1. The accuracy was evaluated by assessing the recoveries of inorganic and organic species of mercury added to the samples, being obtained values in the range of 92 to 113%. The developed method was simple and fast, allowed direct analysis of naphtha and petroleum condensate with a reduced amount of reagents, thus contributing to green chemistry.

This paper presents studies involving the determination of Hg in biological samples by cold vapor atomic absorption spectrometry (CV-AAS) using a simple and inexpensive system for sample digestion. The system consists of a glass tube that is closed with a small glass tube filled with cold water, which is called cold finger, and helps the recirculation of the acids within the bigger tube. The use of cold finger avoided the loss of analyte and the excessive evaporation of the acids during the heating. Thus, lower amount of acid was required, decreasing the risk of contamination. Studies of temperature of the digester block were performed with aqueous standard solutions in an interval between 80 and 120 °C. No significant loss of analyte was observed when compared with the open system. Certified reference materials (CRMs) were used to evaluate the accuracy of the proposed methodology. For this process, samples were digested with HNO3 for 2 h in a digester block between 90 and 120 °C, using the open system with the cold finger. The use of the cold finger system was efficient with similar results to those expected for CRMs for mercury (Hg) concentrations. For the open system, loss of analyte was observed when the digestion temperature was increased. The limit of detection (LOD) was 0.08 μg L− 1. The digestion procedure using cold finger in an open system is useful, at boiling point solution temperature, safe and simple for Hg determination in biological samples. Moreover, it can be used as an alternative to microwave-assisted digestion.

This paper describes the development of methods in micro-scale for the determination of K, Mg, Na and Zn in meat by atomic spectrometry techniques. The limits of detection (LOD) for K and Na by microdigestion were 0.18 and 0.20 mg g-1, respectively whereas LOD for Mg and Zn by microsolubilization with TMAH were 2.40 and 18.4 µg g-1, respectively. The RSD values were lower than 6.0% and the CRMs analyzed showed values with 95% agreement. The proposed methods are simple, fast and use small amounts of sample (around 10 mg) yet do not require special equipment for sample preparation.

In this paper, a simple procedure for the determination of Si in vegetable oils and biodiesel of different origins by high-resolution continuum source flame atomic absorption spectrometry is proposed. Samples were diluted with xylene, and external calibration was performed with calibration solutions prepared with xylene and mineral base oil used for viscosity matching. The accuracy was assessed using recovery tests and comparing the results for a set of vegetable oils and biodiesel to those determined by inductively coupled plasma–optical emission spectroscopy (ICP–OES). Recoveries at 3.0 and 5.0 mg L–1 levels using organic Si standard-spiked solutions ranged from 93 to 113%. The limit of detection at the optimized conditions in the original sample was approximately 0.60 mg kg–1, which is adequate for the analysis of vegetable oils and biodiesel according to the Brazilian legislation.

Cisplatin and carboplatin are the most common platinum-based drugs used in cancer treatment. Pharmacokinetic investigations, the evaluation of the body burden during the treatment, as well as baseline levels of platinum in humans have attracted great interest. Thus, accurate analytical methods for fast and easy Pt monitoring in clinical samples become necessary. In the present study atomic absorption spectrometric methods for the determination of platinum in the forms of cisplatin and carboplatin in human urine were investigated. Platinum, in these different forms, could be determined in urine, after simple sample dilution. Regarding electrothermal atomic absorption spectrometry, the optimum parameters were defined by a central composite design optimization. Multiplicative matrix effects were overcome by using a mixture of HCl and NaCl as modifier. The limit of detection (LOD) was 0.004 mg L−1 of platinum in the original sample. For the analysis of more concentrated samples, high resolution continuous source flame atomic absorption spectrometry was also investigated. Flame conditions were optimized by a multivariate D-optimal design, using as response the sum of the analyte addition calibration slopes and their standard deviations. Matrix matched external calibration with PtCl2 calibration solutions, was possible, and the LOD was 0.06 mg L−1 in the original sample. The results obtained by the proposed procedures were also in good agreement with those obtained by an independent comparative procedure.

