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Analytical and Bioanalytical Chemistry (v.363, #4)
Application of atomic force microscopy to particle sizing by G. Köllensperger; G. Friedbacher; A. Krammer; M. Grasserbauer (pp. 323-332).
AFM has been applied for studying morphology and size distribution of nanometer-sized particles adsorbed on flat surfaces. For the quantitative evaluation of the images an algorithm for automatical particle detection and volume calculation has been developed. In this way a large number of particles can be automatically evaluated in order to derive size distributions or surface coverages. The method has been successfully applied to determine size distributions of environmental aerosol particles collected with an 11-stage low pressure impactor. The first four stages with average aerodynamic equivalent diameters (aed) ranging from 21 to 170 nm were investigated. The calculated aed values were in good agreement with the predicted aed for each stage. Additionally, it could be shown that sampling conditions and storage time affect the derived size distributions. Furthermore, AFM has been applied as reference method for conventional particle sizing techniques. For this purpose technologically relevant powders as titanium oxide powder and tungsten carbide powder were investigated using AFM and the results were compared with conventional techniques such as high resolution SEM and a light scattering method. The derived cumulative size distributions were in good agreement. The results clearly show that AFM constitutes a convenient tool for size determination, not only for ultrafine particles exploiting the high resolving power, but also in the case of larger particles.
Analytical performance of a radiofrequency-powered glow discharge excitation source associated with bias voltage modulation by K. Wagatsuma (pp. 333-338).
A 13.56-MHz Grimm-type glow discharge plasma on which external d.c. voltages are superimposed is investigated for the application to optical emission spectrometry. With a voltage modulation technique associated with phase-sensitive detection, the emission intensities can be measured at very low noise levels, enabling the detection power to be improved. The experimental parameters: d.c. voltage, modulation frequency, and Ar pressure, are investigated for obtaining the optimum conditions. It is possible to obtain a detection limit (Cu I 327.40 nm) of 8 × 10–4 wt.% for Cu in Fe-based alloys, while 6.6 × 10–3 wt.% in the case of conventional detection.
Characterization of acoustic signals produced by ultraviolet laser ablation inductively coupled plasma atomic emission spectrometry by Viktor Kanicky; Vitezslav Otruba; J.-M. Mermet (pp. 339-346).
A simple device was designed to measure the acoustic signal accompanying laser ablation. The potential use of this signal for laser ablation-inductively coupled plasma atomic emission was examined. A frequency quadrupled pulsed Nd:YAG laser radiation was used for the ablation of glass, steel and ceramic samples. The relation between the acoustic signal, the laser energy, the analyte signal and the amount of ablated material was studied and evidence of the use of the acoustic signal for the exact focusing of the laser beam onto the sample surface was given. A more intense acoustic signal was observed for the exact focusing with a formation of larger ablation craters in glass and ceramics.
HPLC/ICP-OES determination of water-soluble silicone (PDMS) degradation products in leachates by R. Grümping; A. V. Hirner (pp. 347-352).
Inductively coupled plasma optical emission spectrometry (ICP-OES) was used for the element-specific determination of water-soluble organosilicon species separated by high-performance liquid chromatography (HPLC). Leachates from different waste deposit sites were investigated. The polydimethylsiloxane (PDMS) degradation product dimethylsilanediol (DMSD) could be detected in almost all samples in the low mg L–1 range, and it was furthermore possible to determine trimethylsilanol (TMSOL) in some leachate samples in the μg L–1 range. TMSOL was additionally analyzed by a method established before (LT-GC/ICP-OES). This study proved the occurrence of silanol compounds in leachates from locations were silicone material is deposited.
Studies on the determination of trace elements in high-purity Sb using GFAAS and ICP-QMS by M. V. Balarama Krishna; D. Karunasagar; J. Arunachalam (pp. 353-358).
Trace element impurities in high-purity antimony were determined employing three different methods for the removal of matrix; on Dowex 50WX 8 by adsorption from 0.1 mol/L HF and elution with 4 mol/L HNO3; on Chelex-100 resin (in NH4 + form) Bi, Cd, Co, Cu, and Pb were separated in the presence of tartaric acid at a pH of 9.0 ± 0.1 with subsequent elution with 2 mol/L HCl; these determinations were carried out by GFAAS. The separation of trace impurities from Sb by volatilization of the matrix from H2SO4 and HBr medium was also investigated. ICP-MS was used for the determination in these cases.All the three procedures showed that the removal of the antimony matrix was nearly quantitative (> 99.99%). The recoveries of trace elements were found to be > 95%. The relative standard deviations were in the range 2–7%. Standard addition calibrations were used. The levels of process blanks indicate that with careful optimization, the volatilization procedure coupled with ICP-QMS can be used for trace impurity characterization of 6N+ Sb.
