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Analytical and Bioanalytical Chemistry (v.366, #8)
Hydrazine reagents as derivatizing agents in environmental analysis – a critical review by M. Vogel; A. Büldt; U. Karst (pp. 781-791).
Hydrazine reagents are a well-known group of derivatizing agents for the determination of aldehydes and ketones in liquid and gaseous samples. Within this article, the most important hydrazine reagents are critically summarized, and their major applications in different fields, including environmental analysis, food chemistry and industrial analysis are introduced. As 2,4-dinitrophenylhydrazine (DNPH) is the basic reagent for several international standard procedures, its properties are discussed in detail. Particular focus is directed on the chemistry of the hydrazine reagents, and chemical interferences are considered. Recent methods for the determination of various oxidants using hydrazine reagents are presented as well. Due to limited space, this review does not cover the related field of carbohydrate analysis, although many chemical aspects are similar.
Certification of trace and major elements and methylmercury concentrations in a macroalgae (Fucus sp.) reference material, IAEA-140 by M. Coquery; F. P. Carvalho; S. Azemard; M. Bachelez; M. Horvat (pp. 792-801).
A marine reference material, IAEA-140, prepared with a macroalgae (Fucus sp.) was recently produced by the International Atomic Energy Agency and certified for trace and major elements and for methylmercury (MeHg). Certification of this material was achieved as an outcome of an international analytical intercomparison study which resulted in 116 independent sets of results reported by participants from 54 countries. The statistical evaluation of the collected data and the criteria used for assignment of the mean and uncertainty values are described. The analysis of data allowed to certify concentration values for 24 elements and MeHg, and to provide information values for another 10 elements. Regarding the elements which could be given certified values, between two and eight different instrumental methods were used to measure metal concentrations, and four independent analytical procedures were used to measure MeHg concentrations. In order to assess the results of the certification procedure, a comparison was made between the certified values obtained from the world-wide intercomparison results and the values obtained from a small subgroup of well-qualified laboratories. The means and 95% confidence intervals for reference values obtained by the two methods are similar for most elements showing that the usual method of certification used by the IAEA, based on large groups of participants, is indeed pertinent.
Quality control of automotive engine oils with mass-sensitive chemical sensors – QCMs and molecularly imprinted polymers by F. L. Dickert; P. Forth; P. A. Lieberzeit; G. Voigt (pp. 802-806).
Molecularly imprinted polyurethanes were used as sensor materials for monitoring the degradation of automotive engine oils. Imprinting with characteristic oils permits the analysis of these complex mixtures without accurately knowing their composition. Mass-sensitive quartz crystal microbalances (QCMs) coated with such layers exhibit mass effects in addition to frequency shifts caused by viscosity, which can be compensated by an uncoated quartz or a non-imprint layer. Incorporation of degradation products into the imprinted coatings is a bulk phenomenon, which is proven by variation of the sensor layer height. Therefore, the resulting sensor effects are determined by the degradation products in the oil.
Polyaniline-coated microtiter plates for use in longwave optical bioassays by S. A. Piletsky; T. L. Panasyuk; E. V. Piletskaya; T. A. Sergeeva; A. V. El’skaya; E. Pringsheim; O. S. Wolfbeis (pp. 807-810).
A technique for coating the wells of microtiterplates with polyaniline layers and with polyaniline/enzyme layers is presented. The resulting wells are shown to be useful for assaying enzyme substrates (as exemplified for glucose via pH) and hydrogen peroxide (via the redox properties of the film). Analyte detection is based on monitoring the absorption spectra of the polyaniline, which turn purple as a result of redox processes, or green on formation of acids by enzymatic reactions. Hydrogen peroxide (a species produced by all oxidases) and glucose (which yields protons on enzymatic oxidation) have been determined in the millimolar to micromolar concentration range. High sensitivity, film stability and good reproducibility of the measurements make the system an attractive alternative to existing biosensing schemes.
A new procedure for the construction of flow-through optodes. Application to determination of copper (II) by C. Sanchez-Pedreño; J. A. Ortuño; M. I. Albero; M. S. Garcia; J. C. Garcia de las Bayonas (pp. 811-815).
A new procedure for constructing an optical fibre reflectance, bulk optode membrane type, sensor is presented. The optode membrane consists of a plasticized poly (vinyl chloride) membrane in which the ionophore is dissolved, entrapped in a cellulose support. The new optode with the dye indicator 1-(2-pyridylazo)-2-naphthol (PAN) was incorporated in a new flow-through cell and the injection system was optimized to determine Cu (II) at 567 nm in the range 5 × 10−5–10−3 M. The response was reproducible and the optode can be regenerated using 10−2 M EDTA followed by water. The method was applied to the determination of copper in real samples.