In this work, an alternative procedure for the determination of As in vegetable oils and biodiesel of different origins by graphite furnace atomic absorption spectrometry (GFAAS) is proposed. The sample stabilization was achieved by the formation of three component solutions prepared mixing the samples with appropriate volumes of propan-1-ol and nitric acid. Palladium was used as a chemical modifier. Pyrolysis and atomization temperatures as well as the sample dilution factor were investigated and optimized. Because no adequate certified reference material was available, accuracy was assessed by recovery tests, using both organic and inorganic species. Recoveries ranged from 95 to 110%. The limit of detection in the original sample was 0.3 mg kg−1, which is adequate for the analysis of vegetable oils and biodiesel, according to the expected Brazilian legislation.

This work presents the development of an on-line pre-concentration system for simultaneous determination of Cd, Cu, Ni, V, Zn, Co and Pb in aqueous environmental samples and detection by inductively coupled plasma mass spectrometry. The system is based on cationic retention of the analytes onto a mini-column filled with silica gel modified with niobium(V) oxide. The effects of chemicals and flow variables have been investigated. The optimized operating conditions, selected as a compromise between sensitivity and analytical frequency were: sample pH 7.0, sample flow rate of 6.0 mL min −1 , eluent flow rate of 2.0 mL min −1 , and eluent (HNO 3 ) concentration of 2.5 mol L −1 . The relative standard deviation ( n = 7), enrichment factor and linear working range were 0.8–4.5%, 23.3–37.2 and 0.05–25.0 μg L −1 , respectively. Limits of detection were between 0.01 and 0.03 μg L −1 . The accuracy of the proposed method was checked with certified materials (NASS-4, NASS-5, CASS-4 and SRM 1643e). Values obtained were in accordance with those reported for the certified materials. Recovery was found to be in the range of 90–110% for a suit of water samples with variable matrices (seawater, tap water and ground water) collected in Florianopolis, Brazil.

Method development for the pre-concentration of mercury in human hair, dogfish liver and dogfish muscle samples using cloud-point extraction and cold vapor atomic absorption spectrometry is demonstrated. Before the extraction, the samples were submitted to microwave-assisted digestion in a mixture of H(2)O(2) and HNO(3). Cloud point extraction was carried out using 0.5% (m/v) ammonium O,O-diethyldithiophosphate (DDTP) as the chelating agent and 0.3% (m/v) Triton X-114 as the non-ionic surfactant. Phase separation was induced after the addition of Na(2)SO(4) to a final concentration of 0.2 mol L(-1). Aliquots of the final extract were transferred to PTFE tubes and NaBH(4) and HCl were added. The mercury vapor was driven to a non-heated quartz tube for measuring the absorbance. The results obtained with salt-induced phase separation were in good agreement with the certified values at a 95% confidence level. An enrichment factor of 10 allowed a detection limit of 0.4 ng g(-1) to be obtained, which demonstrates the high sensitivity of the proposed procedure for the determination of mercury at trace levels.

In order to determine inorganic constituents and contaminants in liquid aspartame sweeteners, different brands of this product were analyzed by ICP OES and ICP-MS. The samples were submitted to acid digestion and parameters such as internal standardization and wavelengths, in the case of ICP OES, and a recovery test were evaluated. The analytes studied were As, Ca, Cd, Co, Cu, K, Fe, Mg, Mn, Na, Ni, Pb, Se and Zn. Since there is not a certified reference material for sweeteners, the accuracy of the proposed method was evaluated by recovery tests and the values were in the range of 90–110% for the majority of the analytes. The detection limits for the elements determined by ICP OES were in the range 0.01 (Mn)– 2.0 (K) µg g−1 while those determined by ICP-MS were 0.001 µg g−1 for all the elements except Mn and As (0.002 µg g−1). The relative standard deviations were below 12% for ICP OES and below 14% for ICP-MS determinations. The mean concentration of the elements detected by ICP OES (Ca, Fe, K, Mg, Na, and Zn) varied according to the brand. The other analytes, were determined by ICP-MS. For these elements, a significant variation in their concentrations was also found for different samples, except for Co and Ni. The use of both multielemental techniques allowed the evaluation of the inorganic composition and the rapid determination of several elements in aspartame sweeteners, with adequate accuracy.