In-situ concentration and determination of mercury by graphite furnace atomic absorption spectrometry with Pd-Rh as the chemical modifier by Zhang De-qiang; Yang Li-li; Sun Jian-min; Sun Han-wen (pp. 359-363).
A method has been proposed for the determination of mercury by cold vapor generation graphite furnace atomic absorption spectrometry (CV-GFAAS) with Pd-Rh as coating and chemical modifier. The trapping efficiency for mercury with Pd-Rh was higher than with Pd alone. The characteristic mass of the method, which gives an integrated absorbance of 0.0044 s, was found to be 55 pg and the absolute detection limit (3 σ) of 37 pg was obtained with the proposed modifier. The method was successfully applied to the determination of mercury in standard reference water samples, wastewater samples and cosmetics with a recovery range of 95–104%.
Analytical control of organic additives in electrolytic baths by UV spectroscopy in combination with multivariate analysis by M. Blanco; J. Coello; H. Iturriaga; S. Maspoch; D. Serrano (pp. 364-368).
A method for the simultaneous determination of organic additives in Zn(II) and Ni(II) electrolytic baths is proposed. Absorbance and first-derivative spectra were subjected to direct and inverse multiple linear regression (CLS and ILS, respectively) in order to choose the optimum alternative. The use of a factor design to prepare the samples enables the identification of interactions between analytes and their correction by ILS. The results provided by first-derivative spectra were slightly better than those obtained with absorbance spectra (prediction errors were always less than 2% with the former). The ILS procedure was applied to three industrial baths used to a different extent, with highly satisfactory results.
The influence of an anionic additive on the properties of cation-exchanger based calcium-selective electrodes by A. Schwake; K. Cammann; A. L. Smirnova; S. S. Levitchev; V. L. Khitrova; A. L. Grekovich; Y. G. Vlasov (pp. 369-375).
Potentiometric and electrochemical impedance spectroscopic investigations of calcium-selective membranes containing poly(vinylchloride), dioctylphenylphosphonate, calcium (bis[4-(1,1,3,3-tetramethylbutyl)phenyl] phosphate) and different amounts of the lipophilic anionic additive tridodecylmethylammonium chloride were carried out. The addition of the lipophilic additive changes the properties of calcium-selective electrodes, e.g. slope and calcium selectivity. The selectivity for calcium in presence of H+, Na+, K+, NH4 +, Mg2+, Ba2+, Sr2+ and (C2H5)4N+ was measured by three different methods, namely separate solution method, fixed interference method and matched potential method. Membranes with different concentration ratios between the calcium-exchanger and tridodecylmethylammonium chloride were investigated within half a year. The tendency of changing from cationic into anionic response for membranes containing nearly equivalent concentrations of cation- and anion-exchanger was shown. This inversion of the electrode response depends not only upon the concentration ratio of both ion-exchangers but also upon the total concentration of calcium-exchanger. Electrochemical impedance spectroscopy was used for monitoring the development of membrane resistances during a soaking period of one month. Based on these results dielectric constants for the calcium-selective membranes depending on the membrane composition were determined. Furthermore, the dependence of the membrane resistance on the membrane thickness and the concentration of tridodecylmethylammonium chloride was evaluated.
Sensitive reaction rate method for the determination of low levels of formaldehyde with photometric detection by A. A. Ensafi; S. Abassi (pp. 376-379).
A simple and rapid method is proposed for the determination of ultra trace amounts of formaldehyde. It is based on the catalytic effect of formaldehyde on the oxidation of Brilliant cresyl blue by bromate. The reaction is monitored photometrically by measuring the decrease in absorbance of the dye. Formaldehyde in the range of 0.005–2.300 μg/mL can be determined with a limit of detection of 0.003 μg/mL. The relative standard deviation for ten replicate measurements of 1.5 μg/mL formaldehyde is 0.1%. The method was used for the determination of formaldehyde in real samples with satisfactory results.
Analysis of urban particulate standard reference materials for the determination of chlorinated organic contaminants and additional chemical and physical properties by D. L. Poster; Michele M. Schantz; Stephen A. Wise; Mark G. Vangel (pp. 380-390).