Synthesis of rhodanine-bonded silica gel and its application in the preconcentration and separation of noble metals by P. Liu; Q. -S. Pu; Q. -Y. Sun; Z. -X. Su (pp. 816-820).
A silica gel based sorbent containing rhodanine as functional group (RDSG) was prepared. Its adsorption and separation characteristics for Ag(I), Au(III) and Pd(II) were studied by flow-injection (FI) on-line preconcentration. Influence of different experimental parameters such as acidity, eluent, co-existing ions were investigated. Trace amounts of Ag, Au and Pd could be efficiently adsorbed by rhodanine-bonded silica gel from acidic solution and eluted with thiourea solution. Common co-existing ions exhibited virtually no interference to the preconcentration and determination. The adsorption capacity of RDSG was 0.0352, 0.107 and 0.122 mmol/g for Ag, Au and Pd, respectively. Detection limits of 0.004, 0.022 and 0.019 μg/mL for Ag, Au and Pd, respectively, were achieved with a sampling time of 60 s at a flow rate of 5.0 mL/min. The relative standard deviation were 0.5%, 0.9% and 1.7% for 0.040 μg/mL Ag, 0.200 μg/mL Au and 0.300 μg/¶mL Pd. The sorption property did not change after 1000 cycles of sorption-desorption. The contents of Ag and Au in three national certified ore samples and Pd in a secondary nickel alloy, an anode slime and a CoCl2 electrolytic solution were determined. The results showed good agreement with the certified values.
Application of an imidazoline group-containing chelating fiber for the determination of trace noble metals in superhigh-temperature alloys by Yi Li; Ruixia Liu; Baowen Zhang (pp. 821-824).
An imidazoline group-containing chelating fiber was prepared by means of the reaction of nitrile groups with ethylenediamine in an hydrazine-modified polyacrylonitrile fiber. The adsorption properties of the chelating fiber for Au(III), Pd(II), Pt(IV), Ir(IV), Os(IV), Rh(III) and Ru(IV) ions, such as binding capacity, distribution coefficient, sorptive rate and quantitative elution of Au(III), Pd(II) and Pt(IV) ions were investigated. The imidazoline group-containing chelating fiber possessed high binding capacities and good adsorption kinetic properties, exhibited high affinity for noble metals in 0.1–1.0 mol/L HCl and could be efficiently re-used. After the separation of trace Au(III), Pd(II) and Pt(IV) ions from a matrix using the chelating fiber, these ions could be determined by ICP-AES with satisfactory results, and the relative standard deviation for Au(III), Pd(II) and Pt(IV) ions was less than 6%.
Rapid and selective determination of ammonium by fluorimetric flow injection analysis by H. Mana; U. Spohn (pp. 825-829).
Selective and sensitive procedures for the determination of ammonium in river water and diluted urine were developed by using flow injection analysis equipment. The methods are based on the derivatization of ammonia with o-phthaldehyde (OPA) and thioglycolate under alkaline conditions. The formed isoindole derivative is detected fluorimetrically at an excitation wavelength of 415 nm and an emission wavelength of 485 nm. The derivatization only takes 15 to 20 s at room temperature to achieve the maximum sensitivity. The optimized OPA reagent shows a surprisingly high selectivity for ammonium in the presence of many primary amines. With respect to the analysis of turbid and fluorescent sample solutions the selectivity can be improved by separating the ammonia through a microporous membrane from the OPA reagent. Without this separation step ammonia can be detected in the range between 0.05 and 100 μM with excellent linearity. After the insertion of an optimized membrane separation cell ammonia can be determined in the linear range between 0.2 μM and 20 mM.
Speciation of arsenic in coarse and fine urban aerosols using sequential extraction combined with liquid chromatography and atomic fluorescence detection by Z. Šlejkovec; I. Salma; J. T. van Elteren; É. Zemplén-Papp (pp. 830-834).
An analytical procedure for speciation of As in urban aerosol samples was developed. The aerosols were collected by sequential filtration through membrane filters. Part of each filter was investigated by INAA for the total amount of As. Another part of the filters was treated by a sequential extraction procedure to differentiate between water-extractable, phosphate-extractable and refractory chemical forms. Water-extractable forms were further differentiated into anionic As species by HPLC-HGAFS. Extractability of As into water exhibited a clear dependency on the aerosol size fraction (12% in coarse fraction and 50% in fine fraction). Dependency of the phosphate extractable As on the aerosol size fraction seems not to be significant (10–15% in both size fractions). The remaining amount, i.e., about 78% of the coarse As and about 40% of the fine As was considered to be refractory or environmentally immobile As. Water-extractable As forms could only be attributed to arsenate.
