15 Nov 2021

15 Nov 2021

Review status: this preprint is currently under review for the journal AMT.

Fragmentation inside PTR-based mass spectrometers limits the detection of ROOR and ROOH peroxides

Haiyan Li1,2,, Thomas Golin Almeida3,, Yuanyuan Luo2, Jian Zhao2, Brett B. Palm4, Christopher D. Daub3, Wei Huang2, Claudia Mohr5, Jordan E. Krechmer6, Theo Kurtén3, and Mikael Ehn2 Haiyan Li et al.
  • 1School of Civil and Environmental Engineering, Harbin Institute of Technology, Shenzhen, 518055
  • 2Institute for Atmospheric and Earth System Research/Physics, Faculty of Science, University of Helsinki, Helsinki, 00014, Finland
  • 3Department of Chemistry, University of Helsinki, Helsinki, 00014, Finland
  • 4Department of Atmospheric Science, University of Washington Seattle, Washington, WA, 98195, USA
  • 5Department of Environmental Science, Stockholm University, 11418, Stockholm, Sweden
  • 6Aerodyne Research, Inc., Billerica, MA, 01821, USA
  • These authors contributed equally to this work.

Abstract. Proton-transfer-reaction (PTR) is a commonly applied ionization technique for mass spectrometers, where hydronium ions (H3O+) transfer a proton to analytes with higher proton affinities than the water molecule. This method has most commonly been used to quantify volatile hydrocarbons, but later generation PTR-instruments have been designed for better throughput of less volatile species, allowing detection of more functionalized molecules as well. For example, the recently developed Vocus PTR time-of-flight mass spectrometer (PTR-TOF) has been shown to agree well with an iodide adduct based chemical ionization mass spectrometer (CIMS) for products with 3-5 O-atoms from oxidation of monoterpenes (C10H16). However, while several different types of CIMS instruments (including those using iodide) detect abundant signals also at “dimeric” species, believed to be primarily ROOR peroxides, no such signals have been observed in the Vocus PTR, even though these compounds fulfil the condition of having higher proton affinity than water.

More traditional PTR instruments have been limited to volatile molecules as the inlets have not been designed for transmission of easily condensable species. Some newer instruments, like the Vocus PTR, have overcome this limitation, but are still not able to detect the full range of functionalized products, suggesting that other limitations need to be considered. One such limitation, well-documented in PTR literature, is the tendency of protonation to lead to fragmentation of some analytes. In this work, we evaluate the potential for PTR to detect dimers and the most oxygenated compounds, as these have been shown to be crucial for forming atmospheric aerosol particles. We studied the detection of dimers using a Vocus PTR-TOF in laboratory experiments as well as through quantum chemical calculations. Only noisy signals of potential dimers were observed during experiments on the ozonolysis of the monoterpene α-pinene, while a few small signals of dimeric compounds were detected during the ozonolysis of cyclohexene. During the latter experiments, we also tested varying the pressures and electric fields in the ionization region of the Vocus PTR-TOF, finding that only small improvements were possible in the relative dimer contributions. Calculations for model ROOR and ROOH systems showed that most of these peroxides should fragment partially following protonation. With inclusion of additional energy from the ion-molecule collisions driven by the electric fields in the ionization source, computational results suggest substantial or nearly complete fragmentation of dimers. Our study thus suggests that while the improved versions of PTR-based mass spectrometers are very powerful tools for measuring hydrocarbons and their moderately oxidized products, other types of CIMS are likely more suitable for the detection of ROOR and ROOH species.

Haiyan Li et al.

Status: open (until 21 Dec 2021)

Comment types: AC – author | RC – referee | CC – community | EC – editor | CEC – chief editor | : Report abuse
  • RC1: 'Comment on amt-2021-384', Anonymous Referee #1, 28 Nov 2021 reply
  • RC2: 'Comment on amt-2021-384', Anonymous Referee #2, 06 Dec 2021 reply

Haiyan Li et al.


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Short summary
This work evaluated the potential for PTR-based mass spectrometers to detect dimers both experimentally and through computations. Laboratory experiments using a Vocus PTR observed only noisy signals of potential dimers during α-pinene ozonolysis and a few small signals of dimeric compounds during cyclohexene ozonolysis. Quantum chemical calculations for model ROOR and ROOH systems showed that most of these peroxides should fragment partially following protonation.