A previously issued National Institute of Standards and Technology (NIST) Standard Reference Material (SRM), SRM 1649, Urban Dust/Organics has been analyzed for chlorinated organic contaminants (polychlorinated biphenyls and chlorinated pesticides) to provide certified values for a new class of compounds relative to the former certification. The material will be reissued as SRM 1649a. Four different analytical techniques were used. Specifically, two different methods of extraction (Soxhlet and pressurized fluid extraction) were used in conjunction with sample analysis by gas chromatography with two different columns (5% phenyl-methyl polysiloxane and 50% methyl C-18 dimethyl polysiloxane) that exhibit distinct selectivity, and with two different modes of detection (electron capture detection and mass spectrometry). The results from these techniques were combined to generate certified concentrations for 35 PCB congeners (some in combination) and 8 chlorinated pesticides. Ancillary assessments of additional chemical and physical properties of SRM 1649a include homogeneity, moisture, total organic carbon, extractable mass, and the particle-size distribution. The approach and the results for the certification of the PCB congeners and chlorinated pesticides in SRM 1649a, and the determination of the additional chemical and physical properties are described. In addition, the determination of PCBs and chlorinated pesticides in SRM 1648, Urban Particulate Matter (a particulate material certified for inorganic constituents), is also discussed although certified values are not presented.
A versatile and uncomplicated method for the analysis of volatile organic compounds in ambient urban air by Markus Haider; H. Malissa (pp. 391-398).
A method was developed for sampling and selective quantitative determination of typical volatile organic compounds (VOCs) in ambient urban air. A mobile and self-contained dual-channel air sampling tool based on solid phase adsorption was constructed. A simple calibration procedure circumventing the adsorption/desorption process was designed. The method was validated for seven “key-analytes”: n-hexane, 3-methyl-2-pentene, benzene, tetrachloroethene, styrene, 1,2,4-trimethylbenzene and acetophenone. The complete air sampling equipment is easily accommodated in a business suitcase. The lower limits of the practical working ranges are between 0.1 μg m–3 (tetrachloroethene) and 1.2 μg m–3 (benzene). Air samples were collected at a location in Salzburg with heavy motor vehicle traffic and measured in order to prove a satisfactory method performance under practical monitoring conditions.
Performance of two different types of passive samplers for the GC/ECD-FID determination of environmental VOC levels in air by Jutta Begerow; Erich Jermann; Türkan Keles; L. Dunemann (pp. 399-403).
Two types of passive samplers differing in their geometry (OVM 3500 by 3M, ORSA 5 by Dräger) were compared with respect to their suitability for typical environmental indoor and outdoor VOC concentrations. Benzene, toluene, o-, m-, p-xylene, ethylbenzene, tetrachloroethene, trichloroethene, nonane and ethyl acetate were representatively analyzed by dual-column capillary gas chromatography with tandem ECD-FID detection. There was a good correlation between the results obtained with OVM 3500 and ORSA 5 monitors indicating that both monitors can be used for this kind of application. The ratio between the results for indoor air sampling with OVM 3500 and ORSA 5 monitors was between 0.89 and 1.14 showing no systematic variation. For outdoor air sampling the ratio was between 1.06 and 1.26 indicating that the results obtained with OVM 3500 monitors were slightly higher. Reproducibility was slightly better when using ORSA 5 monitors. But, due to the higher sampling rates which are a result of the larger cross-sectional area, signal-to-noise ratios obtained with OVM 3500 monitors were between six to nine times higher than those of ORSA 5 samplers. Blank values of the unexposed samplers were comparable for both sampler types. As a consequence, detection limits were by a factor of 1.5 to 4 better for OVM 3500 monitors.
Removal of hexavalent chromium from wastewaters by bone charcoal by S. Dahbi; M. Azzi; M. de la Guardia (pp. 404-407).
The adsorption of hexavalent chromium onto bone charcoal was studied as a function of time, amount of charcoal, pH, concentration of chromium and sample volume. The cross interference with other elements was also investigated. Tests were carried out with solutions of chromium(VI) at concentrations between 5 and 25 mg · L–1. Chromium removal efficiencies higher than 90% were achieved at pH = 1 using 2 g of bone charcoal and a stirring time in the order of 30 min. Acid and alkaline pretreatments of bone charcoal did not improve the sorption capacity of bone charcoal against Cr(VI). The presence of other ions had practically no influence on the chromium removal. The presence of a matrix of tannery effluents did not reduce the removal capacity of bone charcoal for Cr(VI), but it was confirmed that only 47% of Cr(III) can be removed using these conditions.