A sensitive method for the determination of iodine containing diagnostic agents in aqueous matrices using LC-electrospray-tandem-MS detection by R. Hirsch; T. A. Ternes; A. Lindart; K. Haberer; R. -D. Wilken (pp. 835-841).
Iodinated contrast media belong to the most frequently applied compounds in medicine. They exhibit a high polarity and are very persistent against metabolism by the organism and environmental degradation. A sensitive method for the determination of five iodinated contrast media in aqueous matrices is described. Solid phase extraction utilizing Isolute ENV+ material was used for sample enrichment. The contrast media were partially separated on a RP-C18 column, and detection was achieved using electrospray-tandem MS (API III plus and API 365) allowing the sensitive quantitation of these compounds down to the lower ng/L range. The recovery rates generally exceeded 70%, for spiked surface water as well as tap water. The analytes were detected in native samples such as municipal sewage treatment plant (STP) effluent, the river Rhine and even in tap water.
Flame atomic absorption spectrometric determination of lead in waste water and effluent after preconcentration using a rapid coprecipitation technique with gallium phosphate by S. Kagaya; Y. Araki; K. Hasegawa (pp. 842-845).
A determination method for lead in waste water and effluent was studied using flame atomic absorption spectrometry after preconcentration of lead by the rapid coprecipitation technique with gallium phosphate. Lead ranging from 0.5 to 50 μg was quantitatively coprecipitated with gallium phosphate from 100–150 mL sample solution (pH ∼5). The presence of gallium phosphate did not affect the atomic absorbance of lead. Since the concentration of gallium in the final sample solution is also measurable by flame atomic absorption spectrometry at 250.0 nm without further dilution, the rapid coprecipitation technique, which does not require complete collection of the precipitate, becomes possible using a known amount of gallium and measuring the concentrations of both lead and gallium in the final sample solution by flame atomic absorption spectrometry. The 32 diverse ions tested gave no significant interferences in the lead determination. The method proposed here is rapid and has good reproducibility.
Determination of polycyclic aromatic hydrocarbons in marine sediments using a new ASE-SFE extraction technique by M. Notar; H. Leskovšek (pp. 846-850).
In order to determine PAHs in marine sediment samples by GC/MS(SIM) a new extraction approach of ASE-SFE was evaluated using combined accelerated solvent extraction (ASE, dynamic and static mode) and supercritical fluid extraction (SFE, dynamic mode) without further purification of the sample. The solvents used for ASE-SFE were methylene chloride and carbon dioxide. The recovery data, precision and accuracy of the whole method were evaluated statistically. The average recoveries of PAHs, based on deuterated internal standards were 77% for 2–3-ring PAHs, 85% for 4-ring PAHs, 88% for ¶5-ring PAHs and 97% for 6-ring PAHs. The extraction time required for the ASE-SFE technique was 30 min, which is longer than in the case of independent use of ASE and shorter compared to SFE. ASE-SFE recoveries of PAHs from SRM marine sediment are comparable for (2–3-ring, 4-ring PAHs) or higher (5-ring, 6-ring PAHs) than reported for the conventional extraction methods of ASE and SFE. Method detection limits of (MDL) were statistically estimated. MDL values obtained for 15 PAHs compounds vary between 0.06 ngg−1 and 3.54 ngg−1.
Reasons for the decomposition of the fungicide thiram during preparation of fruit and vegetable samples and consequences for residue analysis by S. Heise; H. Weber; L. Alder (pp. 851-856).
The concentration of thiram in aqueous solution decreases by 50–75% within 20 min in the presence of cut pieces of apple, cucumber or celeriac with a section surface area of 160 cm2 each. The decomposition rate is predominantly influenced by the section surface area of the cut fruit and vegetable samples. Denaturing reaction conditions (exchange of the solvent water by methanol; boiling of sample material) will significantly slow down the decomposition rate. It was concluded that the thiram decomposition had been caused by enzymes on the section surface of the fruit and vegetable samples. For a specific determination of thiram, a simple rinsing of the intact fruit and vegetable material was appropriate as extraction method. For the screening of thiram residues, the often used Keppel method, which determines CS2 from thiram or dithiocarbamates seems to be applicable even if samples had been coarsely cut, since decomposition of the CS2-forming intermediates is slower than the breakdown of thiram itself. Therefore, specific determination of thiram is necessary only, if maximum residue limits for dithiocarbamates are not adhered to.
Flow injection spectrophotometric determination of ascorbic acid in soft drinks and beer by E. Luque-Pérez; A. Ríos; M. Valcárcel (pp. 857-862).
