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Analytical and Bioanalytical Chemistry (v.366, #2)
Tungsten atomizer – theory of atomization mechanism of some volatile analytes by E. Krakovská; D. Remeteiová (pp. 127-131).
Several types of chemical reactions may participate in the evolution of free atoms in a tungsten furnace. Reactions may take place either in the homogeneous or heterogeneous phase. The assumed reactions may be classified into four types according to the phases in which they take place. Reactions occurring in the gaseous phase, i.e. in the inner volume of the furnace, are kinetically more significant. However, for atomization of easily volatile analytes heterogeneous reaction between gaseous compounds and between condensed salts of analytes and the solid surface of the furnace become significant. With regards to the reaction mechanisms during drying, pyrolysis and atomization of nitrates of volatile analytes, three basic types of chemical reactions may be assumed. Free atoms of analytes arise by evaporation of the elementary form of analytes at atomization temperature, where the particular analyte in its elementary form is produced by direct reduction of analyte nitrate by tungsten or by hydrogen at higher temperatures. Precursory reactions of atom formation are reduction reactions which occur between analyte nitrates and tungsten, between analyte nitrates and hydrogen, as well as reactions of thermal dissociation of relevant nitrates. The importance of particular types of precursory reactions for formation of metallic analytes or their oxides is documented by dependence of Gibbs energy values of particular reactions on the temperature.
Vanadium in marine mussels and algae by K. -R. Sperling; B. Bahr; J. Ott (pp. 132-136).
A method is presented which is sensitive enough for the determination of vanadium (V) in marine organisms such as mussels and algae. It was sufficiently checked by a reference material and it was applied to V determination in blue mussels and brown algae from the German Bight.
Determination of analytical limits in solid sampling ETAAS: a new approach towards the characterization of analytical quality in rapid methods by E. Lücker; K. Failing; Th. Schmidt (pp. 137-141).
In the present study the lower analytical limits of solid sampling electrothermal atomization atomic absorption spectrometry (SS-ETAAS) were characterized by means of blank measurements and – for the first time – by means of the calibration curve method, where a calibration near the range of these limits (limit of decision, detection and quantification) was performed. The limit of decision as derived from blank measurements was calculated according to the 3σ-criterion to be 0.003 and 0.019 ng for Cd and Pb, respectively. For Pb and Cd a roughly threefold increase of these limits was observed when the calibration method according to DIN 32 645 was applied. When solid reference material was used, only a slight increase could be observed. The analytical limits were 2 to 20 times lower than reported for sample decomposition methods. The blank measurement and conventional calibration curve method, however, do not account for factors relating to solid sampling such as sample mass and matrix. Therefore, the calibration curve model was applied to data derived from comparisons between direct solid sampling ETAAS and a compound reference method (ETAAS following sample homogenization and digestion). The observed analytical limits were not found to be substantially increased if enough samples with low element contents were available for calibration. Coupling of the calibration curve model with the comparison of methods included real test samples and thus the relevant maximum sample mass and analyte content in the range of the lower analytical limits. As validation procedures frequently include comparisons of methods, the present approach might prove to be of some general interest for the characterization of analytical quality in rapid methods.
Determination of soluble and insoluble nickel compounds in airborne particulate matter by graphite furnace atomic absorption spectrometry and inductively coupled plasma mass spectrometry by L. Füchtjohann; N. Jakubowski; D. Gladtke; C. Barnowski; D. Klockow; J. A. C. Broekaert (pp. 142-145).
An extraction procedure for the determination of soluble and insoluble nickel and its compounds in ambient air dust was investigated employing a special device for the generation of test aerosols and using water-soluble NiCl2, partly water-soluble NiCO3 and water-insoluble NiO as model compounds. Additionally, results of the separation and determination of different nickel species down to some ng/m3 in ambient aerosols are discussed. The extraction was carried out with a solution containing 0.01 mol/L EDTA in order to determine partly water-soluble compounds such as NiCO3 and water-soluble, non-toxic nickel compounds in one step. Airborne dust was sampled on filters at locations close to two metallurgical plants in Northrhine-Westphalia (Germany), and first results on the nickel concentration (mean (median) values over a period of 4 months: 8.6 ± 6.5 ng/m3 (6.7 ng/m3) and 27.7 ± 36 ng/m3 (10.8 ng/m3), respectively) in the collected dust are presented. For EDTA-soluble nickel compounds the maximum and mean fractions of total nickel were found to be 77.1% and 18.6 ± 12%, respectively.
