Günther-Leopold Ines, Wernli Beat, Kopajtic Zlatko, Günther Detlef
Laboratory for Materials Behaviour, Paul Scherrer Institute, 5232 Villigen PSI, Switzerland.
Anal Bioanal Chem. 2004 Jan;378(2):241-9. doi: 10.1007/s00216-003-2226-1. Epub 2003 Oct 9.
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).
精确且准确的同位素比值测量在许多应用中都是一项重要任务,例如同位素稀释质谱分析、生物利用度研究,或者地质或核样品中同位素变化的测定。多接收电感耦合等离子体质谱(MC-ICP-MS)技术备受关注,因为它能够精确测量多种元素的同位素组成,且由于高电离效率而具有出色的检测限。然而,其结果主要基于使用连续进样的测量。在本研究中,通过将高效液相色谱与多接收电感耦合等离子体质谱仪联用,实现了对持续时间为30至60秒的各种瞬态信号的同位素比值测定。为了研究这种联用技术中瞬态信号上比值漂移的来源,还使用流动注射装置进样对相同的标准溶液进行了测量。这项应用的结果表明,测量的同位素比值偏差的主要来源在于电感耦合等离子体质谱仪内部,而非色谱柱材料上的分馏效应。对气态样品(干等离子体)短瞬态信号的初步研究表明,与湿等离子体条件(流动注射和高效液相色谱)相比,存在反向分馏效应。