Performance of second generation ICP-TOFMS for (multi-)isotope ratio analysis: a case study on B, Sr and Pb and their isotope fractionation behavior during the measurements

• Published in: Journal of analytical atomic spectrometry Vol. 38; no. 1; pp. 2144 - 2158
• Main Authors: Retzmann, Anika, Faßbender, Sebastian, Rosner, Martin, von der Au, Marcus, Vogl, Jochen
• Format: Journal Article
• Language: English
• Published: London Royal Society of Chemistry 04.10.2023
• Subjects: Dilution; Fractionation; Inductively coupled plasma mass spectrometry; Ion extraction; Isotope ratios; Isotopes; Lead isotopes; Mass spectrometry; Microchannel plates; Microchannels; Ratios; Strontium 87
• ISSN: 0267-9477; 1364-5544
• DOI: 10.1039/d3ja00084b

The performance of second generation ICP-TOFMS, equipped with a micro-channel plate (MCP) enabling multi-isotope detection, in terms of isotope ratio precision and instrumental isotopic fractionation (IIF) for (multi-)isotope ratio analysis was thoroughly assessed for B, Sr and Pb. Experimental isotope ratio precision of 0.14% for 11 B/ 10 B intensity ratio, 0.15% for 87 Sr/ 86 Sr intensity ratio and 0.07% for 208 Pb/ 206 Pb intensity ratio were obtained at high signal levels (≥500 μg L −1 ) which is comparable to first generation ICP-TOFMS. The long-term stability of isotope ratios, measured over several hours and expressed as repeatability, is between 0.05% and 1.8% for B, Sr and Pb. The observed IIF per mass unit is negative for B ( i.e. , −11% for 11 B/ 10 B) which is in accordance with measurements using sector field (MC) ICP-MS. But the observed IIF per mass unit is positive for Sr ( i.e ., 2% for 87 Sr/ 86 Sr) and Pb ( i.e ., 4.5% for 208 Pb/ 206 Pb) which is not in accordance with measurements using sector field (MC) ICP-MS. Furthermore, different IIFs per mass unit were observed for different isotope pairs of the same isotopic system ( i.e. , Sr, Pb) and adjacent isotopic systems ( i.e. , Pb vs. Tl). This and the observations from three-isotope plots for Sr and Pb show that ion formation, ion extraction, ion transmission, ion separation and ion detection in second generation ICP-TOFMS is subject to IIF that does not follow the known mass dependent fractionation laws and is possibly caused by mass independent fractionation and/or multiple (contradictory) fractionation processes with varying contributions. The non-mass dependent IIF behavior observed for second generation ICP TOFMS has profound consequences for the IIF correction of isotope raw data, including application of multi-isotope dilution mass spectrometry (IDMS) using ICP-TOFMS. Hence, only IIF correction models that correct also for mass independent fractionation are applicable to calculate reliable isotope ratios using second generation ICP-TOFMS. In the present study, reliable δ 11 B values, and absolute B, Sr and Pb isotope ratios could be determined using the SSB approach in single-element solutions as well as in a mixture of B, Sr and Pb, where the isotopes were measured simultaneously. The second generation ICP-TOFMS is subject to IIF that does not follow the known mass dependent fractionation laws and is possibly caused by non-mass dependent fractionation and/or multiple fractionation processes with varying contributions.