Standler Alexander, Koellensperger Gunda, Buchberger Wolfgang, Stingeder Gerhard, Hann Stephan
Department of Chemistry, University of Natural Resources and Applied Life Sciences, Muthgasse 18, A-1190 Vienna, Austria.
Electrophoresis. 2007 Oct;28(19):3492-9. doi: 10.1002/elps.200700097.
In the present work the degradation of chloroplatinates emitted into the aquatic environment has been investigated in model studies. CE coupled to inductively coupled plasma sector field MS (ICP-SFMS) was employed as an analytical method of measurement. The CE-ICP-MS interface utilized the functional make-up flow design with a microconcentric nebulizer. Pt(Cl(4)) and Pt(Cl(6)) were separated within 5 min. During a measurement period of 6 h an excellent reproducibility of migration times (RSD 2.3%) could be achieved. The high sensitivity of ICP-SFMS resulted in an LOD of 80 ng/L platinum for the two compounds. External calibration using rhenium as internal standard was linear over three orders of magnitude. However, with external calibration a long-term drift of signal intensity was observed. In order to reduce the uncertainty of the obtained results, quantification of PtCl(6) was performed for the first time by species-specific on-line isotope dilution MS using (194)PtCl(6) as spike. The two different quantification strategies were compared in terms of their total combined uncertainty of measurement according to the EURACHEM guideline. The method was employed for monitoring the time-dependent degradation of Pt(Cl(4)) and Pt(Cl(6)) in water containing 0 and 2.8 mmol/L Cl(-) and river water. Pt(Cl(6)) was stable whereas Pt(Cl(4)) showed rapid degradation following pseudo first-order kinetics.
在本研究中，通过模型研究对排放到水生环境中的氯铂酸盐的降解情况进行了调查。采用毛细管电泳与电感耦合等离子体质谱联用（CE-ICP-SFMS）作为分析测量方法。CE-ICP-MS接口采用了带有微型同心雾化器的功能组合流设计。Pt(Cl(4))和Pt(Cl(6))在5分钟内实现了分离。在6小时的测量期间，迁移时间的重现性极佳（相对标准偏差为2.3%）。ICP-SFMS的高灵敏度使得这两种化合物的铂检测限达到80 ng/L。以铼作为内标的外标法在三个数量级范围内呈线性。然而，采用外标法时观察到信号强度存在长期漂移。为了降低所得结果的不确定性，首次使用(194)PtCl(6)作为加标物，通过物种特异性在线同位素稀释质谱对PtCl(6)进行了定量分析。根据EURACHEM指南，对两种不同的定量策略在其总测量不确定度方面进行了比较。该方法用于监测Pt(Cl(4))和Pt(Cl(6))在含0和2.8 mmol/L Cl(-)的水以及河水中随时间的降解情况。Pt(Cl(6))是稳定的，而Pt(Cl(4))遵循准一级动力学显示出快速降解。
