Abstract
We document the utility for in situ Rb–Sr dating of a one-of-a-kind tribrid mass spectrometer, ‘Proteus’, coupled to a UV laser ablation system. Proteus combines quadrupole mass-filter, collision cell and sector magnet with a multicollection inductively-coupled plasma mass spectrometer (CC-MC-ICPMS/MS). Compared to commercial, single collector, tribrid inductively-coupled plasma mass spectrometers (CC-ICPMS/MS) Proteus has enhanced ion transmission and offers simultaneous collection of all Sr isotopes using an array of Faraday cups. These features yield improved precision in measured 87Sr/86Sr ratios, for a given mass of Sr analysed, approximately a factor of 25 in comparison to the Thermo Scientific™ iCAP TQ™ operated under similar conditions. Using SF6 as a reaction gas on Proteus, measurements of Rb-doped NIST SRM (standard reference material) 987 solutions, with Rb/Sr ratios from 0.01–100, yield 87Sr/86Sr that are indistinguishable from un-doped NIST SRM 987, demonstrating quantitative ‘chemical resolution’ of Rb from Sr. We highlight the importance of mass-filtering before the collision cell for laser ablation 87Sr/86Sr analysis, using an in-house feldspar standard and a range of glass reference materials. By transmitting only those ions with mass-to-charge ratios 82–92 u/e into the collision cell, we achieve accurate 87Sr/86Sr measurements without any corrections for atomic or polyatomic isobaric interferences. Without the pre-cell mass-filtering, measured in situ87Sr/86Sr ratios are inaccurate. Combining in situ measurements of Rb/Sr and radiogenic Sr isotope ratios we obtain mineral isochrons. We utilise a sample from the well-dated Dartmoor granite (285 ± 1 Ma) as a calibrant for our in situ ages and, using the same conditions, produce accurate Rb–Sr isochron ages for samples of the Fish Canyon tuff (28 ± 2 Ma) and Shap granite pluton (397 ± 1 Ma). Analysing the same Dartmoor granite sample using identical laser conditions and number of spot analyses using the Thermo Scientific™ iCAP TQ™ yielded an isochron slope 5× less precise than Proteus. We use an uncertainty model to illustrate the advantage of using Proteus over single collector CC-ICPMS/MS for in situ Rb–Sr dating. The results of this model show that the improvement is most marked for samples that have low Rb/Sr (<10) or are young (<100 Ma). We also report the first example of an in situ, internal Rb–Sr isochron from a single potassium-feldspar grain. Using a sample from the Shap granite, we obtained accurate age and initial 87Sr/86Sr with 95% confidence intervals of ±1.5% and ±0.03% respectively. Such capabilities offer new opportunities in geochronological studies.
| Original language | English |
|---|---|
| Pages (from-to) | 917-931 |
| Number of pages | 15 |
| Journal | Journal of Analytical Atomic Spectrometry |
| Volume | 36 |
| Issue number | 5 |
| Early online date | 1 Apr 2021 |
| DOIs | |
| Publication status | E-pub ahead of print - 1 Apr 2021 |
Bibliographical note
Funding Information:This work was supported by a NERC CASE studentship between the University of Bristol and Thermo Fisher Scientic (NE/ P010342) and two grants from the ERC (ISONEB ERC Adv 321209 & PROCOMM ERC PoC 862389). D. B. would like to thank Dr Stuart Kearns and Dr Benjamin Buse for their patience and guidance during training and analysis in the University of Bristol microbeam laboratory. D. B. also thanks Dr Dhinesh Asogan for his assistance and advice during the operation of the iCAP TQ™. The authors would like to thank Professor Katharine Cashman, Dr Amy Gilmer, Dr Hélène Delavault, Professor Jon Blundy, Dr Ian Parkinson, Damaris Butters and Hannah Buckland for their generosity and help in providing the samples used in this work. Finally, D. B. would like to extend particular thanks to Danny Stubbs for providing much support and amusement during many long days and nights spent below ground.
Publisher Copyright:
© 2021 The Royal Society of Chemistry.