Product ion distributions using H3O+ proton-transfer-reaction time-of-flight mass spectrometry (PTR-ToF-MS): mechanisms, transmission effects, and instrument-to-instrument variability

Published

February 27, 2025

Author(s)

Michael Link, Megan Claflin, Christina Cecelski, Ayomide Akande, Delany Kilgour, Paul Heine, Matthew Coggon, Chelsea Stockwell, Andrew Jensen, Jie Yu, Han Huyhn, Jenna Ditto, Carnsten Warneke, William Dresser, Keighan Gemmell, Spiro Jorga, Rileigh Robertson, Joost de Gouw, Timothy Bertram, Jonathan Abbatt, Nadine Borduas-Dedekind, Dustin Poppendieck

Abstract

Proton-transfer-reaction mass spectrometry (PTR-MS) using hydronium ion (H3O+) ionization is widely used for the measurement of volatile organic compounds (VOCs) both indoors and outdoors. H3O+ ionization, as well as the associated chemistry in an ion–molecule reactor, is known to generate product ion distributions (PIDs) that include other product ions besides the proton-transfer product. We present a method, using gas-chromatography pre-separation, for quantifying PIDs from PTR-MS measurements of nearly 100 VOCs of different functional types including alcohols, ketones, aldehydes, acids, aromatics, organohalides, and alkenes. We characterize instrument configuration effects on PIDs and find that reactor reduced electric field strength (), ion optic voltage gradients, and quadrupole settings have the strongest impact on measured PIDs. Through an interlaboratory comparison of PIDs measured from calibration cylinders, we characterized the variability of PID production from the same model of PTR-MS across seven participating laboratories. Product ion variability was generally smaller (e.g., < 20 %) for ions with larger contributions to the PIDs (e.g., > 0.30) but less predictable for product ions formed through O and NO+ reactions. We present a publicly available library of H3O+ PTR-MS PIDs that will be updated periodically with user-provided data for the continued investigation into instrument-to-instrument variability of PIDs.

Citation

Atmospheric Measurement Techniques

Volume

18

Pub Type

Journals

Download Paper

https://doi.org/10.5194/amt-18-1013-2025

Local Download

Keywords

proton-transfer mass spectrometry, ion chemistry, volatile organic compounds, indoor air

Citation

Link, M. , Claflin, M. , Cecelski, C. , Akande, A. , Kilgour, D. , Heine, P. , Coggon, M. , Stockwell, C. , Jensen, A. , Yu, J. , Huyhn, H. , Ditto, J. , Warneke, C. , Dresser, W. , Gemmell, K. , Jorga, S. , Robertson, R. , de Gouw, J. , Bertram, T. , Abbatt, J. , Borduas-Dedekind, N. and Poppendieck, D. (2025), Product ion distributions using H3O+ proton-transfer-reaction time-of-flight mass spectrometry (PTR-ToF-MS): mechanisms, transmission effects, and instrument-to-instrument variability, Atmospheric Measurement Techniques, [online], https://doi.org/10.5194/amt-18-1013-2025, https://tsapps.nist.gov/publication/get_pdf.cfm?pub_id=958673 (Accessed October 13, 2025)