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Determination of copper, chromium, manganese and zinc by graphite furnace atomic absorption spectrometry after separation on polyacrylamide modified with nitrilo triacetic acid.

A new chelating collector, polyacrylamide modified with nitrilo triacetic acid (NTA) was developed for the separation and preconcentration of copper, chromium, manganese, and zinc prior to their determination by Graphite Furnace Atomic Absorption Spectrometry (GFAAS). The retention and recovery of the analyte elements were investigated by applying batch and column techniques. Cu(II), Cr(III), Mn(II) and Zn(II) were quantitatively retained by the collector at pH 5.5 or above. The chelating kinetics are so fast that in the batch procedure a quantitative separation of the analyte elements can be achieved in a few seconds. Since a very short contact time is enough to retain the analyte elements in column technique, a separation step can be completed quickly by applying fast flow rates in small columns. The elements collected were completely recovered with 2 mol/l of HCl. In the presence of sodium chloride up to 0.5% the analyte elements were quantitatively separated and recovered. Low blank values of the collector is another important advantage.

Journal Article↗

Determination of metals in airborne particulates by LEAFS and ICP-MS after sampling on reusable graphite filters.

Laser excited atomic fluorescence spectrometry combined with electrothermal atomization (ETA-LEAFS) and inductively coupled plasma mass spectrometry combined with electrothermal evaporation (ETV-ICP-MS) were used to measure the concentrations of some metals in ambient air sampled at the outskirts of Berlin. Using graphite to collect airborne particulates the contents of lead, palladium, and thallium could be determined in the pg/m(3) range.

Journal Article↗

Investigation of the automated determination of As, Sb and Bi by flow-injection hydride generation using in-situ trapping on stable coatings in graphite furnace atomic absorption spectrometry.

Flow-injection hydride generation and in situ concentration of As, Sb and Bi hydrides in graphite furnace atomic absorption spectrometry can be automated by means of a long-term stable trapping reagent replacing the Pd modifier. In a systematic study, carbide-forming elements (Zr, Nb, Ta, W) and noble metals (Ir, Ir/Mg, Pd/Ir) were investigated as stable adsorbers which require only a single application. Trapping temperature curves indicate high signals for trapping of As at 750-800 degrees C, Sb at 450-8000 degrees C and Bi at 100-500 degrees C on Zr-coated tubes. Ir- and Ir/Mg-coated tubes showed a high response for Sb and Bi at lower temperatures, but based on signal stability and reproducibility (over 400 trapping and atomization cycles tested) the better performance was found with the Zr-coated tubes. The radiotracers Sb-125 and Bi-207 were used to measure the hydride generation (>95% for both elements) and trapping efficiency (91% for Sb and 56% for Bi) on the Zr-coated tube. An adsorptive "carry-over effect" was observed with Sb and Bi but not with As, and trapping temperatures above 450 degrees C with Sb and 350 degrees C with Bi (the "critical temperatures") can lead to errors in absorbance values. On a Zr-coated tube the characteristic mass was about 16 pg for As, 15 pg for Sb and 9 pg for Bi (peak height) and the detection limits (3 sigma) were about 0.015, 0.010 and 0.027 ng, respectively, with a 1 ml sample loop. The method was tested by the determination of the elements in NIST low-alloy steel certified reference materials.

Journal Article↗

The determination of aluminum in biological fluids by means of graphite furnace atomic absorption spectrometry.

Methods are described for the determination of aluminium in serum and in diluted urine by means of graphite furnace atomic absorption spectrometry. For the analysis of serum, thermal decomposition of the sample in the furnace, using a ramp charring program, was found to be necessary in order to eliminate the organic material. The precision of the method was 10%. For urine the relative deviation was 9%. The precision was markedly improved by the use of an automatic sample injector (5.3%). Since large contamination problems make the determination of Al at the parts per billion (ppb) level very difficult, special attention was paid to the precautions to be taken in order to avoid external aluminum contamination.

Aluminum↗

Determination of lead in blood by graphite furnace atomic absorption spectrometry--a critique.

Graphite furnace atomic absorption spectrometry (GFAAS) is increasingly becoming the method of choice for the determination of Pb in blood. The major GFAAS methods that have been published to date include: (i) direct introduction of the sample into the furnace; (ii) dilution with water, Triton X-100 or acid; (iii) deproteinization with nitric acid; (iv) matrix modification; and (v) solvent extraction. This review focuses on the difficulties associated with each of these methods, and highlights recent attempts to overcome matrix interferences and improve the accuracy and precision of Pb determination in blood using modern furnace technology, especially the stabilized temperature platform furnace.

