Determinação de As, Cd e Pb em amêndoas e mesocarpo de babaçu, sapucaia, xixá e castanha-do-pará por espectrometria de absorção atômica

This work describes methods for the simultaneous determination of Cd and Pb by graphite furnace atomic absorption spectrometry and As by hydride generation atomic absorption spectrometry in Brazilian nuts. The samples (~ 0.300 g) were digested to clear solutions in a closed vessel microwave oven. The pyrolysis and atomization temperatures for simultaneous determinations of Cd and Pb were 1100 and 2100 °C, respectively, using 0.5% (w v-1) NH4H2PO4 + 0.03% (w v-1) Mg(NO3)2 as chemical modifier. The limits of detection (3Δ) were 3.8 μg kg-1 for As, 0.86 μg kg-1 for Cd and 13 μg kg-1 for Pb. The reliability of the entire procedures was confirmed by peach leaves (No. 1547 - NIST) certified reference material analysis and addition and recovery tests. The found concentrations presented no statistical differences at the 95% confidence level.

Systematic investigation of a family of gradient-dependent functionals for solids

Eleven density functionals are compared with regard to their performance for the lattice constants of solids. We consider standard functionals, such as the local-density approximation and the Perdew-Burke-Ernzerhof (PBE) generalized-gradient approximation (GGA), as well as variations of PBE GGA, such as PBEsol and similar functionals, PBE-type functionals employing a tighter Lieb-Oxford bound, and combinations thereof. On a test set of 60 solids, we perform a system-by-system analysis for selected functionals and a full statistical analysis for all of them. The impact of restoring the gradient expansion and of tightening the Lieb-Oxford bound is discussed, and confronted with previous results obtained from other codes, functionals or test sets. No functional is uniformly good for all investigated systems, but surprisingly, and pleasingly, the simplest possible modifications to PBE turn out to have the most beneficial effect on its performance. The atomization energy of molecules was also considered and on a testing set of six molecules, we found that the PBE functional is clearly the best, the others leading to strong overbinding.

Nonempirical hyper-generalized-gradient functionals constructed from the Lieb-Oxford bound

A simple and completely general representation of the exact exchange-correlation functional of density-functional theory is derived from the universal Lieb-Oxford bound, which holds for any Coulomb-interacting system. This representation leads to an alternative point of view on popular hybrid functionals, providing a rationale for why they work and how they can be constructed. A similar representation of the exact correlation functional allows to construct fully nonempirical hyper-generalized-gradient approximations (HGGAs), radically departing from established paradigms of functional construction. Numerical tests of these HGGAs for atomic and molecular correlation energies and molecular atomization energies show that even simple HGGAs match or outperform state-of-the-art correlation functionals currently used in solid-state physics and quantum chemistry.

Simultaneous determination of Cr, Fe, Ni and V in crude oil by emulsion sampling graphite furnace atomic absorption spectrometry

In this work a simple and reliable method for the simultaneous determination of Cr, Fe, Ni and V in crude oil, using emulsion sampling graphite furnace atomic absorption spectrometry is proposed. Under the best conditions, sample masses around 50 mg were weighed in polypropylene tubes and emulsified in a mixture of 0.5% (v v(-1)) hexane + 6% (m v(-1)) Triton X-100 (R). Considering the compromised conditions, the pyrolysis an atomization temperatures for the simultaneous determination of Cr, Fe, Ni and V were 1400 degrees C and 2500 degrees C, respectively. Aliquots of 20 mu L of reference solution and sample emulsion were co-injected into the graphite tube with 10 mu L of 1.0 g L(-1) Mg(NO(3))(2) as chemical modifier. The detection limits (n = 10, 3 sigma) and characteristic masses were, respectively: 0.07 mu g g(-1) and 19 pg for Cr; 2.15 mu g g(-1) and 31 pg for Fe; 1.25 mu g g(-1) and 44 pg for Ni; and 1.15 mu g g(-1) and 149 pg for V. The reliability of the proposed method was checked by fuel oil Standard Reference Material (SRMTriton X-100 (R) 1634c - NIST) analysis. The concentrations found presented no statistical differences compared to the certified values at 95% confidence level.

