Determination of organic chlorine in water via AlCl derivatization and detection by high-resolution continuum source graphite furnace molecular absorption spectrometry.

High-resolution continuum source graphite furnace molecular absorption spectrometry (HR-CS-GF-MAS) was employed for determining adsorbable organic chlorine (AOCl) in water. Organic chlorine was indirectly quantified by monitoring the molecular absorption of the transient aluminum monochloride molecule (AlCl) around a wavelength of 261.42 nm in a graphite furnace. An aluminum solution was used as the molecular-forming modifier. A zirconium coated graphite furnace, as well as Sr and Ag solutions were applied as modifiers for a maximal enhancement of the absorption signal. The pyrolysis and vaporization temperatures were 600 °C and 2300 °C, respectively. Non-spectral interferences were observed with F, Br, and I at concentrations higher than 6 mg L-1, 50 mg L-1, and 100 mg L-1, respectively. Calibration curves with NaCl, 4-chlorophenol, and trichlorophenol present the same slope and dynamic range, which indicates the chlorine atom specificity of the method. This method was evaluated and validated using synthetic water samples, following the current standard DIN EN ISO 9562:2004 for the determination of the sum parameter adsorbable organic halides (AOX) for water quality. These samples contain 4-chlorophenol as the chlorinated organic standard in an inorganic chloride matrix. Prior to analysis, organic chlorine was extracted from the inorganic matrix via solid-phase extraction with a recovery rate >95%. There were no statistically significant differences observed between measured and known values and for a t-test a confidence level of 95% was achieved. The limits of detection and characteristic mass were found to be 48 and 22 pg, respectively. The calibration curve was linear in the range 0.1-2.5 ng with a correlation coefficient R2 = 0.9986.

Determination of heavy metals in activated charcoals and carbon black for Lyocell fiber production using direct solid sampling high-resolution continuum source graphite furnace atomic absorption and inductively coupled plasma optical emission spectrometry.

Reactivity and concentration of additives, especially activated charcoal, employed for the Lyocell process, enhance the complexity of reactions in cellulose/N-methylmorpholine-N-oxide monohydrate solutions. Analytical control of the starting materials is a basic requirement to know the concentration of heavy metals, which are potential initiators of autocatalytic reactions. Seven activated charcoal and two carbon black samples have been analyzed regarding their content of seven elements, Cr, Cu, Fe, Mn, Mo, Ni and V using direct solid sampling high-resolution continuum source graphite furnace AAS (SS-HR-CS GF AAS) and inductively coupled plasma optical emission spectrometry (ICP OES) after microwave-assisted acidic digestion as a reference method. The limits of detection of the former technique are 1-2 orders of magnitude lower than those of ICP OES and comparable to those of more sophisticated techniques. For iron the working range of HR-CS GF AAS has been expanded by simultaneous measurement at two secondary absorption lines (344,099nm and 344,399nm). Partial least-squares regression between measured and calculated temperatures for beginning exothermicity (T(on)) has been used to investigate the prediction capability of the investigated techniques. Whereas the ICP OES measurements for seven elements resulted in an error of prediction of 3.67%, the results obtained by SS-HR-CS GF AAS exhibited a correlation coefficient of 0.99 and an error of prediction of only 0.68%. Acceptable correlation has been obtained with the latter technique measuring only three to four elements.

Simultaneous determination of Cd and Fe in beans and soil of different regions of Brazil using high-resolution continuum source graphite furnace atomic absorption spectrometry and direct solid sampling.

A fast routine screening method for the simultaneous determination of cadmium and iron in bean and soil samples is proposed, using high-resolution continuum source graphite furnace atomic absorption spectrometry and direct solid sampling. The primary absorption line at 228.802 nm has been used for the determination of cadmium, and an adjacent secondary line, at 228.726 nm, for iron. Fourteen bean samples and 10 soil samples from nine states all over Brazil have been analyzed. The limits of detection (3 sigma, n = 10) were 2.0 microg kg(-1) for Cd and 4.5 mg kg(-1) for Fe. The relative standard deviation ranged from 4 to 7% for Cd and from 5 to 28% for Fe, which is usually acceptable for a screening method. The accuracy of the method has been confirmed by the analysis of two certified reference materials; the results were in agreement with the certified values at a 95% confidence interval.