Humans↗

Graphite-furnace atomic absorption spectrometric determination of lead, cadmium, cobalt and nickel in infant formulas and evaporated milks after nitric-perchloric acid digestion and coprecipitation with ammonium pyrrolidine dithiocarbamate.

A graphite-furnace atomic absorption method, developed for lead and cadmium, was modified to enable simultaneous determination of lead, cadmium, cobalt and nickel in infant formulas and evaporated milks. The method was assessed on the basis of analytical quality assurance results during routine analysis of samples. Detection limits (ng g-1 based on 10 g sample size for ready-to-use formulas) were 0.04-0.21 for lead, 0.004-0.015 for cadmium, 0.04-0.2 for cobalt and 0.06-0.26 for nickel. Within-series repeatability and day-to-day reproducibility (among series) coefficients of variation (CVs) were, respectively, 11.7 and 16% for lead, 2.5 and 7.5% for cadmium, 7.2 and 18.8%for cobalt, and 8.1 and 8.6% for nickel at respective concentrations of 1.89, 0.40, 1.25 and 11.8 ng g-1.

Animals↗

Determination of nickel in urine with graphite furnace AAS using Zeeman correction.

We have developed a rapid and direct method for determining urine nickel. The urine specimen is diluted (1 + 1) with 2.0% v/v nitric acid and 0.001% v/v Triton X-100 and absorbance measurements are made with Zeeman-effect graphite furnace atomic absorption. The method is sensitive enough to be used to evaluate "normal" subjects for baseline studies or to evaluate environmental or other nonoccupational exposure to nickel. The characteristic mass (pg/0.0044A.s) is 26 pg, which is comparable to that obtained for aqueous solutions. The observed absorbance is linear up to about 100 micrograms l-1, after which the calibration curve departs from linearity. Procedures are described to rigorously exclude nickel contamination. We evaluated precision and accuracy with a U.S. National Bureau of Standards urine reference material. SRM 2670, with an informational nickel value of 70 micrograms l-1, and with a multielement water reference material, SRM 1643b, with a certified nickel value of 49 ng g-1. Within- and among-run standard deviations for SRM 2670 were calculated to be 9.0 and 2.45 micrograms l-1, respectively, and 2.1 and 1.1 micrograms l-1 for SRM 1643b. The detection limit, calculated as 3 SD of a "low" concentration urine, is about 1.1 micrograms l-1. The proposed method was applied to the determination of nickel in urine of 258 workers in a magnet manufacturing plant, and the data obtained support the usefulness of urine nickel for biological monitoring.

Environmental Exposure↗

A high-performance liquid chromatographic assay for reduced and oxidised glutathione in embryonic, neonatal, and adult tissues using a porous graphite electrochemical detector.

A high-performance liquid chromatographic (HPLC) assay employing a porous graphite electrochemical (EC) detector is described for the simultaneous quantification of reduced glutathione (GSH) and oxidised glutathione (GSSG) in embryonic, neonatal, and adult tissues. Samples were prepared by homogenization in 5% trichloracetic acid, centrifugation, filtration of the supernatant, and injection into the HPLC. Separation was achieved isocratically within 16 min on a 15 cm reversed-phase C18 analytical column with a particle size of 5 micron using an inexpensive mobile phase containing 2-propanol and water (2.8:100) with camphorsulfonic acid and phosphoric acid. The respective limits of detection for GSH and GSSG were 1.5 and 3 ng with a 6 microliter sample using a 3:1 signal to noise ratio. In addition to routine samples, the assay was sufficiently sensitive to detect picomole quantities of GSH and GSSG in small samples, such as a single mouse embryo, gestational day 9, weighing approximately 1 mg. The advantages and disadvantages of the method are compared with other assays for GSH and GSSG published in the literature.

Animals↗

Determination of lithium in rat brain regions and synaptosomes by graphite furnace atomic absorption spectrophotometry.

A graphite furnace atomic absorption spectrophotometric method for the analysis of very low concentrations of lithium in brain tissue and subcellular fractions is described. The method has a picogram sensitivity and shows a precision value of 10.1% expressed as the per cent variation coefficient for the tissue analysis of the metal. Lithium concentration in eight regions of the rat brain and regional synaptosomal lithium contents were analyzed with the method described. Results from these determinations show that lithium is heterogeneously distributed among rat brain regions 24 hr after a single s.c. lithium administration; hypothalamus, corpus striatum and midbrain were the regions with the highest lithium accumulation. Lithium is homogeneously concentrated in the synaptosomes obtained from rat brain regions. The method proposed may be considered adequate for trace lithium analysis in pharmacological studies of the metal.

Animals↗

An amperometric glucose sensor made by modification of a graphite electrode surface with immobilized glucose oxidase and adsorbed mediator.