Paste Residence Time in a Spouted Bed Dryer. IV: Effect of the Inert Particle Size Distribution

The residence time distribution and mean residence time of a 10% sodium bicarbonate solution that is dried in a conventional spouted bed with inert bodies were measured with the stimulus-response method. Methylene blue was used as a chemical tracer, and the effects of the paste feed mode, size distribution of the inert bodies, and mean particle size on the residence times and dried powder properties were investigated. The results showed that the residence time distributions could be best reproduced with the perfect mixing cell model or N = 1 for the continuous stirred tank reactor in a series model. The mean residence times ranged from 6.04 to 12.90 min and were significantly affected by the factors studied. Analysis of variance on the experimental data showed that mean residence times were affected by the mean diameter of the inert bodies at a significance level of 1% and by the size distribution at a level of 5%. Moreover, altering the paste feed from dripping to pneumatic atomization affected mean residence time at a 5% significance level. The dried powder characteristics proved to be adequate for further industrial manipulation, as demonstrated by the low moisture content, narrow range of particle size, and good flow properties. The results of this research are significant in the study of the drying of heat-sensitive materials because it shows that by simultaneously changing the size distribution and average size of the inert bodies, the mean residence times of a paste can be reduced by half, thus decreasing losses due to degradation.

Europium luminescent polymeric microspheres fabricated by spray drying process

The spray drying method was used to prepare luminescent microspheres. These microspheres were prepared by spraying an aqueous solution of dextrin and an europium(III) complex with subsequent drying in a hot medium. The spray dried powder was characterized by scanning electron microscopy (SEM) and photoluminescence spectroscopy (PL). Particle size distribution was estimated from SEM images. The ultrasonic spray drying technique was successfully applied to yield a microparticulated and red luminescent powder composed by the [Eu(dpa)(3)](3-) stop (dpa = dipicolinic acid) complex incorporated in dextrin microspheres.

Tightened Lieb-Oxford Bound for Systems of Fixed Particle Number

The Lieb-Oxford bound is a constraint upon approximate exchange-correlation functionals. We explore a nonempirical tightening of that bound in both universal and electron number-dependent form. The test functional is PBE. Regarding both atomization energies (slightly worsened) and bond lengths (slightly improved), we find the PBE functional to be remarkably insensitive to the value of the Lieb-Oxford bound. This both rationalizes the use of the original Lieb-Oxford constant in PBE and suggests that enhancement factors more sensitive to sharpened constraints await discovery.

Determination of cadmium and lead in cetacean Dolphinidae tissue from the coast of Bahia state in Brazil by GFAAS

In the present study, cadmium and lead in the muscle, lung, liver and kidney of dolphins (Sotalia guianensis and Stenella clymene) of the Bahia coast in the northwest of Brazil were determined by graphite furnace atomic absorption spectrometry. Samples were digested using a diluted oxidant mixture (HNO(3) + H(2)O(2)) with a microwave heating program performed in five steps. The optimized temperatures and chemical modifier for the pyrolysis and atomization were 700 degrees C, 1400 degrees C and Pd plus Mg for Cd, and 900 degrees C, 1800 degrees C and NH(4)H(2)PO(4) for Pb, respectively. Characteristic masses and limits of detections (n = 20, 3 sigma) for Cd and Pb were 1.6 and 9.0 pg and 0.82 ng g(-1) and 0.50 ng g(-1), respectively. Repeatability ranged from 0.87 to 8.22% for Cd and 4.31 to 8.09% for Pb. The found concentrations presented no statistical differences at the 95% confidence level when compared with the ICP OES methods. Addition and recovery tests were also performed and the results ranged between 87 and 112% for both elements. Samples of cetacean Dolphinidae (S. guianensis and S. clymene) were analyzed, and the higher concentrations ranged from 0.09 to 46.2 mu g g(-1) for Cd and 0.04 to 0.47 mu g g(-1) for Pb in liver, and from 0.133 to 277 mu g g(-1) for Cd in the kidney. (C) 2010 Elsevier By. All rights reserved.

