Laboratory of Inorganic Chemistry, ETH Zurich, Vladimir-Prelog-Weg 1, 8093, Zurich, Switzerland.
Büchi Labortechnik AG, Meierseggstrasse 40, 9230, Flawil, Switzerland.
Anal Bioanal Chem. 2019 Jan;411(3):591-602. doi: 10.1007/s00216-018-1314-1. Epub 2018 Aug 22.
Pulsed laser ablation sampling and sequential isotope detection can lead to signal beat in the registered signal intensities. In particular, if aerosol transport systems deliver ablated aerosol with temporal duration close to that of a single mass scan, such signal beat can become significant and lead to biased intensity ratios and concentrations. Averaging signal intensities based on the least common multiple of scan duration and laser pulse period can eliminate such a systematic bias and improve the accuracy of quantitative laser ablation experiments. The method was investigated for experiments using an ablation cell that provided aerosol washout times near 200 ms and quadrupole-based ICP-MS acquisition using different dwell and settling times that were compared with and extended by numerical simulations. It was found that the systematic bias of acquired data could exceed the inherent noise of laser ablation inductively couple plasma mass spectrometry experiments and that the averaging method could successfully minimize the bias due to beating. However, simulations revealed that this was only the case for combinations of pulse frequency and scan duration in which the number of laser pulses within the averaged period was an integer multiple of the number of isotopes in the acquisition method. In element imaging applications, this averaging will necessarily increase the size of individual pixels and it depends not only on the laser beam size but also pulse repetition rate and the acquisition settings for a sequential mass spectrometer. Graphical abstract LCM averaging can prevent occurrence of a systematic bias in LA-ICPMS measurements.
脉冲激光烧蚀采样和顺序同位素检测可能导致记录的信号强度中的信号拍频。特别是,如果气溶胶传输系统输送的烧蚀气溶胶的时间持续时间接近单个质量扫描的时间持续时间,则这种信号拍频可能变得显著,并导致强度比和浓度出现偏差。基于扫描持续时间和激光脉冲周期的最小公倍数来平均信号强度,可以消除这种系统偏差并提高定量激光烧蚀实验的准确性。该方法针对使用烧蚀池的实验进行了研究,该烧蚀池提供了接近 200ms 的气溶胶冲洗时间,以及使用不同停留时间和沉降时间的基于四极杆的 ICP-MS 采集,并与数值模拟进行了比较和扩展。结果发现,采集数据的系统偏差可能超过激光烧蚀电感耦合等离子体质谱实验的固有噪声,并且平均方法可以成功地最小化由于拍频引起的偏差。然而,模拟表明,只有在脉冲频率和扫描持续时间的组合中,即在平均周期内的激光脉冲数是采集方法中同位素数的整数倍的情况下,才会出现这种情况。在元素成像应用中,这种平均化必然会增加单个像素的大小,并且不仅取决于激光束的大小,还取决于脉冲重复率和顺序质谱仪的采集设置。
图形摘要 LCM 平均化可以防止 LA-ICPMS 测量中出现系统偏差。