A method for the multi-elemental determination of As, Ge, Hg, Pb, Sb, Se and Sn in coal reference materials by slurry sampling chemical vapor generation (CVG) using external calibration and isotopic dilution (ID) calibration and detection by electrothermal vaporization inductively coupled plasma mass spectrometry (ETV-ICP-MS) is proposed. As, Ge, Sb, Se and Sn were determined using the external calibration, while, Hg, Pb, Se and Sn were determined by isotopic dilution. About 50–250 mg of sample was mixed with an acid solution, containing aqua regia and HCl, in an ultrasonic bath. For the isotopic dilution calibration, the enriched isotopes 201Hg, 206Pb, 77Se and 119Sn were added to the slurry in an adequate amount in order to produce an altered isotopic ratio close to 1. The vapor produced by the reaction of the sample slurry with the reducing agent was transported to the vaporizer and trapped in a Ir-treated graphite tube at 200 °C, before vaporization at 2100 °C and transportation of the vapor to the plasma. The accuracy of the method was assured by the analysis of four certified reference coal samples, using external calibration with aqueous solutions, prepared in the same medium and subjected to the same CVG and trapping procedure as the slurries and also by isotopic dilution calibration. The obtained concentrations were in agreement with the certified values, using the t-Student test for a confidence level of 95%. The detection limits (3 s; n = 5) of isotopic dilution, in ng g− 1, were: 0.4 for Hg, 900 for Pb, 0.3 for Se and 0.2 for Sn. For external calibration, the detection limits, in ng g− 1, were: 1.6 for As, 0.1 for Ge, 0.3 for Sb, 0.9 for Se and 7.5 for Sn. The relative standard deviations generally were lower than 14%, adequate for slurry analysis.

A method for the determination of Cd, Hg, Pb and Se in sediments reference materials by slurry sampling chemical vapor generation (CVG) using isotopic dilution (ID) calibration and detection by inductively coupled plasma mass spectrometry (ICP-MS) is proposed. Two different systems were used for the investigation: an on-line flow injection system (FI-CVG-ICP-MS) and an off-line system with in situ trapping electrothermal vaporization (CVG-ETV-ICP-MS). About 100 mg of the reference material, ground to a particle size ≤50 μm, was mixed with acid solutions ( aqua regia , HF and HCl) in an ultrasonic bath. The enriched isotopes 111 Cd, 198 Hg, 206 Pb and 77 Se were then added to the slurry in an adequate amount in order to produce an altered isotopic ratio close to 1. For the on-line system, a standing time for the slurry of 12 h before measurement was required, while for the batch system, no standing time is needed to obtain accurate results. The conditions for the formation of the analyte vapor were optimized for the evaluated systems. The following altered isotope ratios were measured: 111 Cd/ 114 Cd, 198 Hg/ 199 Hg, 206 Pb/ 208 Pb e 77 Se/ 82 Se. The obtained detection limits in the on-line system, in μg g −1 , were: Cd: 0.15; Hg: 0.09; Pb: 6.0 and Se: 0.03. Similar detection limits were obtained with the system that uses the ETV: 0.21 for Hg, 6.0 for Pb and 0.06 μg g −1 for Se. No signal for Cd was obtained in this system. One estuarine, two marine and two river certified sediments were analyzed to check the accuracy. The obtained values by both systems were generally in agreement with the certified concentrations, according to the t -test for a confidence level of 95%, demonstrating that isotope equilibration was attained in the slurries submitted to a chemical vapor generation procedure and detection by ICP-MS. The relative standard deviations were lower than 10%, adequate for slurry analysis. The almost quantitative analytes extractions to the aqueous phase of the slurry must favor equilibration of the added enriched isotope with the isotope in the sample, allowing the use of isotopic dilution calibration for slurry analysis.

Two procedures for the determination of Co in biological samples by graphite furnace atomic absorption spectrometry (GF AAS) were compared: solid sampling (SS) and alkaline treatment with tetramethylammonium hydroxide (TMAH) using two different instruments for the investigation: a conventional line-source (LS) atomic absorption spectrometer and a prototype high-resolution continuum source atomic absorption spectrometer. For the direct introduction of the solid samples, certified reference materials (CRM) were ground to a particle size ≤50 μm. Alkaline treatment was carried out by placing about 250 mg of the sample in polypropylene flasks, adding 2 mL of 25% m/v tetramethylammonium hydroxide and de-ionized water. Due to its unique capacity of providing a 3-D spectral plot, a high-resolution continuum source (HR-CS) graphite furnace atomic absorption spectrometry was used as a tool to evaluate potential spectral interferences, including background absorption for both sample introduction procedures, revealing that a continuous background preceded the atomic signal for pyrolysis temperatures lower than 700 °C. Molecular absorption bands with pronounced rotational fine structure appeared for atomization temperatures >1800 °C probably as a consequence of the formation of PO. After optimization had been carried out using high resolution continuum source atomic absorption spectrometry, the optimized conditions were adopted also for line-source atomic absorption spectrometry. Six biological certified reference materials were analyzed, with calibration against aqueous standards, resulting in agreement with the certified values (according to the t-test for a 95% confidence level) and in detection limits as low as 5 ng g−1.

