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Analytical and Bioanalytical Chemistry (v.360, #5)
Certified reference material for the quality control of EDTA- and DTPA-extractable trace metal contents in calcareous soil (CRM 600) by P. Quevauviller; M. Lachica; E. Barahona; A. Gomez; G. Rauret; A. Ure; H. Muntau (pp. 505-511).
Single extraction tests are commonly used to study the eco-toxicity and mobility of metals in soils, e.g. to assess the bioavailable metal fraction (and thus to estimate the related phyto-toxic and nutritional deficiency effects) and the environmentally accessible trace metals upon disposal of e.g. sediment on to a soil (e.g. contamination of ground waters). However, the lack of uniformity in the different procedures does not allow the results to be compared worldwide nor the procedures to be validated. This paper describes the interlaboratory testing of EDTA- and DTPA-extraction procedures for soil analysis, followed by the preparation of a calcareous soil reference material (CRM 600), the homogeneity and stability studies and the analytical work performed for the certification of the EDTA- and DTPA- extractable contents of some trace metals (following the standardized extraction procedures).
Long term stability of organic selenium species in aqueous solutions by R. Muñoz Olivas; Philippe Quevauviller; O. F. X. Donard (pp. 512-519).
Long term stability of organic selenium compounds (selenocystine, selenomethionine, trimethylselenonium ion) has been studied over a one year period for 2 analyte concentrations: 25 and 150 μg/L Se, at pH 4.5 in the dark, under different storage conditions: temperature of –20°C, 4°C, 20°C, 40°C; in Pyrex, Teflon, or polyethylene containers; in an aqueous matrix or in the presence of a chromatographic counter ion (pentyl sulfonate at 10–4 mol/L concentration). Light effects have also been tested. The stability of the selenium species was monitored by HPLC-ICP/MS.Storage conditions can drastically alter the stability of organic selenium species. Organoselenium compounds were shown to be stable in the dark over a one year period in an aqueous matrix at pH 4.5 in Pyrex containers at both 4°C and 20°C. Pyrex vials exposed to natural sunlight at room temperature resulted in a steady decrease of the selenoamino acid concentration. Teflon containers caused losses of less than 25% at both 4° C and 20° C in the dark. However, polyethylene vials presented, at all temperatures tested, a rapid decrease of the TMSe+ concentration. The stability of the Se species studied did not show significant differences between 4° C and 20° C in any container material used. Storage of solutions at 40° C led to slight differences between the Pyrex and Teflon containers. However, polyethylene presented a drastic decrease of the three species over time at this higher temperature. Solutions frozen at –20° C in polyethylene vials did not stabilize the TMSe+ signal. Finally, concentrations and matrices of the samples did not significantly affect the stability of the species.
Electrothermal vaporization-ICP-MS for the determination of metals in micro amounts of high-purity non-metals (P, As, Sb, S, Se, Te, I) by H. Wildner; G. Wünsch (pp. 520-526).
A thermal trace-matrix separation procedure has been developed for the determination of ultra-traces of metals in solid non-metals (P, As, Sb, S, Se, Te and I). These matrices are dissolved in high-purity hydrogen peroxide to form the corresponding acids. By applying a suitable temperature profile, coating the graphite tube with WC and using hydrogen as a gaseous modifier more than 90% of the matrix can be removed. Analyte recoveries are 90 to 105% with a standard deviation of 5 to 10%. Since the separation principle is not specific, non-metallic analytes show poor recoveries of 10 to 40% (20–100% RSD). Elements forming persistent carbides, such as refractory metals, require either HF or freon as an additional modifier. Separation of the matrix leads to higher sensitivities, fewer spectral and non-spectral interferences and to better precision. The graphite tube is only little contaminated and its lifetime is drastically increased. The improvements result in limits of detection in the lower pg/g-range in the solid non-metals. Furthermore, this method can be employed for amounts of sample around 1 mg at absolute detection limits below 1 pg. Best performance of the coupling of ETV to ICP-MS is only obtained in the single-ion monitoring mode which means only semi-sequential multi-element capabilities.
Determination of uranium, thorium, and 20 other elements in high-purity tungsten by radiochemical neutron activation analysis by V. Krivan; K.-H. Theimer; M. Lucic (pp. 527-534).