Simultaneous determination of chromium and manganese in alumina by slurry sampling graphite furnace atomic absorption spectrometry using NbC and NaF as modifiers

This paper reports a method for the direct and simultaneous determination of Cr and Mn in alumina by slurry sampling graphite furnace atomic absorption spectrometry (SiS-SIMAAS) using niobium carbide (NbC) as a graphite platform modifier and sodium fluoride (NaF) as a matrix modifier. 350 mu g of Nb were thermally deposited on the platform surface allowing the formation of NbC (mp 3500 degrees C) to minimize the reaction between aluminium and carbon of the pyrolytic platform, improving the graphite tube lifetime up to 150 heating cycles. A solution of 0.2 mol L(-1) NaF was used as matrix modifier for alumina dissolution as cryolite-based melt, allowing volatilization during pyrolysis step. Masses (c.a. 50 mg) of sample were suspended in 30 ml of 2.0% (v/v) of HNO(3). Slurry was manually homogenized before sampling. Aliquots of 20 mu l of analytical solutions and slurry samples were co-injected into the graphite tube with 20 mu l of the matrix modifier. In the best conditions of the heating program, pyrolysis and atomization temperatures were 1300 degrees C and 2400 degrees C, respectively. A step of 1000 degrees C was optimized allowing the alumina dissolution to form cryolite. The accuracy of the proposed method has been evaluated by the analysis of standard reference materials. The found concentrations presented no statistical differences compared to the certified values at 95% of the confidence level. Limits of detection were 66 ng g(-1) for Cr and 102 ng g(-1) for Mn and the characteristic masses were 10 and 13 pg for Cr and Mn, respectively.

Theoretical Characterization of Hydrogen Polyoxides: HOOH, HOOOH, HOOOOH, and HOOO

We have investigated the polyoxides HOOH, HOOOH, HOOOOH, and HOOO employing the CCSD(T) methodology, and the correlation consistent basis sets. For all molecules, we have computed fundamental vibrational frequencies, structural parameters, rotational constants, and rotation-vibration corrections. For HOOOH, we have obtained a good agreement between our results and microwave and infrared spectra measurements, although for the symmetric OO stretch some important differences were found. Heats of formation were computed using atomization energies, and our recommendation is as follows: Delta H degrees(f,298)(HOOOH) = -21.50 kcal/mol and Delta H degrees(f,298)(HOOOOH) = -10.61 kcal/mol. In the case of HOOO, to estimate the heat of formation, we have constructed three isodesmic reactions to cancel high order correlation effects. The results obtained confirmed that the latter effects are very important for HOOO. The new Delta H degrees(f,298)(HOOO) obtained is 5.5 kcal/mol. We have also calculated the zero-point energies of DO and DOOO to correct the experimental lower limit determined for the Delta H degrees(f,298)(HOOO). The Delta(Delta ZPE) decreases the binding energy of HOOO by 0.56 kcal/mol. Employing the latter value, the new experimental lower limit for Delta H degrees(f,298)(HOOO) is 3.07 kcal/mol, just 2.4 kcal/mol lower than our determination. We expect that the fundamental vibrational frequencies and rotational constants determined for HOOOOH and DOOOOD contribute to its identification in the gas phase. The vibrational spectrum of HOOOOH shows some overlapping with that of HOOOH thus indicating that one may encounter some difficulties in its characterization. We discuss the consequences of the thermochemical properties determined in this work, and suggest that the amount of HOOO present in the atmosphere is smaller than that proposed recently in this journal (J. Phys. Chem A 2007, 111, 4727).

Spin contamination in XOO radicals X = F, Cl, Br, HO: How is the investigation of the HOOO radical affected

We have analysed the effect of spin contamination in the wavefunction of HOOO. At least, two solutions can be found for the HF wavefunction. One, lower in energy, presents a high spin contamination and gives qualitatively incorrect structural parameters. On the other hand, the less contaminated HF reference gives structural parameters that are in better agreement with experiment, and positive spin densities on all atoms. Some of the problems described during previous investigations of HOOO can now be traced to problems in the HF reference. For the first time we report a CCSD(T) estimation of the structure of HOOO cis employing a HF reference with small spin contamination. (C) 2008 Elsevier B.V. All rights reserved.