A method for the simultaneous determination of As, Hg, Se and Sn in sediment slurries using chemical vapor generation (CVG), in situ trapping electrothermal vaporization inductively coupled plasma mass spectrometry, is proposed. The vapors produced by the reaction of the sample slurry with the reducing agent are transported to the vaporizer and trapped at 150 °C in a graphite tube, treated with Ir as a permanent modifier, before vaporization at 2000 °C and transport to the plasma. The accuracy of the method was assured by the analysis of certified reference sediment samples, using external calibration with aqueous solutions, prepared in the same medium and subject to the same CVG and trapping procedure as the slurries. The obtained concentrations were in agreement with the certified values, using the t-Student test for a confidence level of 95%. The detection limits, in ng g−1, were: 0.8 for Hg, 0.04 for As, 0.01 for Se and 0.30 for Sn.

This paper describes the evaluation of a method for determination of Cd and Pb in xanthan gum samples by Graphite Furnace Atomic Absorption Spectrometry (GF AAS) using NH4H2PO4 as the chemical modifier. The sample preparation was performed using a reflux system adapted in the digestion tubes. With this system it was possible to increase the temperature of the digester block above the boiling point of the reaction medium, preventing loss of analyte and excessive evaporation of acids during heating. Samples were digested with HNO3 for 3 h in a digester block at 220 oC. The limits of detection for Cd and Pb were 2.2 and 33.8 ng g-1, respectively. The RSDs for both analytes were, on average, lower than 5.0% and accuracy was verified by recovery tests, yielding values in the 83-100% range.

This paper describes the evaluation of simple and fast solubilization methods for the determination of Ca, Mg, and K in glycerin samples from biodiesel production by atomic spectrometry. The solubilization in water was compared with two other methods: solubilization in formic acid and solubilization in ethanol. Using solubilization in water, determination of the three analytes was possible; the values of limits of detection for Ca, K, Mg were 0.31, 0.06, and 0.16 mg kg−1, respectively. Because no adequate reference material was available, the accuracy was evaluated by assessing the recoveries tests with both solubilization methods; the evaluation ranged from 90% to 115%, with values of relative standard deviation >8%, indicating good accuracy of the measure. Four crude glycerin samples obtained from biodiesel plants of Rio Grande do Sul were analyzed after treatment with the different methods of solubilization, and the obtained results of Ca, Mg, and K concentration were in agreement with the values obtained from both solubilization methods. Therefore, solubilization in water is concluded to be a simpler, faster, and viable method for sample preparation of glycerin.