A membrane-free glucose sensor was made by covalent immobilization of glucose oxidase on graphite followed by adsorption of N-methyl-phenazinium ion (PMS+). The mediator was found to be necessary for the electron transfer between the enzyme and the electrode. beta-D-glucose was determined amperometrically at an applied potential of +50 mV vs SCE. The current was independent of the rotational speed which indicates a kinetically controlled response. The response was strictly linear from the detection limit, 0.5, to 150 microM and usable up to about 2 mM beta-D-glucose. The immobilized enzyme was stable over several months but the mediator had to be renewed daily.

Electrodes↗

Improved high-performance liquid chromatographic procedure for the determination of lasalocid in chicken tissues and egg using polymeric and porous graphitic carbon columns.

A high-performance liquid chromatographic (HPLC) method for the determination of the ionophore coccidiostat lasalocid in poultry muscle and eggs was developed. The drug was extracted from tissue with acetonitrile. The extract was partitioned between saturated salt and carbon tetrachloride and the organic layer evaporated to dryness. Clean-up was by solid-phase extraction on a silica column. HPLC analysis was carried out on either a polymeric PLRP-S or a porous graphitic carbon Hypercarb column with a basic mobile phase and fluorescence detection with excitation at 310 nm and emission at 420-430 nm. Average recoveries from poultry muscle at the 0.002, 0.010 and 0.050 mg kg-1 levels were 65.7, 72.0 and 77.9%, respectively. Average recoveries from egg at the 0.010 and 0.100 mg kg-1 levels were 76.2 and 76.4%, respectively.

Animals↗

N-linked oligosaccharide analysis of rat brain Thy-1 by liquid chromatography with graphitized carbon column/ion trap-Fourier transform ion cyclotron resonance mass spectrometry in positive and negative ion modes.

We have previously described the site-specific glycosylation analysis of rat brain Thy-1 by LC/multistage tandem mass spectrometry (MS(n)) using proteinase-digested Thy-1. In the present study, detailed structures of oligosaccharides released from Thy-1 were elucidated by mass spectrometric oligosaccharide profiling using LC/MS with a graphitized carbon column (GCC-LC/MS). First, using model oligosaccharides, we improved the oligosaccharide profiling by ion trap mass spectrometry (IT-MS) coupled with Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS). Sequential scanning of a full MS(1) scan with FT-ICR-MS followed by data-dependent MS(n) with IT-MS in positive ion mode, and a subsequent full MS(1) scan with FT-ICR-MS followed by data-dependent MS(n) with IT-MS in negative ion mode enabled the monosaccharide composition analysis as well as profiling and sequencing of both neutral and acidic oligosaccharides in a single analysis. The improved oligosaccharide profiling was applied to elucidation of N-linked oligosaccharides from Thy-1 isolated by sodium dodecyl sulfate-polyacrylamide gel electrophoresis. It was demonstrated that Thy-1 possesses a significant variety of N-linked oligosaccharides, including Lewis a/x, Lewis b/y, and disialylated structure as a partial structure. Our method could be applicable to analysis of a small abundance of glycoproteins, and could become a powerful tool for glycoproteomics.

Animals↗

Evaluation of porous graphitic carbon stationary phase for simultaneous preconcentration and separation of organic and inorganic selenium species in "clean" water systems.

A high performance liquid chromatography procedure, based on porous graphitic carbon stationary phase, was evaluated for simultaneous on-line preconcentration and separation of organic and inorganic selenium species. Detection was achieved by inductively coupled plasma mass spectrometry with collision/reaction cell (ICP-CRC-MS). Different concentrations of formic acid were tested as mobile phase. A 240 mmol L(-1) concentration with pH adjusted to 2.6, allowed the separation of five species, i.e. selenite, selenate, selenomethionine, selenocystine and selenoethionine. On-line preconcentration of these five species was achieved when heptafluorobutyric acid was used as injection medium, inducing an enrichment of solutes at the top of the column which allowed large volumes (up to 1 mL) to be injected. Combining these injection conditions and 80Se monitoring with ICP-CRC-MS, detection limits between 2 and 8 ng (Se)L(-1), depending on the species, were obtained. Because of the extremely low detection limits obtained, the method was successfully applied to mineral waters.

Carbon↗

One-dimensional assemblies of platinum nanoparticles on a graphite surface using nonionic/ionized mixed hemicylindrical micelle templates.

