Simultaneous determination of As, Cu, Mn, Sb, and Se in drinking water by GRAS with transversely heated graphite atomizer and longitudinal Zeeman-effect background correction

A method has been developed for the direct and simultaneous determination of As, Cu, Mn, Sb, and Se in drinking water by electrothermal atomic absorption spectrometry (ETAAS) using a transversely heated graphite tube atomizer (THGA) with longitudinal Zeeman-effect back- ground correction. The thermal behavior of analytes during the pyrolysis and atomization stages was investigated in 0.028 mol L-1 HNO3, 0.14 mol L-1 HNO3 and 1 + 1 (v/v) diluted water using mixtures of Pd(NO3)(2) + Mg(NO3)(2) as the chemical modifier, With 5 mug Pd + 3 mug Mg as the modifier, the pyrolysis and atomization temperatures of the heating program of the atomizer were fixed at 1400degreesC and 2100degreesC, respectively, and 20 muL of the water sample (sample + 0.28 mol L-1 HNO3, 1 + 1, v/v), dispensed into the graphite tube, analytical curves were established ranging from 5.00 - 50.0 mug L-1 for As, Sb, Se; 10.0 - 100 mug L-1 for Cu; and 20.0 - 200 mug L-1 for Mn. The characteristic masses were around 39 pg As, 17 pg Cu, 60 pg Mn, 43 pg Sb, and 45 pg Se, and the lifetime of the tube was around 500 firings. The limits of detection (LOD) based on integrated absorbance (0.7 mug L-1 As, 0.2 mug L-1 Cu, 0.6 mug L-1 Mn, 0.3 mug L-1 Sb, 0.9 mug L-1 Se) exceeded the requirements of the Brazilian Food Regulations (decree # 310-ANVS from the Health Department), which established the maximum permissible level for As, Cu, Mn, Sb, and Se at 50 mug L-1, 1000 mug L-1, 2000 mug L-1, 5 mug L-1, and 50 mug L-1, respectively. The relative standard deviations (n = 12) were typically < 5.3% for As, < 0.5% for Cu, < 2.1% for Mn, < 11.7% for Sb, and < 9.2% for Se. The recoveries of As, Cu, Mn, Sb, and Se added to the mineral water samples varied from 102-111%, 91-107%, 92-109%, 89-97%, and 101-109%, respectively. Accuracy for the determination of As, Cu, Mu Sb and Se was checked using standard reference materials NIST SRM 1640 - Trace Elements in Natural Water, NIST SRM 1643d - Trace Elements in Water, and 10 mineral water samples. A paired t-test showed that the results were in agreement with the certified values of the standard reference materials at the 95% confidence level.

Direct determination of arsenic in sugar by GFAAS with transversely heated graphite atomizer and longitudinal Zeeman-effect background correction

A method has been developed for the direct determination of As in sugar by graphite furnace atomic absorption spectrometry with a transversely heated graphite atomizer (end-capped THGA) and longitudinal Zeeman-effect background correction. The thermal behavior of As during the pyrolysis and atomization steps was investigated in sugar solutions containing 0.2% (v/v) HNO3 using Pd, Ni, and a mixture of Pd + Mg as the chemical modifiers. For a 60-muL sugar solution, an aliquot of 8% (m/v) in 0.2% (v/v)HNO3 was dispensed into a pre-heated graphite tube at 70 degreesC. Linear analytical curves were obtained in the 0.25 - 1.50-mug L-1 As range. Using 5 mug Pd and a first pyrolysis step at 600 degreesC assisted by air during 40 s, the formation of a large amount of carbonaceous residue inside the atomizer was avoided. The characteristic mass was calculated as 24 pg As and the lifetime of the graphite tube was around 280 firings. The limit of detection (L.O.D.) based on integrated absorbance was 0.08 mug L-1 (4.8 pg As) and the typical relative standard deviation (n = 12) was 7% for a sugar solution containing 0.5 mug L-1. Recoveries of As added to sugar samples varied from 86 to 98%. The accuracy was checked in the direct analysis of eight sugar samples. A paired t-test showed that the results were in agreement at the 95% confidence level with those obtained for acid-digested sugar samples by GFAAS.