It is presented an alternative procedure for preparation of biodiesel samples for elemental determination by inductively coupled plasma optical emission spectrometry (ICP OES), based on the sample (10% m/v) emulsion formation with formic acid (15% v/v) and Triton X-100 (0.1% m/v). These concentrations were optimized and the stability of emulsified aqueous standards and samples was found to be of at least 3 h. Experimental conditions (1500 W of RF power and 0.5 L min-1 of Ar nebulizer flow rate) were optimized from those recommended by the equipment manufacturer, with a solution containing 10 mg L-1 of each analyte prepared with mineral oil in the same conditions of the emulsion. Matrix effects were investigated by observing the slopes of analyte addition curves for different biodiesel samples. Results showed that external calibration with inorganic aqueous standard solutions in the emulsion medium should be used. Limits of detection obtained (in mg kg-1) were 0.121, 0.008, 0.006, 0.001, 0.006, 0.071, 0.241 and 0.024 for Ca, Cu, Fe, Mn, Mg, Na, K and Si, respectively. The accuracy of the procedure for Ca, Mg, K and Na was assessed by the analysis of a multi-element standards B100 biodiesel (Conostan) and the recoveries ranged from 91 to 107%. The proposed procedure used low toxicity reagents and showed to be a simple and straightforward alternative of sample preparation for metal determination in biodiesel by ICP OES with limits of detection adequate for those analyses. Apresenta-se um procedimento alternativo para o preparo das amostras de biodiesel para a determinação elementar por espectrometria de emissão óptica com plasma indutivamente acoplado (ICP OES), baseado na formação de emulsão da amostra (10% m/v) com ácido fórmico (15% v/v) e Triton X-100 (0,1% m/v). Estas concentrações foram otimizadas e os padrões e amostras emulsionados mostraram-se estáveis por pelo menos 3 h. As condições experimentais (1500 W de potência da radiofrequência e 0,5 L min-1 de vazão do Ar nebulizador) foram otimizadas a partir das recomendadas pelo fabricante do equipamento, com uma solução contendo 10 mg L-1 de todos os analitos, preparada com óleo base nas mesmas condições da emulsão. Os efeitos de matriz foram investigados, observando as inclinações das curvas de adição de analito para diferentes amostras de biodiesel. Os resultados mostraram que a calibração externa com soluções contendo padrões inorgânicos emulsionados pode ser utilizada. Os limites de detecção encontrados (em mg kg-1) foram 0,121; 0,008; 0,006; 0,001; 0,006; 0,071; 0,241 e 0,024 para Ca, Cu, Fe, Mn, Mg, Na, K e Si, respectivamente. A exatidão do procedimento para o Ca, Mg, K e Na foi avaliada por meio da análise de um padrão multielementar de biodiesel B100 (Conostan) e as recuperações variaram entre 91 a 107%. O procedimento proposto usa reagentes com baixa toxicidade e mostrou ser uma alternativa simples e direta de preparação de amostras para determinação de metais em biodiesel por ICP OES com limites de detecção adequados para essas análises.

Two different sample preparation methods were evaluated for meat samples employing the solubilization in alkaline or acidic media. The aim of this study was to determine Na and K levels after sample solubilization with tetramethylammonium hydroxide (TMAH) at room temperature, and with formic acid and heating in a digester block at 50 ºC for ca. 2 h. The alkaline solubilization showed to be a simple and robust method and the better alternative in relation to the mineralization conventional procedures, allowing the complete solubilization of the samples even when small quantities of TMAH were used. The method was validated by using certified reference material as well as by comparing with samples digested with nitric acid. The limits of detection obtained were 0.8 and 2.0 μg g-1 for Na and K, respectively, and showed to be adequate for the analysis purposes. Foram avaliados dois métodos diferentes de preparo de amostras de carnes baseados na solubilização em meios alcalino ou ácido. O objetivo deste estudo foi determinar os teores de Na e K após solubilização com hidróxido de tetrametilamônio (TMAH) temperatura ambiente, e com ácido fórmico e aquecimento em bloco de digestão a 50 ºC por cerca de 2 h. A solubilização alcalina se apresentou como uma metodologia simples e robusta e a melhor alternativa frente aos procedimentos de mineralização convencional, permitindo a solubilização completa das amostras usando pequenas quantidades de TMAH. O método foi validado empregando-se materiais de referência certificada assim como pela comparação com método de digestão convencional com ácido nítrico. Os limites de detecção obtidos foram de 0,8 e 2,0 mg g-1 para Na e K, respectivamente, e se mostraram adequados para o objetivo das análises.

A low power atmospheric pressure plasma source, furnace atomization plasma emission spectrometry (FAPES), was directly coupled to both a conventional chemical vapor generation system based on use of tin chloride reductant as well as a UV-photoreduction system for detection of cold vapor mercury. The resonance line emission at 253.7 nm was monitored. The 70 W low power He plasma was tolerant to the introduction of water vapor from the gas–liquid separator and, with the furnace heated to 400 °C, a precision of measurement of 2.4% RSD at 1 ng mL−1 was achieved. A limit of detection of 250 pg mL−1Hg in river water samples via UV-photoreduction and 240 pg mL−1 using conventional tin chloride reduction was obtained. The LOD could be improved 5-fold through use of a simple gold amalgamation system. Conventional chemical generation of mercury using the NaBH4/HCl system produced too much hydrogen to permit efficient coupling to the FAPES source as the He plasma is extinguished by the load of molecular vapor (i.e., hydrogen).