Direct determination of iron in sand using solid sampling graphite furnace atomic absorption spectrometry

A fast and reliable method for the direct determination of iron in sand by solid sampling graphite furnace atomic absorption spectrometry was developed. A Zeeman-effect 3-field background corrector was used to decrease the sensitivity of spectrometer measurements. This strategy allowed working with up to 200 mu g of samples, thus improving the representativity. Using samples with small particle sizes (1-50 mu m) and adding 5 mu g Pd as chemical modifier, it was possible to obtain suitable calibration curves with aqueous reference solutions. The pyrolysis and atomization temperatures for the optimized heating program were 1400 and 2500 degrees C, respectively. The characteristic mass, based on integrated absorbance, was 56 pg, and the detection limits, calculated considering the variability of 20 consecutive measurements of platform inserted without sample was 32 pg. The accuracy of the procedure was checked with the analysis of two reference materials (IPT 62 and 63). The determined concentrations were in agreement with the recommended values (95% confidence level). Five sand samples were analyzed, and a good agreement (95% confidence level) was observed using the proposed method and conventional flame atomic absorption spectrometry. The relative standard deviations were lower than 25% (n = 5). The tube and boat platform lifetimes were around 1000 and 250 heating cycles, respectively.

A method for Ca, Fe, Ga, Na, Si and Zn determination in alumina by inductively coupled plasma optical emission spectrometry after aluminum precipitation

In this present work a method for the determination of Ca, Fe, Ga, Na, Si and Zn in alumina (Al(2)O(3)) by inductively coupled plasma optical emission spectrometry (ICP OES) with axial viewing is presented. Preliminary studies revealed intense aluminum spectral interference over the majority of elements and reaction between aluminum and quartz to form aluminosilicate, reducing drastically the lifetime of the torch. To overcome these problems alumina samples (250 mg) were dissolved with 5 mL HCl + 1.5 mLH(2)SO(4) + 1.5 mL H(2)O in a microwave oven. After complete dissolution the volume was completed to 20 mL and aluminum was precipitated as Al(OH)(3) with NH(3) (by bubbling NH(3) into the solution up to a pH similar to 8, for 10 min). The use of internal standards (Fe/Be, Ga/Dy, Zn/In and Na/Sc) was essential to obtain precise and accurate results. The reliability of the proposed method was checked by analysis of alumina certified reference material (Alumina Reduction Grade-699, NIST). The found concentrations (0.037%w(-1) CaO, 0.013% w w(-1) Fe(2)O(3), 0.012%w w(-1)Ga(2)O(3), 0.49% w w(-1) Na(2)O, 0.014% w w(-1) SiO(2) and 0.013% w w(-1) ZnO) presented no statistical differences compared to the certified values at a 95% confidence level. (C) 2011 Elsevier B.V. All rights reserved.

Feasibility study for the preparation of a tuna fish candidate reference material for total As determination

This work describes the evaluation of several parameters for the preparation of a tuna fish candidate as a reference material (RM) in order to measure the total As mass fraction by slurry sampling graphite furnace atomic absorption spectrometry (SLS-GF AAS) and slurry sampling hydride generation atomic absorption spectrometry (SLS-HG AAS). The main parameters investigated were the homogeneity, analyte segregation and composition during material production. For candidate RM preparation, tuna fish was collected at a local market, cleaned, freeze-dried and treated using different procedures as follows: (1) ground in a cutting mill and separated in different particle sizes (2) ground in cryogenic mill. The mass fraction of As in the cryogenically ground sample was (4.77 +/- A 0.19) mu g g(-1) for SLS-GF AAS and (4.61 +/- A 0.34) mu g g(-1) for SLS-HG AAS. The accuracy of the procedures was checked with tuna fish certified reference material (BCR 627) with recoveries of 102 and 94% for SLS-GF AAS and SLS-HG AAS, respectively. The homogeneity factor was calculated for different pretreatment procedures and for particle sizes in the range of 500-150 mu g, indicating good homogeneity, except for raw fish. There was no observed analyte segregation and no losses, no contamination and no changes in the microdistribution of material during preparation.