A radiochemical neutron activation analysis method for the determination of 22 elements in high-purity tungsten has been developed. For the assay of indicator radionuclides with long half-lives, the radiochemical separation was performed from HF/H2O2, HF/NH4F and HCl/H2SO4 media by a combination of cation and anion exchange on a Dowex 50 W × 8 and Dowex 1 × 8 column. An effective removal of the matrix-produced radionuclides of W and Re was achieved. U was determined via 140La, the daughter nuclide of the fission product 140Ba. Limits of detection of 2 ng/g for U and 0.02 ng/g for Th can be achieved. For the other elements, the limits of detection are between 0.004 ng/g (Sc) and 200 ng/g (Sr). The elements Hf, Ta and Sb could be determined by instrumental neutron activation analysis. This method was applied to the analysis of two tungsten powder samples of different purity grade. The results and limits of detection are compared with those of other methods.
Spectrophotometric reaction rate method for the determination of molybdenum by its catalytic effect on the oxidation of pyrogallol red with hydrogen peroxide by A. A. Ensafi; A. Haghighi (pp. 535-538).
A kinetic spectrophotometric method for the determination of molybdenum is based on its catalytic effect on the oxidation of pyrogallol red with hydrogen peroxide. The decrease of the absorbance of pyrogallol red in the presence of hydrogen peroxide with time from 0.5 to 4.5 min is proportional to the concentration of Mo(VI) over the range 0.010–0.500 μg/mL. The limit of detection is 0.008 μg Mo/mL. The precision and the effect of the presence of more than forty ions on the molybdenum determination are reported. Probable interferences are completely removed by a cation exchange resin. The procedure was successfully applied to the determination of molybdenum in plant materials and steels.
Hydrocarbon group type analysis of petroleum heavy fractions using the TLC-FID technique by B. K. Sharma; S. L. S. Sarowha; S. D. Bhagat; R. K. Tiwari; S. K. Gupta; P. S. Venkataramani (pp. 539-544).
Hydrocarbon group type analysis is important in all conversion processes and in preparation of feed for these conversion processes so as to learn the selectivity of the different type of catalysts for product yield and quality. The use of the Mark 5 Iatroscan detector and the method reported here allowed for a rapid and quantitative hydrocarbon group type analysis of petroleum residues without prior separation of asphaltenes. SARA type analyses of petroleum residues have been performed by a three stage development using n-hexane, toluene and DCM (95%):MeOH (5%). The standard deviation and coefficient of variation in repeated measurements by this method were as low as 0.65 wt% or less and 3.5 wt% or less, respectively. The time required for analysis of 10 samples could be as short as 90 min.
Cr(III)/Cr(VI) determination in waste water by ICP/AES with on-line HPLC (HHPN) sample introduction by Shen-Kay Luo; Harald Berndt (pp. 545-549).
Using hydraulic high-pressure nebulization (HHPN) for sample introduction, an on-line high-pressure flow system (HPLC system) becomes a functional component of the ICP spectrometer. By placing additionally an HPLC column between the sample valve and the high-pressure injection/nebulization nozzle, an improved species analysis is attained. An example is given by on-line separation and determination of Cr(III)/Cr(VI) in real waste water samples with ICP/AES. The detection limit of each Cr oxidation state is 4 μg L–1 with an analysis cycle time of 5 min. In comparison to conventional coupling of HPLC and ICP spectrometry a considerably higher sensitivity is achieved. Using spiked samples the recovery of HHPN-ICP/AES was on an average better than 98% in contrast to only 79% for Cr(VI) determination with a UV photometric reference method. Due to chromatographic separation of Cr(VI) from matrix components and Cr (III), the technique no longer shows the typical spectral interferences caused by Ca (267.716 nm Cr line) and Fe (283.563 nm Cr line).
Chelating resin preconcentration and Hg(II) assisted elution followed by differential-pulse anodic stripping voltammetry for the determination of Cd, Cu, and Pb in seawater by Y.-C. Sun; Y.-L. Tu; Jerzy Mierzwa (pp. 550-555).
A new and efficient Hg(II) back-elution method for the desorption of Cd, Cu, and Pb from Chelex-100 chelating resin was developed. A smaller eluent volume and shorter elution time can be achieved using an Hg(II) containing eluent rather than pure nitric acid. Owing to the remaining Hg(II) ion in the effluent, a mercury thin-film electrode is formed in-situ during the anodic stripping voltammetric determination without any further addition of Hg(II). The results indicate that all the analytes in seawater matrix can be completely adsorbed on Chelex-100 resin from the sample at pH 6.5, and subsequently eluted from the resin with an acid solution of 5 × 10–4 mol/L Hg2+ + 1 mol/L HClO4. The detection limits obtained from the differential-pulse anodic (μg L–1 to ng L–1) stripping voltammetry are at sub-ppb to ppt (μg L–1 to ng L–1) levels permitting to determine Cd, Cu and Pb traces in seawater. The analytical reliability was confirmed by the analysis of the certified reference material CASS-II (open ocean seawater).