Correction of structured molecular background by means of high-resolution continuum source electrothermal atomic absorption spectrometry--determination of antimony in sediment reference materials using direct solid sampling.

A simple, fast and accurate procedure is proposed for the determination of antimony in certified sediment reference materials using direct solid sampling high-resolution continuum source electrothermal atomic absorption spectrometry and iridium as a permanent modifier. The less sensitive resonance line at 231.147 nm has been used in order to allow the introduction of larger sample mass. Six certified reference materials, one river, one estuarine and four marine sediments have been analyzed. The use of iridium as a permanent modifier caused an increase of 30% in sensitivity and stabilized antimony in the sediment to a pyrolysis temperature of 1100 degrees C. Significant background absorption with pronounced rotational fine structure was observed at the optimum atomization temperature of 2100 degrees C, which coincided with the analyte atomic absorption in time. This background was found to be due to the electron excitation spectra of mostly the SiO and in part the PO molecules, and could be eliminated by applying a least-squares background correction algorithm. A characteristic mass of 28 pg Sb was obtained, and the limit of detection (3sigma, n=10) was 0.02 microg g(-1), calculated for 0.2 mg of sample. The results obtained for six certified reference materials with concentrations between 0.40 and 11.6+/-2.6 microg g(-1) Sb were in agreement with the certified values according to a Student's t-test for a 95% confidence level, using aqueous standards for calibration. The precision, expressed as relative standard deviation, ranged between 7% and 17% (n=5).

Determination of phosphorus, sulfur and the halogens using high-temperature molecular absorption spectrometry in flames and furnaces--A review.

The literature about the investigation of molecular spectra of phosphorus, sulfur and the halogens in flames and furnaces, and the use of these spectra for the determination of these non-metals has been reviewed. Most of the investigations were carried out using conventional atomic absorption spectrometers, and there were in essence two different approaches. In the first one, dual-channel spectrometers with a hydrogen or deuterium lamp were used, applying the two-line method for background correction; in the second one, a line source was used that emitted an atomic line, which overlapped with the molecular spectrum. The first approach had the advantage that any spectral interval could be accessed, but it was susceptible to spectral interference; the second one had the advantage that the conventional background correction systems could be used to minimize spectral interferences, but had the problem that an atomic line had to be found, which was overlapping sufficiently well with the maximum of the molecular absorption spectrum. More recently a variety of molecular absorption spectra were investigated using a low-resolution polychromator with a CCD array detector, but no attempt was made to use this approach for quantitative determination of non-metals. The recent introduction and commercial availability of high-resolution continuum source atomic absorption spectrometers is offering completely new possibilities for molecular absorption spectrometry and its use for the determination of non-metals. The use of a high-intensity continuum source together with a high-resolution spectrometer and a CCD array detector makes possible selecting the optimum wavelength for the determination and to exclude most spectral interferences.

Quantification of cell labeling with micron-sized iron oxide particles using continuum source atomic absorption spectrometry.

Detection of cells after transplantation is necessary for quality control in regenerative medicine. Labeling with micron-sized iron oxide particles enables noninvasive detection of single cells by magnetic resonance imaging. However, techniques for evaluation of the particle uptake are challenging. The aim of this study was to investigate continuum source atomic absorption spectrometry (CSAAS) for this purpose. Porcine liver cells were labeled with micron-sized iron oxide particles, and the iron concentration of the cell samples was investigated by a CSAAS spectrometer equipped with a Perkin-Elmer THGA graphite furnace. The weak iron line at 305.754 nm provides only about 1/600 sensitivity of the iron resonance line at 248.327 nm and was used for CSAAS measurements. Iron concentrations measured from labeled cells ranged from 5.8 +/- 0.3 to 25.8 +/- 0.9 pg Fe/cell, correlating to an uptake of 8.2 +/- 0.5 to 25.7 +/- 0.8 particles/cell. The results were verified by standardized morphometric evaluation. CSAAS enabled rapid quantification of particle load from small quantities of cells without extensive preparation steps. Thereby, CSAAS could be used for quality control in a clinical setting of cell transplantation.

Simultaneous determination of Cd and Fe in grain products using direct solid sampling and high-resolution continuum source electrothermal atomic absorption spectrometry.