Accurate and precise spectrochemical analysis of Bi-Pb-Sr-Ca-Cu-O high-temperature superconductor materials by R. Kucharkowski; C. Vogt; D. Marquardt (pp. 146-151).
For quality tests of ceramic Bi-Pb-Sr-Ca-Cu-O superconductor materials (precursors and final products) accurate stoichiometric determinations of the metallic major components are necessary. Three methods were developed during the last decade in our group. Their properties and the results obtained are compared. The first classical analytical procedure requires to much manpower. The second combined chemical-spectrometric procedure is a routine method today, but also unsuitable for rapid tests. A new fully spectrometric procedure was recently developed using a simultaneously working Echelle spectrometer with CID detector, autosampler and a special self-made data evaluation software. The basis of this method are multi-line measurements of each analyte element, a new method of spectral line selection for main component precision determinations, multi-component calibrations, and frequent external standardizations. For this method the sum of the confidence intervals of all element determinations was less than 1%, and no systematic error was detected.
Analytical application of 2f-wavelength modulation for isotope selective diode laser graphite furnace atomic absorption spectroscopy by H. D. Wizemann (pp. 152-155).
Experiences in the analytical application of the 2f-wavelength modulation technique for isotope selective atomic absorption spectroscopy in a graphite furnace are reported. Experimental as well as calculated results are presented, mainly for the natural lithium isotopes. Sensitivity, linearity, and (isotope) selectivity are studied by intensity modulation and wavelength modulation. High selectivities can be attained, however, on the cost of detection power. It is shown that the method enables the measurement of lithium isotope ratios larger than 2000 by absorption in a low-pressure graphite tube atomizer.
Laser atomic absorption spectrometry of excited Hg in a discharge applying sum frequency mixing of two diode lasers (preliminary results) by R. Uhl; O. Wolff; J. Franzke; U. Haas (pp. 156-158).
Wavelength modulation diode laser atomic absorption spectrometry is applied to the detection of atomic mercury. Transitions from metastable energy levels highly populated in a radio-frequency discharge are induced with laser diodes by use of nonlinear techniques. The wavelength of one strong transition at 365.119 nm with a high oscillator strength is obtained by sum frequency generation of two diode lasers. The cold vapor technique is used to transfer ionic into atomic mercury. The mercury in the vapor phase is transported by an argon stream into the discharge tube. From the time-dependent absorption signals detection limits of 100 ng/L are achieved at this state of research.
Inductively coupled plasma mass spectrometry: a versatile tool for a variety of different tasks by C. Moor; W. Devos; M. Guecheva; J. Kobler (pp. 159-164).
In a laboratory that is working in many different fields, a systematic approach is needed to decide ¶efficiently how a given analytical task should be handled. Four typical examples are presented to show how ICP-MS may be used to solve client’s problems. The examples are: the identification of lead projectiles, the determination of total and leachable fractions of impurities in a polymer (PVDF), used for manufacturing components of ultra-pure water distribution systems, the authentication of ¶antique silver alloys, and the determination of rare earth elements in geological materials. These examples demonstrate not only typical challenges for the instruments and the analysts handling them, but also ways to reach ¶a satisfactory solution within a reasonable amount of time.
Use of ultrasonic nebulizer with desolvator membrane for the determination of titanium and zirconium in human serum by means of inductively coupled plasma – mass spectroscopy by J. Kunze; S. Koelling; M. Reich; M. A. Wimmer (pp. 165-166).
A technique for the determination of titanium and zirconium in human blood serum, after pressurized digestion utilizing ICP-MS coupled to an ultrasonic nebulizer (USN) and desolvating membrane is described. As no CRM for titanium is available, zirconium has been determined in order to demonstrate the accuracy of the technique, as the limits in blood are well known. Bone cement consists basically of a polymer, namely polymethylmethacrylate (PMMA). For better X-ray contrast some manufacturers use incorporated ZrO2 with a volume fraction of 10 to 15%. Thus, the zirconium present in the PMMA matrix can be used as an indicator for the PMMA particulate debris.
Application of laser ablation inductively coupled mass spectrometry (LA-ICP-MS) for the determination of major, minor, and trace elements in bark samples by U. Narewski; G. Werner; H. Schulz; C. Vogt (pp. 167-170).
