High-precision potassium (K) isotope measurements in marine carbonates allow using this novel geochemical proxy to constrain seawater chemistry through geologic time. However, these measurements are still scarce due to the challenges of low-K contents in carbonates during K ion chromatography, such as insufficient sample purification, non-quantitative yield, and high accumulative blank. Here we optimize a dual-column K purification method that addresses these challenges, achieving a satisfactory K separation using 100–150 mg carbonates for routine high-precision K isotope analysis on the Sapphire™ MC-ICP-MS. We then report K isotope compositions in multiple certified reference materials, including limestone, dolostone, coral, and basalt for future inter-laboratory comparisons. The optimized K purification method provides great potential for future K isotope studies of marine carbonates.
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High precision analysis of stable potassium (K) isotopes by the collision cell MC-ICP-MS “Sapphire” and a correction method for concentration mismatch
Stable potassium (K) isotopes (41K/39K) have shown great promise as novel chemical tracers for a wide range of bio-, geo-, and cosmo-chemical processes, but high precision stable K isotope analysis remains a challenge for plasma source mass spectrometry due to intense argon-related interferences produced directly from argon plasma. Here we provide an assessment on the analytical figures of merit of a new generation collision-cell equipped multi-collector inductively coupled plasma mass spectrometer (MC-ICP-MS), Sapphire from Nu Instruments, for K isotope analysis based on our extensive tests over a duration of ~8 months. Because use of helium and hydrogen as collision/reaction gases can reduce argon-related interferences to negligible levels at optimal flow rates, the collision-cell mode can operate at low mass resolution during K isotope analysis, providing >2 orders of magnitude higher K sensitivity (>1000 V per μg mL-1 K), as compared to the widely used “cold plasma” method, and the capability for direct 40K measurement. One challenge of the collision/reaction cell analysis on Sapphire is its higher susceptibility to matrix effects, requiring effective sample purification prior to analysis. Also, the collision-cell mode on Sapphire shows a pronounced effect associated with concentration (or ion intensity) mismatch between the sample and the bracketing standard during analysis, and this effect may not be fully eliminated through conventional concentration matching practice. Instead, we developed a correction method for this concentration/ion intensity mismatch effect. Our method reduces the burden to the operator and increases sample throughput. This method allows for accurate K isotope analysis with an intermediate precision of ≤0.05 ‰ (2SD) to be routinely achieved using the collision cell on Sapphire, representing a major advance to stable K isotope analysis.
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- Award ID(s):
- 1946945
- PAR ID:
- 10323842
- Date Published:
- Journal Name:
- Journal of Analytical Atomic Spectrometry
- ISSN:
- 0267-9477
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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