Chlorobiphenyls in sewage sludge; comparison of extraction methods by M. S. Rahman; M. Parreño; R. Bossi; A. B. Payá-Pérez; B. Larsen (pp. 556-563).
Six extraction methods for the analysis of PCBs (CB-28, CB-52, CB-101, CB-118, CB-138, CB-153 and CB-180) in sewage sludge were tested. A certified reference material (CRM 392) was used for the evaluation of the performance of the methods. Soxhlet-Dean-Starch with toluene as solvent, Soxhlet with hexane:acetone (2:3), cold digestion/saponification with 2 mol/L KOH in methanol followed by partition with hexane, and sonicated liquid-solid extraction with hexane:acetone (1:1) produced accurate results (97%, 93%, 104%, and 88%, respectively) with acceptable precisions (6.2%, 6.8%, 15% and 12%, respectively). Results in close agreement with the certified value for all congeners were obtained by treatment with BF3-methanol prior to partition with dichloromethane. However, this is a tedious procedure and involves the use of hazardous compounds. Cyclic steam distillation produced results with an accuracy of around 80% and a good precision (5.2%). The very low consumption of solvents and other expensive chemicals by this technique and the possibility of analyzing the extract directly without clean-up make it an interesting alternative to the more sophisticated methods. Column elution with dichloromethane was found to be less efficient (61%), but it is a rapid, direct method with a low consumption of solvents and it may therefore serve as screening method.
Determination of triallate and its metabolite 2,3,3-trichloro-prop-2-en-sulfonic acid in soil and water samples by W. Wang; R. Kreuzig; M. Bahadir (pp. 564-567).
A method based on solid phase extraction was developed for the determination of the herbicide triallate and its metabolite 2,3,3-trichloro-prop-2-en-sulfonic acid (TCPSA). Soil samples were extracted with methanol and diluted with water to yield a methanol/water ratio of 1 : 4. Triallate was adsorbed on C18 cartridges while TCPSA was enriched on quaternary amine anion exchange resins. Cartridges were eluted with methanol/ethyl acetate and methanol/sulfuric acid mixture, respectively. TCPSA methyl ester was formed using trimethyl orthoformate and subsequently analyzed by GC/ECD. Determination limits of both target compounds were 5 μg/kg soil with recoveries of 100 ± 12% for triallate and 57 ± 5% for TCPSA. In water analysis, determination limits were 0.05 μg/L with recoveries of 84 ± 14% for triallate and 100 ± 22% for TCPSA. In laboratory batch experiments, concentration of triallate decreased from 2690 to 1550 μg/kg soil within 59 days. 14 days after triallate application, TCPSA was determined to be 14 μg/kg which increased to 98 μg/kg soil at the end of the incubation period. Soil/water distribution coefficients in loamy sand soil were 102 for triallate and 0.02 for TCPSA which indicated a higher leaching tendency of the polar metabolite.
Determination of endosulfan and some pyrethroids in waters by micro liquid-liquid extraction and GC-MS by A. Fernández-Gutiérrez; J. L. Martínez-Vidal; F. J. Arrebola-Liébanas; A. Gonzalez-Casado; J. L. Vílchez (pp. 568-572).
A simple, rapid and reproducible method for the determination of some pesticide residues in water was developed using micro liquid-liquid extraction and gas chromatography - mass spectrometry with selected ion monitoring (GC/MS-SIM). The chlorinated insecticides α- and β-endosulfan and endosulfan-sulfate as well as the synthetic pyrethroids bifenthrin, permethrin, cypermethrin, fenvalerate and deltamethrin can be separated from a 500 mL sample water extracted with 0.5 mL of n-hexane containing anthracene-d10 as internal standard without clean-up in only 13 min. The recovery efficiencies of the tested compounds yielded more than 93.0% at a fortification level of 5 ng mL–1 and their relative standard deviations were between 1.9 and 11.7%. Detection limit of each compound ranged between 3 and 35 pg mL–1. The method was applied to ground, sea and tap waters from Almería (Spain). The solubilities in water at 20° C were determined.