Two spectrophotometric methods, a photochemical and a non-photochemical, for the determination of ascorbic acid in soft drinks and beer using a flow-injection system are proposed. The non-photochemical method is based on the redox reaction that takes place between ascorbic acid and Fe(III), yielding dehydroascorbic acid and Fe(II). Fe(II) reacts with 1,10-phenantroline, originating the reddish orange Fe(phen)3 2+ complex (ferroin). This complex is spectrophotometrically monitored at 512 nm, and the signal is directly related to the concentration of ascorbic acid in the sample. The photochemical method has the same basis, nevertheless, uses the irradiation with visible light to enhance the redox reaction and so achieve higher sensitivities in the analysis. The non-photochemical method shows a linear range between 5 and 80 μg mL−1, with a relative standard deviation of 1.6% (n = 11), a detection limit of 2.7 μg mL−1 and a sample throughput of ¶60 samples h−1. The photochemical method shows a linear range between 1 and 80 μg mL−1, with a relative standard deviation of 1.0% (n = 11), a detection limit of 0.5 μg mL−1 and a sample throughput of 40 samples h−1.
Determination of proteins at nanogram levels by their quenching effect on large particle scattering of colloidal silver chloride by C. -Q. Zhu; D. -H. Li; Q. -Z. Zhu; H. Zheng; Q. -Y. Chen; H. -H. Yang; J. -G. Xu (pp. 863-868).
A novel quantitative method for the determination of proteins in aqueous solutions has been based on the quenching of the resonance scattering light of colloidal silver chloride in the presence of proteins. The detection limits for eight kinds of proteins (BSA, HSA, egg albumin, human γ-IgG,α-chymotrypsin, E. Coli. alpsase, myoglobin, α-casein) were at about 8 ng/mL; the linear ranges of the calibration curves were 10–400 ng/mL ¶under optimal conditions,except for human γ-IgG (20–¶400 ng/mL), myoglobin (10–300 ng/mL), and α-casein (10–300 ng/mL). Three wavelengths (398 nm, 475 nm, 499 nm) were all suitable for the determination and any acidity from pH 3.0 to pH 9.0 could be chosen. A few non-protein substances at high concentration levels interfered with this method, but this problem could simply be overcome by diluting the samples before the assay. Mechanism studies showed that the quenching effect of proteins on the scattering light of colloidal silver chloride was mainly due to the coagulation of AgCl particles retarded by protein. The method was employed for the determination of total protein in human serum with sactifactory results.
Selectively conjugated melittins for liposome time-resolved fluoroimmunoassay of theophylline in serum by A. Ius; M. A. Bacigalupo; R. Longhi; G. Meroni (pp. 869-872).
Theophylline (Th) has been selectively conjugated to the four amino groups of melittin (Mel) by solid phase peptide synthesis. The cytolytic activity of the resultant Th-Mel compounds was tested on liposomes trapping the bovine serum albumin (BSA) conjugate with 4,7-bis(chlorosulfophenyl)-1,10-phenanthroline-2,9-dicarboxylic acid (BCPDA). The loss of lytic activity was the highest for Th-K7-Mel. Th-G1-Mel retains almost the same lytic activity as Mel. A homogeneous liposome time-resolved fluoroimmunoassay (LITRFIA) of Th in serum has been carried out with Th-G1-Mel between 5 ng and 10 μg.
Laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) for spatially resolved trace analysis of early-medieval archaeological iron finds by W. Devos; M. Senn-Luder; C. Moor; C. Salter (pp. 873-880).
The suitability of laser ablation ICP-MS for minor and trace analysis of archaeological iron finds, produced by a direct reduction process in a ‘bloomery’ furnace, is reported. The analysis of elemental impurities in the iron can provide useful archaeometallurgical information on the production process and the provenance of the iron. Since, even after refinement, the iron resulting from this process may contain many inclusions (slag, charcoal, holes, etc.), a method should be used with sufficient spatial resolution to preclude the inclusions from the analysis. The ablation parameters are selected such that ablation craters of approx. 100 μm in diameter are obtained. The method is validated with low alloy steel and cast iron standard reference materials and by a comparative analysis with electron probe microanalysis (EPMA). The precision is limited mainly by the homogeneity of the iron, rather than by instrumental reproducibility. The advantages and drawbacks of the method are briefly compared with EPMA. Preliminary results from the analysis of archaeological iron samples from excavations at Develier-Courtételle (Canton Jura, CH), Neftenbach (Canton Zurich, CH), Wartau (Canton St Gallen, CH) and Mont Chemin (Canton Valais, CH) are given.