Determination of carbon isotopes in carbonates (calcite, dolomite, magnesite, and siderite) by femtosecond laser ablation multi-collector ICP-MS

This study reports a method for in situ determination of stable carbon ( δ 13 C‰) isotope compositions for calcite, dolomite, magnesite and siderite by femtosecond laser ablation multi-collector inductively coupled plasma mass spectrometry (fs-LA-MC-ICP-MS). The chemical and bulk C isotope compositi...

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Bibliographic Details
Published in:Journal of analytical atomic spectrometry 2022-01, Vol.37 (2), p.278-288
Main Authors: Lu, Jue, Chen, Wei, Zhang, Wen, Liu, Hong, Simonetti, Antonio, Hu, Zhaochu, Liu, Yongsheng, Zhao, Kuidong, Jiang, Shaoyong
Format: Article
Language:English
Subjects:
Ablation
Calcite
Calibration
Carbon
Carbon 12
Carbon isotopes
Carbonates
Chemical composition
Dolomite
Emission spectroscopy
Fractionation
Inductively coupled plasma mass spectrometry
Isotope ratios
Isotopes
Laser ablation
Lasers
Magnesite
Magnesium carbonate
Mass spectrometry
Scientific imaging
Siderite
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Summary:This study reports a method for in situ determination of stable carbon ( δ 13 C‰) isotope compositions for calcite, dolomite, magnesite and siderite by femtosecond laser ablation multi-collector inductively coupled plasma mass spectrometry (fs-LA-MC-ICP-MS). The chemical and bulk C isotope compositions of various carbonates have been characterized by LA-ICP-MS and isotope ratio mass spectrometry (IRMS), respectively. Magnesite shows limited chemical variation, whereas the major element compositions of dolomite and siderite vary greatly among samples and individual grains. The spectral interference of doubly charged ions ( 24 Mg 2+ for 12 C + and 26 Mg 2+ for 13 C + ) and polyatomic species ( 12 CH + for 13 C + ) was evaluated. The associated internal precision of in situ C isotope analysis correlates with intensities and is better than 0.20‰ (2SE) when the measured 12 C ion signal is >12.5 volts. Carbonate samples DOL-8, MGS-1 and SD-5 show relatively uniform bulk and in situ carbon isotope compositions with precisions better than 0.24‰ and 0.45‰ (2SD) and are adopted as in-house standards. The laser ablation analysis results of various calcite, dolomite, magnesite and siderite samples with δ 13 C in the range of −6.28‰ to 0.32‰ agree excellently with IRMS determined values using standard-sample bracketing (SSB) calibration, with a precision of 0.37–0.68‰ (2SD). Matrix effects have been investigated and determined to be insignificant for the same carbonate matrix with variable chemical compositions when adopting a femtosecond laser. Instrumental carbon isotope fractionation observed among different carbonate matrices is non-negligible ( e.g. , up to 4.29‰ between calcite and magnesite) using fs-LA-MC-ICP-MS, and an external multi-reference calibration can be applied for non-matrix matched analyses.
ISSN:0267-9477
1364-5544
DOI:10.1039/D1JA00356A