GC-ECD determination of cypermethrin and its major metabolites in soil, elm bark, and litter by Heng Jin; G. R. B. Webster (pp. 573-579).
An analytical method has been developed for the simultaneous determination of residues of four pairs of isomers of the pyrethroid insecticide cypermethrin, and their main metabolites, cis- and trans-3-(2,2-dichlorovinyl)-2,2-dimethyl-cyclopropanecarboxylic acid (CCA) and 3-phenoxybenzoic acid (PBA), in elm bark, litter, and soil in the control of elm bark beetles, the vector of the Dutch elm disease. The residues of cypermethrin isomers and their metabolites were extracted with methanol under acidic conditions from elm bark, litter, and soil, cleaned up with liquid-liquid partitioning, and chromatographed by GC-ECD together after the CCA and PBA in the sample had been derivatized with α-bromo-2,3,4,5,6-pentafluorotoluene. The average recoveries of cypermethrin isomer pairs were 82 to 112% with relative standard deviations (RSDs) of 2.3 to 10% at the fortification levels of 2, 10, 100 μg/g in elm bark, 2, 15, 150 μg/g in litter, and 0.2, 2, 20 μg/g in soil. The recoveries of cypermethrin metabolites were 83 to 107% with RSDs from 2 to 12% at the fortification levels of 0.5, 5, and 10 μg/g in elm bark, and litter, and 0.1, 1, and 10 μg/g in soil.
Arylesters of alkylsulfonic acids in sediments Part III of organic compounds as contaminants of the Elbe River and its tributaries by S. Franke; J. Schwarzbauer; W. Francke (pp. 580-588).
Sediments from the Elbe River and from its major tributaries are shown to be contaminated with arylesters of alkylsulfonic acids. Here we report on the structure elucidation and quantification of aryl esters of alkylsulfonic acids. Chromatographic separation and mass spectrometric properties are discussed. Congener-specific analyses revealed a highly similar pattern throughout the area investigated. Alkylsulfonic acid phenylesters were present at almost all sampling locations. Amounts ranged from 33 000 μg/kg near the industrial region of Bitterfeld to 15 μg/kg in wadden sea sediments. Concentrations of alkylsulfonic acid cresylesters were between 10–40% of the phenylesters, and fell below the detection limit only in the Elbe estuary. The presence of aryl esters of alkylsulfonic acids in all sediment samples analyzed indicates a widespread distribution of these compounds in the environment. Previous literature described these compounds erroneously as phenoxyalkanes.
Strategy of analysis for the estimation of the bioavailability of zinc in foodstuffs by G. Schwedt; Abu Baker Tawali; Kerstin Koch (pp. 589-594).
After the application of simulated digestive fluids (gastric and intestinale fluid) as extraction solutions, AAS and differential pulse anodic-stripping voltammetry (DPASV) were used as analytical methods in combination with ion-exchange procedures for the determination of zinc species and total zinc contents. The ion exchange procedure and the shifting of electrochemical potentials as well as changes of the calibration slope after standard addition in the polarographic analysis allowed discriminating statements with regard to a possible resorption of zinc. On the basis of these methods, a strategy is presented for in vitro investigations of the bioavailability of zinc in foodstuffs.
Capillary gas-chromatographic method for determining non-derivatized sterols – some results for duplicate 24 h diet samples collected in 1994 by A. A. Jekel; H. A. M. G. Vaessen; R. C. Schothorst (pp. 595-600).
A gas-chromatographic method for the determination of non-derivatized sterols in duplicate 24 h diet was developed and validated. In the spring and autumn of 1994, 123 people participated in a duplicate 24 h diet study. Each participant collected one duplicate of the food and drink consumed in a continuous 24 h period. The first analytical step involved hydrolysis of the test portion, to which an internal standard solution was added. The sterols were extracted with cyclohexane and determined by capillary gas chromatography with flame ionization detection. Samples were analyzed for cholesterol, coprosterol, brassicasterol, campesterol, stigmasterol and β-sitosterol. The quality control checks showed that the sterol contents of 26 lyophilized subsamples were unstable. In these cases, non-lyophilized subsamples were taken for analysis. The mean intake for all participants was: for cholesterol 202 mg/day per person, for campesterol 27 mg/day per person, for stigmasterol 15 mg/day per person and for β-sitosterol 102 mg/day per person. The mean intake for brassicasterol could not be calculated because too many values were below the limit of detection. Coprosterol could not be detected in the samples.