Electrochemical studies of the interaction of tetraphenylporphyrin tetrasulfonate (TPPS) with albumin by H.-M. Zhang; Zhiwei Zhu; N.-Q. Li (pp. 408-412).
An electrochemical investigation of the interaction of TPPS with BSA on a Hg electrode is reported for the first time. The addition of BSA to TPPS solution results in a decrease of both the reduction and the oxidation current with no change of the peak potentials. In presence of BSA, no new peaks appear, and the standard rate constant k s is not significantly changed. The reaction of TPPS with BSA yields a kind of supramolecular complex TPPS-BSA, which is electrochemically non-active. The equilibrium constant for the complex has been calculated. The decrease of the peak current can be used to determine BSA concentrations.
The non-destructive determination of REE in fossilized bone using synchrotron radiation induced K-line X-ray microfluorescence analysis by K. Janssens; L. Vincze; B. Vekemans; C. T. Williams; M. Radtke; M. Haller; A. Knöchel (pp. 413-420).
The sensitivity and applicability of the synchrotron radiation induced X-ray microfluorescence (μ-SRXRF) spectrometer at the Hamburg synchrotron laboratory Hasylab for the determination of the distribution of trace concentrations of rare-earth elements (REE) in fossilized bone are discussed and critically compared to those of other trace analytical methods such as instrumental neutron activation analysis (INAA) and LAMP-ICPMS (laser ablation microprobe inductively-coupled plasma mass spectrometry). Measurements were carried out on two bone samples from contrasting terrestrial depositional environments at Olduvai Gorge (Tanzania). Results indicate that the microdistribution of the REE in these biological materials is not homogeneous and that the relative abundance of these elements can provide information on the palaeoenvironment during the fossilization process. The heterogeneous distribution of the REE can be determined in a quantitative and completely non-destructive manner provided the concentrations of individual REE are above 10 μg/g.
Selective voltammetric determination of chromium (VI) with DTPA and nitrate by Mieczysław Korolczuk; Malgorzata Grabarczyk (pp. 421-423).
A voltammetric determination of Cr(VI) in a flow system is described based on the selective accumulation of the reduction product of Cr(VI) on an HMDE, its complexation with DTPA and subsequent reduction of the complex in presence of nitrate. The calibration graphs were linear up to 100 and 5 nmol/L for deposition times 120 and 600 s, respectively. The relative standard deviation was 2.8% (n = 5) for Cr(VI) concentrations of 5 × 10–8 mol/L. The detection limits (3 σ) for Cr(VI) were 1.0 and 0.12 nmol/L at deposition times of 120 and 600 s, respectively. Typical interferences derived from real water samples are discussed. The method has been applied for the determination of Cr(VI) in spiked natural water samples.
Mixture of HIBA and glycolic acid as eluent for effective separation of yttrium and dysprosium by HPLC by Haizhou Wu; Noriyuki Watanabe; Yohichi Gohshi; Ryuji Kotama (pp. 424-426).
A mixture of 2-hydroxy-2-methylpropanoic acid (HIBA) and glycolic acid, with 1-octanesulfonate (OS) as hydrophobic ion proved to be successful for the separation of rare-earth elements (REE). If the ratio of HIBA and glycolic acid is suitably adjusted, it is possible to separate Y from Dy. The resolution of Y and Dy was further improved by controlling the concentration of HIBA and glycolic acid. The technique was applied successfully to the separation and analysis of highly pure Y2O3 and Dy2O3.
Solubility and partitioning studies with polycyclic aromatic hydrocarbons using an optimized SPME procedure by A. Paschke; Peter Popp; Gerrit Schüürmann (pp. 426-428).
In order to determine the water solubilitiy (S W) and octanol/water partition coefficient (K OW) of polycyclic aromatic hydrocarbons, we have optimized the direct solid-phase microextraction (SPME) of selected compounds (fluoranthene (FLU), phenanthrene (PHE), pyrene (PYR), benz[a]anthracene (BaA), benz[a]pyrene (BaP), and coronene) from the matrices water and octanol-saturated water. By the use of a 100 μm polydimethylsiloxane fibre and magnetic stirring of the sample with glass-coated mini-impellers in combination with gas chromatography we obtained limits of determination (GC-MS) comparable to standard HPLC procedures. Only coronene could not be quantified. The determined S W of FLU agree with reference data; for B[a]P we have obtained a 2 to 3 times higher value than described in recent literature. The obtained K OW values are close to reference data for both single components. For a mixture of FLU, PHE, PYR, and B[a]A the measured K OW values are 0.2–0.3 log units below tabulated values for the single components.