The large surface area of barks from many tree species enables the effective accumulation of pollutants. Therefore, the analysis of bark material will provide useful information about the degree of pollution of a certain region. The determination of main, minor, and trace elements (Al, Ca, Cd, Ce, Cr, Cu, Fe, Mn, P, Pb, S, Ti and Zn) in bark was performed with an Nd:YAG laser coupled to an ICP-MS system. Bark standards for the calibration by laser ablation ICP-MS were prepared from different bark layers which differ for some relevant elements in concentrations. Four digestion procedures for the decomposition of the standard pellets, the numbers of laser shots per sample and of samples per region necessary have been investigated. Representative results were obtained for 5 or more samples taken from different individuals of one species of a sampling area and the averaged element concentrations of 10 separately placed laser shots for each sample. Laser ablation ICP-MS was applied for the characterization of real bark samples from different regions with high and low pollution burden. It was shown that the method is well suited to characterize different degrees of environmental impact. Anthropogenic sources were responsible for the higher concentrations of most of the elements under investigation.
Lead isotope measurements on aerosol samples with ICP-MS by C. R. Widmer; U. Krähenbühl; J. Kramers; L. Tobler (pp. 171-173).
Size fractionated aerosols were collected with low pressure Berner impactors on a radio/TV tower 110 m above ground on a hill 10 km east of Bern at a total elevation of 1060 m asl. Two different wind sectors were chosen with the goal of assessing any differences in lead concentration and the 3 radiogenic lead isotopes (206,207,208) for east and west wind, respectively. A leaching technique was used to extract the lead quantitatively from the surface of the impaction foils. This method has been proven to be better suited for airborne particles than complete microwave digestion because it is less time consuming and contamination risk is smaller. Blank considerations played a major role in choosing all the chemicals, tubes, beakers and selecting the analytical method. Lead concentrations were determined with GF-AAS and lead isotopes with two different ICP-MS systems, one being a multicollector system. Precision of the simultaneous multicollector system was found to be at least a factor of 3 better than that of the sequentially operating ICP-MS. The small variations in isotope ratios from the two wind sectors can be distinctly seen with this enhanced precision. The observed relative difference in isotope ratios between east- and westwind was ∼0.6% for 207Pb/206Pb and ∼0.5% for 208Pb/206Pb.
Fast determination of trace elements on aerosol-loaded filters by X-ray fluorescence analysis considering the inhomogeneous elemental distribution by G. Steinhoff; O. Haupt; W. Dannecker (pp. 174-177).
X-ray fluorescence (XRF) analysis was successfully applied for the determination of Ca, Cu, Fe, Mn, Ni, Pb, V and Zn on aerosol filters with a diameter of 150 mm. Ambient aerosol was collected on quartz-fibre filters by Digitel high-volume samplers. For XRF analysis three small filter pieces with a diameter of 32 mm were cut out of each filter, considering the radial dependence of elemental distribution on the filter. Elemental concentration decreases by 8–10% from the centre to the outer circle for coarse mode elements. Distribution of fine mode elements display only small radial dependence (2–4%). Results of quantitative analysis by XRF were compared with atomic spectrometric methods (GF-AAS, ICP-OES). The good agreement between the methods confirmed the application of XRF spectrometry for routine analysis of filter samples loaded with ambient aerosol.
Online monitoring of aerosols with an energy-dispersive X-ray spectrometer by R. Harmel; O. Haupt; W. Dannecker (pp. 178-181).
A continuously working sampling and analyzing device was developed and tested. It is suitable for monitoring of metals bound to particulate matter in emissions of stack gases. The samples were precipitated on a pure quartz fiber filter tape and analyzed shortly afterwards non-destructively by an energy dispersive X-ray spectrometer (EDXRS). By using this method a wide range of elements with atomic numbers from 19 (K) ¶to 82 (Pb) can be analyzed. New experiments have shown that the novel combined particle sampling and analysis system ¶(X-DUST) could also successfully be used for the monitoring of toxic elements in ambient air.
Determination of cadmium by flow injection-chemical vapor generation-atomic absorption spectrometry by C. Vargas-Razo; J. F. Tyson (pp. 182-190).