Comparison of different methods for the determination of the water content and the dry mass correction factor in various plant samples by S. Stegen; F. Queirolo; P. Ostapczuk; A. Groemping; M. Paz; M. Restovic; C. Carrasco (pp. 601-604).
The water content was measured by microwave-, oven-, and freeze-drying in different vegetables like beans, corn, potato, alfalfa, garlic, and onions. Apart from beans and bean shells, all procedures resulted in similar values. Oven-drying seemed to be less suitable for beans. In samples which were in equilibrium with the laboratory environment for a longer time, the correction factor to dry mass was determined using a freeze-drying device, infrared-, microwave- and oven-drying. All the procedures yielded similar values for this factor.
Micellar-stabilized room-temperature phosphorimetric determination of the fungicide thiabendazole in canned pineapple samples by A. Segura Carretero; C. Cruces Blanco; R. Estrada Fernández; A. Fernández Gutiérrez (pp. 605-608).
A method for the determination of the fungicide thiabendazole (TBZ) by micellar-stabilized room-temperature phosphorescence is described. It does not require any separation step and allows the direct determination of the fungicide in canned pineapple samples. The effect of various experimental conditions is discussed in detail. The analytical curve of thiabendazole gives a linear dynamic range of 23.8–500.0 ng mL–1 and a detection limit of 23.8 ng mL–1. Recoveries of 103.9 and 89.2% for syrup and canned pineapple pulp, respectively, were obtained for 250 ng mL–1 thiabendazole.
Investigation of skin and skin lesions by NIR-FT-Raman spectroscopy by S. Fendel; B. Schrader (pp. 609-613).
There is a vast demand for in vivo methods for the detection of skin cancer, one of the most dangerous skin lesions. Use of near infrared Fourier transform (NIR-FT)-Raman spectroscopy virtually eliminates the fluorescence of the normal cell constituents and provides a signal to noise ratio, r SN, large enough to successfully evaluate the spectra using chemometric methods. A novel fiber optic probe for NIR-FT-Raman spectroscopy was used, which allows sterilization and the prevention of hazards due to laser radiation and makes in vivo measurements possible. The Raman spectra of normal skin are dominated by the connective tissue, mainly collagen type I. The Raman spectra of skin with inflammatory diseases show an increased lipid and water content. Kaposi sarcomas show typical features of tumors mainly in the amide III and the protein backbone range. A clear separation of Raman spectra of normal skin from those of benign and malignant neoplasms can be achieved by cluster analysis. However, the unequivocal diagnosis of skin cancer needs investigation of a larger number of more defined skin samples, taking into consideration the concurrent appearance of different skin symptoms like coloring and inflammation.
Preconcentration and voltammetric determination of trace myoglobin at a 6-mercaptopurine modified silver electrode by Y.-T. Long; Jun-Jie Zhu; H.-Y. Chen (pp. 614-617).
6-Mercaptopurine(6-MP) is covalently modified onto a silver electrode to construct a chemically modified electrode (CME). It exhibits the capability of selectively complexing myoglobin and can be applied as a selective biosensor for this compound. Myoglobin is accumulated onto the CME at 0.32 V (vs. SCE); after exchanging the medium it is determined by differential pulse stripping voltammetry. A cathodic stripping peak is obtained at 0.15 V (vs. SCE) by scanning the potential from 0.35 to –0.1 V. The peak currents are linearly proportional to the concentration of myoglobin in the range of 0.2 ∼ 4 μg/mL with a relative standard deviation of 7.8%. The detection limit is about 0.1 μg/mL. The mechanism of the complexation is also discussed.
Supercritical fluid extraction combined with solid phase extraction as sample preparation technique for the analysis of β-blockers in serum and urine by G. Meissner; Kari Hartonen; M.-L. Riekkola (pp. 618-621).
A method is developed for the determination of β-blockers in serum and urine at levels of 0.5 μg/mL. The technique uses a combination of solid phase extraction (SPE) with in situ derivatization and supercritical fluid extraction (SFE) with subsequent gas chromatography mass spectrometry. The optimization of the SFE step shows that a static extraction period can be eliminated. The method gives good linearity (r = 0.991–0.999) and repeatability in the concentration range of 0.5 to 5 μg/mL. Relative standard deviations for oxprenolol, propanolol and metoprolol were less than 5% in serum and 5–11% in urine.