A simple and robust method for the determination of arsenic in sediments by hydride generation atomic absorption spectrometry (HG-AAS) using slurry sampling is proposed. Aqua regia (5% v/v) and hydrofluoric acid (1% v/v) were mixed with an aliquot of the sediment with particle size of 50 µm in an ultrasonic bath for 30 min. The slurry was allowed to stand for 48 h for an effective extraction of the analyte to the aqueous phase. The final volume of the slurry was made up with HCl 1 mol L-1. A NaBH4 solution stabilized with NaOH was used as reducing agent. The arsine was transported to the quartz T-tube heated at 900 °C for detection. Five certified reference materials of sediment were analyzed and the obtained concentrations were in good agreement with the certified values, according to the t-test for a 95% confidence level with RSD (relative standard deviation) lower than 13%. The limit of detection (LOD) in the sample was 0.6 µg g-1. The proposed procedure for arsenic determination in sediment is precise, accurate and adequate for the environmental samples routine analyses. Um método simples e robusto para a determinação de arsênio em sedimentos por espectrometria de absorção atômica com geração de hidreto (HG-AAS) usando a amostragem em suspensão é proposto. Água régia (5% v/v) e ácido fluorídrico (1% v/v) foram misturados a uma alíquota do sedimento com tamanho de partícula 50 µm e colocados no banho ultra-sônico por 30 min. A suspensão foi deixada em repouso por 48 h para uma extração eficaz do analito para a fase aquosa. O volume final da suspensão foi ajustado com HCl 1 mol L-1. Uma solução de NaBH4 estabilizada com NaOH foi usada como agente redutor. A arsina foi transportada ao tubo T de quartzo aquecido a 900 °C para detecção. Cinco materiais de referência certificados de sedimento foram analisados e as concentrações obtidas foram concordantes com os valores certificados, de acordo com o teste-t para um nível da confiança de 95%, com RSD (desvio padrão relativo) menor que 13%. O limite de detecção (LOD) na amostra foi de 0,6 µg g-1. O procedimento proposto para a determinação de arsênio em sedimentos é preciso, exato e adequado para a análise de rotina de amostras ambientais.

Cold vapor atomic absorption spectrometry (CV-AAS) based on photochemical reduction by exposure to UV radiation is described for the determination of methylmercury and total mercury in biological samples. Two approaches were investigated: (a) tissues were digested in either formic acid or tetramethylammonium hydroxide (TMAH), and total mercury was determined following reduction of both species by exposure of the solution to UV irradiation; (b) tissues were solubilized in TMAH, diluted to a final concentration of 0.125% m/v TMAH by addition of 10% v/v acetic acid and CH(3)Hg(+) was selectively quantitated, or the initial digests were diluted to 0.125% m/v TMAH by addition of deionized water, adjusted to pH 0.3 by addition of HCl and CH(3)Hg(+) was selectively quantitated. For each case, the optimum conditions for photochemical vapor generation (photo-CVG) were investigated. The photochemical reduction efficiency was estimated to be approximately 95% by comparing the response with traditional SnCl(2) chemical reduction. The method was validated by analysis of several biological Certified Reference Materials, DORM-1, DORM-2, DOLT-2 and DOLT-3, using calibration against aqueous solutions of Hg(2+); results showed good agreement with the certified values for total and methylmercury in all cases. Limits of detection of 6 ng/g for total mercury using formic acid, 8 ng/g for total mercury and 10 ng/g for methylmercury using TMAH were obtained. The proposed methodology is sensitive, simple and inexpensive, and promotes "green" chemistry. The potential for application to other sample types and analytes is evident.

A method for the determination of Sn in slurry samples of sediment and coal by hydride generation graphite furnace electrothermal atomic absorption spectrometry (HG-GF AAS) is proposed. The slurries were prepared by mixing the ground sample (particle sizeor =50 microm) with 2.0 mol L(-1) HCl for the sediment samples or with 2.0 mol L(-1) HCl+1.0% v/v HF in a saturated boric acid medium for the coal samples. The slurry was placed in an ultrasonic bath for 30 min, before and after standing for 24 h, with occasional manual stirring. The graphite tube was treated with 0.5 mg of Th or W as a permanent modifier. Sn determination was carried out by electrothermal atomic absorption spectrometry at the optimized retention temperatures of 450 and 300 degrees C for Th and W treatment, respectively. With this coupling, kinetic interference in the formation of the hydrides is avoided, and excellent detection limits can be obtained by using peak height. For the chemical vapor generation device, an optimized volume of 2 mL of sample slurry and an optimized NaBH4 concentration of 5% m/v were employed. The vapor produced was transported and retained on the graphite tube surface, which was further heated for Sn atomization. The accuracy of the method was verified by analyzing five certified sediments and three coals. By using the external calibration against aqueous standard solutions, the results obtained were in agreement with the certified values only for the sediment samples. For the coal samples, an addition calibration curve, obtained for one certified coal, was necessary to achieve accurate results. The obtained limits of detection were 0.03 microg g(-1) for sediment and 0.09 microg g(-1) for coal with Th as permanent modifier. The relative standard deviations were lower than 15%, demonstrating an adequate precision for slurry analysis. Sediment and coal samples from Santa Catarina, Brazil, were also analyzed.

