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Elemental quantitation of carbon via production of polyatomic anions in gas chromatography-plasma assisted reaction chemical ionization mass spectrometry

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Abstract

Elemental mass spectrometry offers quantitation and isotopic analysis without the need for compound-specific standards. We have recently introduced plasma assisted reaction chemical ionization (PARCI) as an efficient elemental ionization method for halogens. Here, we report a new ionization chemistry in PARCI for facile quantitation of elemental carbon in gas chromatography eluates. We demonstrate that in-plasma reactions of organic compounds followed by afterglow ionization lead to formation of polyatomic anions (CN−, OCN−, and CO3 −), among which CN− offers the best analytical sensitivity with a detection limit of ~25 pg (21 pg/s) carbon on column. Using a mixture of pesticides with wide variations in structures and heteroatom content, we demonstrate that CN− ion response is quantitatively correlated with the carbon concentration over two orders of magnitude (r 2 = 0.985). We show that the novel GC-PARCI-MS method provides recoveries within 80–120% using a single standard for all analytes, highlighting the strength of elemental quantitation. Further, the ability of GC-PARCI-MS to identify 13C-tagged molecules without a priori knowledge of chemical formulas of analytes is demonstrated.

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Acknowledgements

This material is based upon work supported by the National Science Foundation (NSF) under CHE-1507304. We thank PerkinElmer Inc. for the loan of the mass spectrometers and for financial support. We are grateful to Dr. Hamid Badiei of PerkinElmer for discussions during the course of this work.

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Author notes

  1. Haopeng Wang

    Present address: Agilent Technologies Inc., Santa Clara, 95051, CA, USA

Authors and Affiliations

  1. Department of Chemistry, Georgetown University, Washington, DC, 20057, USA

    Peter J. Haferl, Kunyu Zheng, Haopeng Wang & Kaveh Jorabchi

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  1. Peter J. Haferl
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  2. Kunyu Zheng
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  3. Haopeng Wang
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  4. Kaveh Jorabchi
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Correspondence to Kaveh Jorabchi.

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Haferl, P.J., Zheng, K., Wang, H. et al. Elemental quantitation of carbon via production of polyatomic anions in gas chromatography-plasma assisted reaction chemical ionization mass spectrometry. Anal Bioanal Chem 409, 3843–3851 (2017). https://doi.org/10.1007/s00216-017-0328-4

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