Simultaneous determination of As, Cu, Mn, Sb, and Se in drinking water by GFAAS with transversely heated graphite atomizer and longitudinal zeeman-effect background correction

A method has been developed for the direct and simultaneous determination of As, Cu, Mn, Sb, and Se in drinking water by electrothermal atomic absorption spectrometry (ETAAS) using a transversely heated graphite tube atomizer (THGA) with longitudinal Zeeman-effect background correction. The thermal behavior of analytes during the pyrolysis and atomization stages was investigated in 0.028 mol L-1 HNO3, 0.14 mol L-1 HNO3 and 1 + 1 (v/v) diluted water using mixtures of Pd(NO3)2 + Mg(NO3)2 as the chemical modifier. With 5 μg Pd + 3 μg Mg as the modifier, the pyrolysis and atomization temperatures of the heating program of the atomizer were fixed at 1400°C and 2100°C, respectively, and 20 μL of the water sample (sample + 0.28 mol L-1 HNO3, 1 + 1, v/v), dispensed into the graphite tube, analytical curves were established ranging from 5.00 -50.0 μg L-1 for As, Sb, Se; 10.0 - 100 μg L-1 for Cu; and 20.0 - 200 μg L-1 for Mn. The characteristic masses were around 39 pg As, 17 pg Cu, 60 pg Mn, 43 pg Sb, and 45 pg Se, and the lifetime of the tube was around 500 firings. The limits of detection (LOD) based on integrated absorbance (0.7 μg L-1 As, 0.2 μg L-1 Cu, 0.6 μg L-1 Mn, 0.3 μg L-1 Sb, 0.9 μg L-1 Se) exceeded the requirements of the Brazilian Food Regulations (decree # 310-ANVS from the Health Department), which established the maximum permissible level for As, Cu, Mn, Sb, and Se at 50 μg L-1, 1000 μg L-1, 2000 μg L-1, 5 μg L-1, and 50 μg L-1, respectively. The relative standard deviations (n = 12) were typically < 5.3% for As, < 0.5% for Cu, < 2.1% for Mn, < 11.7% for Sb, and < 9.2% for Se. The recoveries of As, Cu, Mn, Sb, and Se added to the mineral water samples varied from 102-111%, 91-107%, 92-109%, 89-97%, and 101-109%, respectively. Accuracy for the determination of As, Cu, Mn, Sb, and Se was checked using standard reference materials NIST SRM 1640 - Trace Elements in Natural Water, NIST SRM 1643d - Trace Elements in Water, and 10 mineral water samples. A paired t-test showed that the results were in agreement with the certified values of the standard reference materials at the 95% confidence level.

Zeeman effect in atmospheric O₂ measured by ground-based microwave radiometry

In this work we study the Zeeman effect on stratospheric O₂ using ground-based microwave radiometer measurements. The interaction of the Earth magnetic field with the oxygen dipole leads to a splitting of O₂ energy states, which polarizes the emission spectra. A special campaign was carried out in order to measure this effect in the oxygen emission line centered at 53.07 GHz. Both a fixed and a rotating mirror were incorporated into the TEMPERA (TEMPERature RAdiometer) in order to be able to measure under different observational angles. This new configuration allowed us to change the angle between the observational path and the Earth magnetic field direction. Moreover, a high-resolution spectrometer (1 kHz) was used in order to measure for the first time the polarization state of the radiation due to the Zeeman effect in the main isotopologue of oxygen from ground-based microwave measurements. The measured spectra showed a clear polarized signature when the observational angles were changed, evidencing the Zeeman effect in the oxygen molecule. In addition, simulations carried out with the Atmospheric Radiative Transfer Simulator (ARTS) allowed us to verify the microwave measurements showing a very good agreement between model and measurements. The results suggest some interesting new aspects for research of the upper atmosphere.

Mixing of 0(+) and 0(-) observed in the hyperfine and Zeeman structure of ultracold Rb-2 molecules

We study the combination of the hyperfine and Zeeman structure in the spin-orbit coupled A(1)Sigma(+)(u) = b(3)Pi(u) complex of Rb-87(2). For this purpose, absorption spectroscopy at a magnetic field around B = 1000 G is carried out. We drive optical dipole transitions from the lowest rotational state of an ultracold Feshbach molecule to various vibrational levels with 0(+) symmetry of the A - b complex. In contrast to previous measurements with rotationally excited alkali-dimers, we do not observe equal spacings of the hyperfine levels. In addition, the spectra vary substantially for different vibrational quantum numbers, and exhibit large splittings of up to 160 MHz, unexpected for 0(+) states. The level structure is explained to be a result of the repulsion between the states 0(+) and 0(-) of b(3)Pi(u), coupled via hyperfine and Zeeman interactions. In general, 0(-) and 0(+) have a spin-orbit induced energy spacing Delta, that is different for the individual vibrational states. From each measured spectrum we are able to extract Delta, which otherwise is not easily accessible in conventional spectroscopy schemes. We obtain values of Delta in the range of +/- 100 GHz which can be described by coupled channel calculations if a spin-orbit coupling is introduced that is different for 0(-) and 0(+) of b(3)Pi(u).