The aim of this study was to present three sample preparation methods for the determination of Cd, Pb and Sn in meat by Graphite Furnace Atomic Absorption Spectrometry (GFAAS): acid digestion, solubilization with tetramethylammonium hydroxide and formic acid. For the digestion with HNO3, a conventional open system with a cold finger was used. This system helped to avoid losses of analytes and reagents by volatilization, permitting to operate at high temperatures applied at a digester block and reducing the digestion time (∼1 h). Solubilizations were performed at room temperature. The slurry was left standing overnight and remained closed until achieving complete solubilization. The temperature program of the graphite furnace was optimized for each element in the different means of preparation samples using a mixture of Pd–Mg. The figures of merit were similar for all sample preparation methods evaluated. The limits of detection obtained for the acid digestion procedure were 0.0006, 0.0164 and 0.0520 μg g−1 for Cd, Pb and Sn, respectively. In order to evaluate the accuracy of the results obtained by the three sample preparation methods, recovery tests for four real meat samples were performed and the recoveries ranged from 93.7 to 109%, supporting the accuracy of the method. Also, different certified reference materials of meat were analyzed and the results obtained were in agreement with the certified value at 95% of confidence (t-test). The best results were obtained by the acid digestion procedure with the cold finger system. This procedure is faster, the system is semi-closed with no significant contamination or loss of analytes by volatilization and it provides a better signal/noise ratio.

A new procedure based on exposure of ethanol biofuel samples to UV radiation in the presence of low molecular weight organic acids was developed for the determination of total Hg (inorganic and organometallic species: Hg2+, CH3Hg+ and CH3CH2Hg+) by photochemical vapor generation coupled with atomic absorption spectrometry (photo-CV-AAS). For each species, the optimum conditions for photochemical generation were investigated, including the effects of medium composition, exposure time to the UV radiation and transfer gas flow rate. The accuracy was evaluated by assessing the recoveries of species-specific spikes (91–107%) as well as by assessing recovery from a mixture of all species of the mercury added to the ethanol biofuel samples based on calibration standards prepared in high purity bidistilled ethanol. The limits of detection ranged from 0.05 to 0.09 μg L−1 for all addition and recovery tests, enabling the determination of total Hg. The proposed method is sensitive, simple (no sample pretreatment) and provides a direct approach to the generation of mercury vapor from ethanol biofuel samples while promoting “green” chemistry.

A very simple procedure is proposed for the determination of total and inorganic Hg in biological materials. Organic Hg (methylmercury) can be obtained from the difference. After treating the sample at room temperature with tetramethylammonium hydroxide (TMAH), inorganic Hg is obtained by cold vapor atomic absorption spectrometry (CV-AAS), keeping the quartz cell at room temperature, while total Hg is obtained by the same technique, heating the quartz cell in an air–acetylene flame. By analyzing several biological certified materials, it was evident that the difference between the mentioned concentrations corresponds to methylmercury. Cold vapor graphite furnace atomic absorption spectrometry (CV-GF-AAS) with retention of the vapor in a heated Au-treated graphite tube was used to optimize the vapor generation conditions and also to determine total Hg. In a general way, the concentrations obtained by both techniques were in agreement with the certified values or with differences of the certified values for total, Hg2+ and CH3Hg+, according to the t-test for a 95% confidence level. Total Hg results obtained by the two techniques were also in agreement. The relative standard deviations were lower than 10% for most of the results. The detection limits in the sample were: 0.13 μg g−1 for total Hg and 0.025 μg g−1 for Hg2+ by CV-AAS. The detection limit for total Hg by CV-GF-AAS was 0.001 μg g−1. It is amazing how this very simple method is able to provide very important information on mercury speciation.