Cadmium and iron are antagonistic elements in the sense that they produce different effects in the human body. Both elements have to be determined routinely in grain products, cadmium because of its toxicity, and iron because all grain products, according to Brazilian law, have to contain a minimum of 42 mg kg(-1) Fe to combat anemia. A routine screening method has been developed for the quasi simultaneous determination of cadmium and iron using high-resolution continuum source electrothermal atomic absorption spectrometry and direct solid sampling. The primary absorption line at 228.802 nm has been used for Cd, and an adjacent secondary line at 228.726 nm for the determination of Fe. Various chemical modifiers have been investigated, and a mixture of tungsten and iridium, applied as a permanent modifier, showed the best performance; it stabilized Cd up to a pyrolysis temperature of 700 degrees C and did not over-stabilize Fe. Two atomization temperatures were used sequentially, 1700 degrees C for Cd and 2600 degrees C for Fe, because of their significantly different volatilities. The characteristic masses obtained were 0.9 pg for Cd and 1.2 ng for Fe. The limits of detection (3 sigma, n=10) were 0.6 microg kg(-1) for Cd and 0.5 mg kg(-1) for Fe. The relative standard deviation ranged from 3 to 7% for Cd and from 4 to 13% for Fe, which is satisfactory for the purpose. The accuracy of the method was confirmed by the analysis of three certified reference materials; the results were in agreement with the certified values at a 95% confidence interval. The Cd content in the investigated grain products was between 0.9 and 10.5 microg kg(-1), but most of them did not contain the required minimum amount of iron.

Determination of sulfur forms in wine including free and total sulfur dioxide based on molecular absorption of carbon monosulfide in the air-acetylene flame.

A new method for the determination of sulfur forms in wine, i.e., free SO(2), total SO(2), bound SO(2), total S, and sulfate, is presented. The method is based on the measurement of the carbon monosulfide (CS) molecular absorption produced in a conventional air-acetylene flame using high-resolution continuum source absorption spectrometry. Individual sulfur forms can be distinguished because of the different sensitivities of the corresponding CS molecular absorption. The sensitivity of free SO(2) is about three times higher than the value for bound SO(2) and sulfate. The method makes use of procedures similar to those used in classic reference methods. Its performance is verified by analyzing six wine samples. Relative standard deviations are between 5 and 13% for free SO(2) and between 1 and 3% for total SO(2). For the validation of the accuracy of the new method, the results are compared with those of reference methods. The agreement of the values for total SO(2) with values of the classic method is satisfactory: five out of six samples show deviations less than 16%. Due to the instability of free SO(2) in wine and the known problems of the used reference method, serious deviations of the free SO(2) results are found for three samples. The evaluation of the limits of detection focuses on the value for free SO(2), which is the sulfur form having by far the lowest concentration in wine. Here, the achievable limit of detection is 1.8 mg L(-1). [figure: see text] Detection of non-metal elements using continuum source flame absorption spectrometry.

Direct determination of total sulfur in wine using a continuum-source atomic-absorption spectrometer and an air-acetylene flame.

Determination of sulfur in wine is an important analytical task, particularly with regard to food safety legislation, wine trade, and oenology. Hitherto existing methods for sulfur determination all have specific drawbacks, for example high cost and time consumption, poor precision or selectivity, or matrix effects. In this paper a new method, with low running costs, is introduced for direct, reliable, rapid, and accurate determination of the total sulfur content of wine samples. The method is based on measurement of the molecular absorption of carbon monosulfide (CS) in an ordinary air-acetylene flame by using a high-resolution continuum-source atomic-absorption spectrometer including a novel high-intensity short-arc xenon lamp. First results for total sulfur concentrations in different wine samples were compared with data from comparative ICP-MS measurements. Very good agreement within a few percent was obtained.

Microanalysis by laser-induced plasma spectroscopy in the vacuum ultraviolet.

A new setup for microanalysis by laser-induced plasma spectroscopy in the VUV range is presented and described in detail. The system features an integrated ablation and detection module with a newly designed VUV echelle system. The echelle permits a full spectral coverage between 150 and 300 nm with a resolving power lambda/Deltalambda between 11,000 and 15,000. At present, the ablation module permits a microanalysis with a crater size of 25 microm and a nominal depth resolution with an ablation rate of 150 nm/pulse. The VUV performance was demonstrated for bulk analysis of steel; detection limits for sulfur, carbon, and phosphorus were in the lower milligram per kilogram range. The VUV scanning and mapping performance for heterogeneous matrixes was illustrated for mineral bottom ash samples from a waste incineration process.