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111.
Günther-Leopold I Wernli B Kopajtic Z Günther D 《Analytical and bioanalytical chemistry》2004,378(2):241-249
Precise and accurate isotope ratio measurements are an important task in many applications such as isotope-dilution mass spectrometry, bioavailability studies, or the determination of isotope variations in geological or nuclear samples. The technique of MC-ICP–MS has attracted much attention because it permits the precise measurement of isotope compositions for a wide range of elements combined with excellent detection limits due to high ionisation efficiencies. However, the results are based mainly on measurements using continuous sample introduction. In the present study the determination of isotope ratios on various transient signals with a time duration of 30 to 60 s has been achieved by coupling high-performance liquid chromatography to a multicollector inductively coupled plasma mass spectrometer. In order to investigate the origin of ratio drifts across the transient signals for this hyphenated technique, measurements with the same standard solutions were also carried out using a flow-injection device for sample introduction. As a result of this application it could be concluded that the main source of the bias in the measured isotope ratios is within the ICP–MS instead of fractionation effects on the chromatographic column material. Preliminary studies on short transient signals of gaseous samples (dry plasma) showed a reverse fractionation effect compared with wet plasma conditions (flow injection and HPLC).Presented at the 2003 European Winter Conference on Plasma Spectrochemistry, Garmisch-Partenkirchen, Germany, January 2003 相似文献
112.
Observation of cerium isotope fractionation in ion-exchange chromatography of Ce(III)-malate complex
The cerium isotope fractionation between Ce(III)-malate complex in aqueous solution and cerium ions in a cation-exchange resin was conducted by displacement chromatography. The pH and the chemical composition of the eluent were optimized for maintaining the self-sharpening band boundaries and the 21 m chromatographic migration of the Ce band underwent. Graphite slurry was coated on the tantalum filament prior to sample loading for reducing the isobaric interferences in cerium isotopic ratio determination by mass spectrometry. From the experimental results, it was found that the heavier isotope was enriched in the front boundary part of the cerium adsorption band, which meant that the heavier isotope was preferentially fractionated into the Ce3+ malate complex rather than simply hydrated Ce3+ ions. The isotope separation coefficient for the 136Ce/140Ce and 142Ce/140Ce was 5.2 x 10(-5) and -1.9 x 10(-5), respectively, at 298 K. 相似文献
113.
We report here our investigations using Monte Carlo and molecular dynamics (MD) simulations, as well as quasi-elastic neutron
scattering experiments, to study the adsorption and diffusion of H2 and D2 in zeolite Rho. In the simulations, quantum effects are incorporated via the Feynman-Hibbs variational approach. At low temperatures,
we observe a reversal of kinetic molecular sieving in which D2 diffuses faster than H2. Based on fits of bulk data, we suggest new set of potential parameters for hydrogen, with the Feynman-Hibbs variational
approach used for quantum corrections. The transport properties obtained from MD simulations are in excellent agreement with
the experimental results, with both showing significant quantum effects on the transport at low temperature. The MD simulation
results on two different structures of zeolite Rho clearly demonstrate that the quantum effect is very sensitive to pore size.
High transport flux selectivity is noted at low temperatures, suggesting feasibility of kinetic isotope separation. 相似文献
114.
痕量铼的同位素稀释中子活化分析 总被引:6,自引:2,他引:6
将同位素稀释法的准确性与中子活性分析(NAA)的高灵敏度相结合,建立了一种新的痕量铼的测试方法,实验中对Re的检出限为0.004ng,全流程空白为0.05ng,地于Re含量为64ng/g的样品,在取样量为50mg时,单次测定误差(2σ)为3.1%,测定Re一为30ng/g的样品,本方法的2σ在3%以内,4次分析的RSD为4.1%,而采用一般的NAA,结果偏低约20%,并且RSD大于5%。 相似文献
115.
《Analytical letters》2012,45(6):1073-1085
Abstract This paper describes the behaviour of various caffeine deutero isotopo-mers analyzed using gas chromatography coupled wiih atomic emission detection. Results are given concerning the linearity of the response and the detection limits for carbon, nitrogen, hydrogen and deuterium. It is demonstrated that neither the number of deuterium atoms per isotopomer nor the location of deuterium labeling modify the analytical response. 相似文献
116.
117.
Guiwan Koh Ee‐mei Gui Tang‐Lin Teo Tong‐Kooi Lee 《Journal of separation science》2013,36(6):1054-1060
A high‐accuracy double isotope dilution mass spectrometric method using an exact matching approach with GC coupled to a mass spectrometer for the analysis of cyanuric acid in fortified milk powder was developed. Various parameters for sample clean‐up such as the type of SPE cartridge, GC column and type of derivatizing agent used were investigated. The method was found to be linear in the concentration range of 0.03 to 2 mg/kg of cyanuric acid in milk powder. LOD and LOQ were found to be 0.9 and 3 μg/kg, respectively. Recoveries in the range of 95.7 to 102.2% were obtained for the in‐house fortified milk powder samples, with RSD of measurements in the range of 0.2 to 3.0%. A metrological approach was undertaken to examine all possible biases that contributed to the combined measurement uncertainty of the method. This high‐accuracy method can serve as a reference method for techniques commonly applied in routine testing laboratories. 相似文献
118.
119.
Xavier de la Torre Cristiana Colamonici Davide Curcio Francesco Molaioni Francesco Botrè 《Analytica chimica acta》2012
The confirmation by GC/C/IRMS of the exogenous origin of pseudo-endogenous steroids from human urine samples requires extracts of adequate purity. A strategy based on HPLC sample purification prior to the GC/C/IRMS analysis of human urinary endogenous androgens (i.e. testosterone, androsterone and/or androstenediols), is presented. A method without any additional derivatization step is proposed, allowing to simplify the urine pretreatment procedure, leading to extracts free of interferences permitting precise and accurate IRMS analysis, without the need of correcting the measured delta values for the contribution of the derivatizing agent. The HPLC extracts were adequately combined to both reduce the number of GC/C/IRMS runs and to have appropriate endogenous reference compounds (ERC; i.e. pregnanediol, 11-keto-etiocholanolone) on each GC–IRMS run. The purity of the extracts was assessed by their parallel analysis by gas chromatography coupled to mass spectrometry, with GC conditions identical to those of the GC/C/IRMS assay. The method has been validated according to ISO17025 requirements (within assay precision below 0.3 ‰ 13C delta units and between assay precision below 0.6 ‰ 13C delta units for most of the compounds investigated) fulfilling the World Anti-Doping Agency requirements. 相似文献
120.
This paper mainly introduces the role of isotopes in exploring the origin of life and related principles. In addition, by reviewing the discovery history of isotopes and summarizing the contributions of major scientists, we hope to show the general process of science developments to the public. 相似文献