One-dimensional (1-D) self-assemblies of Pt nanoparticles on a graphite surface have been synthesized via a template-directed sintering process of individual nanoparticles, using nonionic/cationic mixed hemicylindrical micelle templates of dodecyldimethylamine oxide surfactant at graphite/solution interfaces. The dimension and morphology of Pt nanoparticles can be widely controlled by the concentration of Pt ions equivalent to the mixing ratio of nonionic and cationic species in the surfactant micelle. This approach could be extended to fabricate a wide range of self-assembling metallic nanostructures on surfaces using various nonionic/cationic mixed micelle-like self-assemblies carrying metal ions at interfaces, while providing a fundamental insight into a 1-D self-assembly from individual nanoparticles.

Journal Article↗

Cloud point extraction and graphite furnace atomic absorption spectrometry determination of manganese(II) and iron(III) in water samples.

Cloud point extraction (CPE) was applied as a preconcentration step prior to graphite furnace atomic absorption spectrometry (GFAAS) determination of manganese(II) and iron(III) in water samples. After complexation with 1-phenyl-3-methyl-4-benzoyl-5-pyrazolone (PMBP), the analytes could be quantitatively extracted to the phase rich in the surfactant p-octylpolyethyleneglycolphenylether (Triton X-100) and be concentrated, then determined by GFAAS. The parameters affecting the extraction efficiency, such as solution pH, concentration of PMBP and Triton X-100, equilibration temperature and time, were investigated in detail. Under the optimum conditions, preconcentration of 10 ml of sample solution permitted the detection of 0.02 ng ml(-1) of Mn(II) and 0.08 ng ml(-1) of Fe(III) with enrichment factors of 31 and 25 for Mn(II) and Fe(III), respectively. The proposed method was applied to determination of trace manganese(II) and iron(III) in water samples with satisfactory results.

Iron↗

Adsorption of volatile organic compounds onto carbon nanotubes, carbon nanofibers, and high-surface-area graphites.

The adsorption of different alkanes (linear and cyclic), aromatics, and chlorohydrocarbons onto different nonmicroporous carbons--multiwalled carbon nanotubes (CNTs), carbon nanofibers (CNFs), and high-surface-area graphites (HSAGs)--is studied in this work by inverse gas chromatography (IGC). Capacity of adsorption was derived from the isotherms of adsorption, whereas thermodynamic properties (enthalpy of adsorption, surface free energy characteristics) have been determined from chromatographic retention data. HSAGs present the highest adsorption capacity, followed by CNTs and CNFs (although CNTs present an intermediate surface area between the two HSAG studied). Among the different adsorbates tested, benzene exhibits the highest adsorption capacity, and the same trend is observed in the enthalpy of adsorption. From surface free energy data, enthalpies of adsorption of polar compounds were divided into dispersive and specific contributions. The interactions of cyclic (benzene and cyclohexane) and chlorinated compounds (trichloroethylene, tetrachloroethylene, and chloroform) with the surfaces are mainly dispersive over all the carbons tested, CNTs being the material with the highest dispersive contribution, as was deduced also from the entropy parameter. Adsorption parameters were correlated with morphological and chemical properties of the materials.

Journal Article↗

A study on pore-opening behaviors of graphite nanofibers by a chemical activation process.

In this work, porous graphite nanofibers (GNFs) were prepared by a KOH activation method in order to manufacture porous carbon nanofibers. The process was conducted in the activation temperature range of 900-1100 degrees C, and the KOH:GNFs ratio was fixed at 3.5:1. The textural properties of the porous carbons were analyzed using N2 adsorption isotherms at 77 K. The BET, D-R, and BJH equations were used to observe the specific surface areas and the micro- and mesopore structures, respectively. From the results, it was found that the textural properties, including the specific surface area and the pore volumes, were proportionally enhanced with increasing activation temperatures. However, the activation mechanisms showed quite significant differences between the samples activated at low and high temperatures.

Journal Article↗

Determination of trace nickel in water samples by cloud point extraction preconcentration coupled with graphite furnace atomic absorption spectrometry.

A new method based on the cloud point extraction (CPE) preconcentration and graphite furnace atomic absorption spectrometry (GFAAS) detection was proposed for the determination of trace nickel in water samples. When the micelle solution temperature is higher than the cloud point of surfactant p-octylpolyethyleneglycolphenyether (Triton X-100), the complex of Ni2+ with 1-phenyl-3-methyl-4-benzoyl-5-pyrazolone (PMBP) could enter surfactant-rich phase and be concentrated, then determined by GFAAS. The main factors affecting the cloud point extraction were investigated in detail. An enrichment factor of 27 was obtained for the preconcentration of Ni2+ with 10 mL solution. Under the optimal conditions, the detection limit of Ni2+ is 0.12 ng mL(-1) with R.S.D. of 4.3% (n = 10, c = 100 ng mL(-1)). The proposed method was applied to determination of trace nickel in water samples with satisfactory results.

Nickel↗