Antilocalization of hole carriers in Pb(1-x)Eu(x)Te alloys in the metallic regime

Magnetoresistance measurements in p-type Pb(1-x)Eu(x)Te alloys, for x varying from 0% up to 5%, have been used to investigate localization and antilocalization effects. These are attributed to both the spin-orbit scattering and to the large Zeeman splitting present in these alloys due to the large values of the effective Lande g factor. The magnetoresistance curves are analyzed using the model of Fukuyama and Hoshino, which takes into account the spin-orbit and Zeeman scattering mechanisms. The spin-orbit scattering time is found to be independent of the temperature, while the inelastic-scattering time increases with decreasing temperature suggesting the electron-phonon interaction as the main scattering mechanism.

Determinação de fósforo em aços por espectrometria de absorção atômica no forno de grafite

A method for the determination of phosphorus in steel samples by graphite furnace atomic absorption spectrometry, using the Zeeman effect background correction and the STPF conditions is proposed. The effect of iron (III) on the phosphorus signal was studied. It was verified, through the pyrolysis temperature curves, that iron (III) is an efficient chemical modifier, thermically stabilizing phosphorus up to 1400ºC. The phosphorus signal increases with the iron (III) concentration, but in the range, which corresponds to the usual concentrations of iron in the sample solutions, the increase is small. Phosphorus was determined in three standard reference materials, after its dissolution in a mixture of hydrochloric and perchloric acids in a PTFE bomb. The agreement with the certified concentration values was excellent. Iron (III) was added to the reference analytical solutions prepared in the blank of the dissolution, while the sample solutions were measured directly, since they already contained the modifier. The detection limit (k = 2) was 0.0042% of phosphorus in the steel sample.

Determinação direta de crômio em açúcar e leite por espectrometria de absorção atômica com atomização eletrotérmica em forno de grafite

A fast and direct method for the determination of Cr in milk and cane sugar suspensions using graphite furnace atomic absorption spectrometry with Zeeman-effect background correction is described. No sample pre-treatment was necessary, minimizing the risk of contamination. The concentration of chromium in cane sugar was evaluated using Cr reference solutions prepared in 1% v/v HNO3 solution. The milk samples were introduced into the furnace with a mixture of amines for avoiding the autosampler blockage and foaming of milk. Chromium determination in milk was based on the standard additions method (SAM). The limit of detection and characteristic mass for cane sugar sample (30 muL) were 0,13 ng/ml and 4,3 pg, and for milk sample (10 muL) were 0,23 ng/ml and 7,8 pg, respectively. The graphite tube lifetime was 300 firings for sugar-cane sample and 100 firings for milk sample. The heating program was implemented in 68 s.

Determinação direta de selênio em água de coco e em leite de coco utilizando espectrometria de absorção atômica com atomização eletrotérmica em forno de grafite

Selenium is both essential and toxic to man and animals, depending on the concentration and the ingested form. Most fruits and vegetables are poor sources of selenium, but coconut can be a good selenium source. Samples were suspended (1 + 4 v/v) in a mixture of tertiary amines soluble in water (10% v/v CFA-C). This simple sample treatment avoided contamination and decreased the analysis time. The standard additions method was adopted for quantification. The action of the autosampler was improved by the presence of the amines mixture in the suspension. A Varian model AA-800 atomic absorption spectrometer equipped with a graphite furnace and a GTA 100 autosampler was used for selenium determination in coconut water and coconut milk. Background correction was performed by means of the Zeeman effect. Pyrolytically coated graphite tubes were employed. Using Pd as chemical modifier, the pyrolysis and the atomization temperatures were set at 1400 and 2200ºC, respectively. For six samples, the selenium concentration in coconut water varied from 6.5 to 21.0 mug L-1 and in coconut milk from 24.2 to 25.1 mug L-1. The accuracy of the proposed method was evaluated by an addition-recovery experiment and all recovered values are in the 99.5-102.3% range. The main advantage of the proposed method is that it can be directly applied without sample decomposition.