A method was developed for the generation of a “cold vapor” of cadmium by means of flow injection-chemical vapor generation from aqueous samples, the determination being conducted with an atomic absorption spectrometer (Pyrex glass T-cell). Several gas-liquid separator designs, atomizer designs, and the effect of several reagents previously reported as sensitivity enhancers (including cobalt, nickel, thiourea and didodecyl-dimethylammonium bromide) were investigated. The limit of detection, calculated as the concentration giving a signal equal to three times the standard deviation of the blank, was 16 ng L–1, and the relative standard deviation was 1.4% for a concentration of 2 μg L–1 and 3.8% for 0.1 μg L–1. The addition of nickel and thiourea to the samples provided improved tolerance to the interference of coexisting ions. Two NIST certified reference materials, Montana Soil and Apple Leaves (respectively containing ¶41.7 ± 0.25 mg kg–1 Cd and 0.013 ± 0.002 mg kg–1 Cd) were accurately analyzed. The interference of lead was overcome by coprecipitation with barium sulfate, and the experimental values obtained were 41 ± 1 mg kg–1 Cd and 0.013 ± 0.002 mg kg–1 Cd, respectively.
Monitoring of total Hg in the river Elbe: FIA-device for on-line digestion by O. Wurl; O. Elsholz; Jörn Baasner (pp. 191-195).
The development of an apparatus for the on-line sampling, digestion and quantification of total mercury in surface water is described. Detection and quantification is done by flow injection cold vapor atomic absorption spectroscopy (FI-CVAAS). Three digestion methods were tested, chemical, microwave and UV. The influence of the digestion parameters (digestion method, digestion time, microwave power, concentration of oxidation solution) on the recovery of mercury in water of the river Elbe have been investigated. Mercury can be determined almost quantitatively (recovery rate > 85%) with some digestion procedures described. The best results were reached by UV digestion. The technique is fast, simple ¶to handle and robust. Each complete analysis only take four minutes. The working range is 10 to 1000 ng/L. The measuring arrangement has been applied successfully in a governmental monitoring station at Schnackenburg/Elbe, Germany.
On-line determination of mercury in river water at the German monitoring station Schnackenburg/Elbe by Olaf Elsholz; Carsten Frank; Birgit Matyschok; Frank Steiner; Oliver Wurl; Burkhard Stachel; Heinrich Reincke; Manfred Schulze; Ralf Ebinghaus; Maximilian Hempel (pp. 196-199).
A monitor is described which provides the on-line determination of mercury in river water at concentrations from 20 to 1000 ng/L. The measurement includes an on-line digestion with Br–/BrO3 – and UV-radiation. Each determination is controlled by an on-line addition of 50 and 100 ng/L mercury carried out by pre-dilution of a 500 and 1000 ng/L stock solution using sequential injection analysis (SIA). One cycle of analysis takes 20 min and results in nine signals. A five days stand-alone operation has been performed successfully. Details are also published at web page: “http/www.rzbd.fh-hamburg.de/¶∼prmercol”
Determination of arsenic species in water, soils and plants by J. Mattusch; R. Wennrich; A. -C. Schmidt; W. Reisser (pp. 200-203).
Ion chromatographic separation coupled with ICP-MS was used to determine arsenic species in plant and soil extracts. A scheme for growth, harvesting, sample pre-treatment and analysis was developed for the arsenic species to enable determination. Preliminary results obtained with ten herb plants grown on arsenic-contaminated soil compared to non-contaminated soil show a heterogeneous pattern of accumulation rate, metabolization and detoxification mechanisms in monocots and dicots. Arsenite appears to be the major component in plants with good growth. Organic arsenic species were even detected at very low concentrations (< 150 μg kg–1 (dry mass)).
Solar blind photocell – a simple element specific detector in Hg, As and Se speciation by Ch. Lüdke; E. Hoffmann; J. Skole; E. Ullrich (pp. 204-208).
An element-specific detection method, based on atomic absorption spectrometry (AAS) using solar blind photocells instead of a dispersion system, is described for the determination of Hg-, As-, and Se-species. Spectrometric investigations of AAS background lamps for As and Se measured with a CsI-cathode photocell shows its quality as narrow band detector. Species determination can be carried out subsequently to prior separation by HPLC or GC. The LODs for alkylated Hg species were below 1 ng/L, and for methylated As species below 1 μg/L. The relative standard deviation was < 10%. With the components described the production of cheap and automated dedicated speciation spectrometers is possible.
Speciation of copper, lead and cadmium in aquatic systems by circulating dialysis combined with flame AAS by K. Novotný; A. Turzíková; J. Komárek (pp. 209-212).
The assessment of free Cu(II), Pb(II) and Cd(II) ions in the presence of complexed species was realised by a circulating dialysis with Cuprophan planar membranes and subsequent quantification by flame atomic absorption spectrometry. The effect of the flow rate, the time of equilibration, pH and the presence of various complexing agents in the donor solutions were studied. The determination of free Cu(II), Pb(II) and Cd(II) ions in the presence of soil humic substances resulted from the above studies.