Determinação simultânea de As, Cd e Pb em amostras de água purificada para hemodiálise por espectrometria de absorção atômica com forno de grafite, após otimização multivariada baseada no uso de planejamento experimental

This paper reports the development of a methodology for simultaneously determining As, Cd and Pb, employing GF AAS with polarized Zeeman-effect background correction. In order to make the procedure applicable, the influence of pyrolysis and atomization temperatures and the amount of chemical modifiers were studied. Factorial and central composite designs were used to optimize these variables. Precision and accuracy of the method were investigated using Natural Water Reference material, Nist SRM 1640. Results are in agreement with certified values at the 95% confidence limit when the Student t-test is used. This methodology was used for quality control of purified water for hemodialysis.

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.

Application of solid sampling device for direct determination of chromium and nickel in lubricating oils by graphite furnace atomic absorption spectrometry

One method using a solid sampling device for the direct determination of Cr and Ni in fresh and used lubricating oils by graphite furnace atomic absorption spectrometry are proposed. The high organic content in the samples was minimized using a digestion step at 400 degrees C in combination with an oxidant mixture 1.0% (v v(-1)) HNO3+15% (v v(-1)) H2O2+0.1% (m v(-1)) Triton X-100 for the in situ digestion. The 3-field mode Zeeman-effect allowed the spectrometer calibration up to 5 ng of Cr and Ni. The quantification limits were 0.86 mu g g(-1) for Cr and 0.82 mg g(-1) for Ni, respectively. The analysis of reference materials showed no statistically significant difference between the recommended values and those obtained by the proposed methods.

The Schrodinger and Pauli-Dirac Oscillators in Noncommutative Phase Space

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Evaluation and application of bismuth as an internal standard for the determination of lead in wines by simultaneous electrothermal atomic absorption spectrometry

A method for the direct determination of Pb in wines by simultaneous multi-element atomic absorption spectrometry (SIMAAS) using a transversely heated graphite atomizer, Zeeman-effect background corrector and internal standardization is proposed. Bismuth was used as an internal standard and Pd(NO3)(2) plus Mg(NO3)(2) as chemical modifier,to stabilize both the analyte and the internal standard. The implementation of two pyrolysis steps avoided any build-up of carbonaceous residues on the graphite platform. All diluted samples (1 + 1 v/v) in 0.2% v/v HNO3 and reference solutions (5.0-50 mug l(-1) Ph in 0.2% v/v HNO3) were spiked with 25 mug l(-1) Bi. For a 20 mul aliquot dispensed into the graphite tube, a good correlation (r = 0.9997) was obtained between the ratio of the analyte signal to the internal standard signal and the analyte concentration of the reference solutions. The electrothermal behaviour of Pb and Bi in red, white and rose wines were compared. In addition, absorbance variations due to changes in experimental conditions, such as atomizer temperature, integration time, injected sample volume, radiation beam intensity, graphite tube surface, dilution and sample composition, were minimized by using Bi as internal standard. Relative standard deviations of measurements based on integrated absorbance varied from 0.1 to 3.4% and from 0.5 to 7.3% (n = 12) with and without internal standard correction, respectively. Good recoveries (91-104%) for Pb spikes were obtained. The characteristic mass was 45 pg Pb and the limit of detection based on integrated absorbance was 0.9 mug l(-1) Pb. Internal standardization increased the lifetime of the tube by 25%. Direct determinations of Pb in wines with and without internal standardization approaches were in agreement at the 95% confidence level. The repeatability and the tube lifetime were improved when using Bi as internal standard. The improvement in accuracy using an internal standard was only observed when the analytical results were affected by errors.

Electrothermal AAS determination of Ni in soft drinks using Co as the internal standard

A method for the direct determination of Ni in soft drinks by graphite furnace atomic absorption spectrometry using a transversely heated graphite atomizer (THGA), Zeeman-effect background corrector, and Co as the internal standard (IS) is proposed. Magnesium nitrate was used to stabilize both Ni and Co. All diluted samples (1+1) in 0.2% (v/v) HNO3 and reference solutions [5.0-50 mu g L-1 Ni in 0.2% (v/v) HNO3] were spiked with 50 mu g L-1 Co. For a 20-mu L sample dispensed into the atomizer, correlations between the ratio of absorbance of Ni to absorbance of Co and the analyte concentration were close to 0.9996. The relative standard deviation of the measurements varied from 0.5 to 3.4% and 1.0 to 7.0% (n=12) with and without IS, respectively. Recoveries within 98-104% for Ni spikes were obtained using IS. The characteristic mass was calculated as 43 pg Ni and the limit of detection was 1.4 mu g L-1. The accuracy of the method was checked for the direct determination of Ni in soft drinks and the results obtained with IS were better than those without IS.