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Atmospheric Measurement Techniques An interactive open-access journal of the European Geosciences Union
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Discussion papers
https://doi.org/10.5194/amt-2018-407
© Author(s) 2018. This work is distributed under
the Creative Commons Attribution 4.0 License.
https://doi.org/10.5194/amt-2018-407
© Author(s) 2018. This work is distributed under
the Creative Commons Attribution 4.0 License.

Research article 10 Dec 2018

Research article | 10 Dec 2018

Review status
This discussion paper is a preprint. It is a manuscript under review for the journal Atmospheric Measurement Techniques (AMT).

Evaluating the performance of five different chemical ionization techniques for detecting gaseous oxygenated organic species

Matthieu Riva1,2, Pekka Rantala1, Jordan E. Krechmer3, Otso Peräkylä1, Yanjun Zhang1, Liine Heikkinen1, Olga Garmash1, Chao Yan1, Markku Kulmala1,4, Douglas Worsnop1,3, and Mikael Ehn1 Matthieu Riva et al.
  • 1Institute for Atmospheric and Earth System Research/Physics, Faculty of Science, University of Helsinki, Helsinki, 00140, Finland
  • 2Univ Lyon, Université Claude Bernard Lyon 1, CNRS, IRCELYON, 69626, Villeurbanne, France
  • 3Aerodyne Research Inc., Billerica, MA, USA
  • 4Aerosol and Haze Laboratory, Beijing Advanced Innovation Center for Soft Matter Science and Engineering, Beijing University of Chemical Technology (BUCT), Beijing, China

Abstract. The impact of aerosols on climate and air quality remains poorly understood due to multiple factors. One of the current limitations is the incomplete understanding of the contribution of oxygenated products, generated from the gas-phase oxidation of volatile organic compounds (VOC), to aerosol formation. Indeed, atmospheric gaseous chemical processes yield thousands of (highly) oxygenated species, spanning a wide range of chemical formulas, functional groups and, consequently, volatilities. While recent mass spectrometric developments have allowed extensive on-line detection of a myriad of oxygenated organic species, playing a central role in atmospheric chemistry, the detailed quantification and characterization of this diverse group of compounds remains extremely challenging. To address this challenge, we evaluated the capability of current state-of-the-art mass spectrometers equipped with different chemical ionization sources to detect the oxidation products formed from α-pinene ozonolysis under various conditions. Five different mass spectrometers were deployed simultaneously for a chamber study. Two chemical ionization atmospheric pressure interface time-of-flight mass spectrometers (CI-APi-TOF) with nitrate and amine reagent ion chemistries and an iodide chemical ionization time-of-flight mass spectrometer (TOF-CIMS). Additionally, a proton transfer reaction time-of-flight mass spectrometer (PTR-TOF 8000) and a new “Vocus” PTR-TOF were also deployed. In the current study, we compared around 1000 different compounds between each of the five instruments, with the aim to determine which oxygenated VOC (OVOC) the different methods were sensitive to, and identifying regions where two or more instruments were able to detect species with similar molecular formulae. We utilized a large variability in conditions (including different VOC, ozone, NOx and OH scavenger concentrations) in our newly constructed atmospheric simulation chamber for a comprehensive correlation analysis between all instruments. This analysis, combined with estimated concentrations for identified molecules in each instrument, yielded both expected and surprising results. As anticipated based on earlier studies: the PTR instruments were the only ones able to measure the precursor VOC; the iodide TOF-CIMS efficiently detected many semi-volatile organic compounds (SVOC) with 3 to 5 oxygen atoms; and the nitrate CI-APi-TOF was mainly sensitive to highly-oxygenated organic (O>5) molecules (HOM). In addition, the Vocus showed good agreement with the iodide TOF-CIMS for the SVOC, including also a range of organonitrates. The amine CI-APi-TOF agreed well with the nitrate CI-APi-TOF for HOM dimers. However, the loadings in our experiments caused the amine reagent ion to be considerably depleted, causing non-linear responses for monomers. This study explores and highlights both benefits and limitations of currently available chemical ionization mass spectrometry instrumentation for characterizing the wide variety of OVOC in the atmosphere. While specifically shown for the case of α-pinene ozonolysis, we expect our general findings to be valid also for a wide range of other VOC-oxidant systems. As discussed in this study, no single instrument configuration can be deemed better or worse than the others, as the optimal instrument for a particular study ultimately depends on the specific target of the study.

Matthieu Riva et al.
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Short summary
The impact of aerosol particles on climate and air quality remains poorly understood due to multiple factors. One of the current limitations is the incomplete understanding of the contribution of oxygenated species, formed from the oxidation of volatile organic compounds (VOC), to aerosol formation. Taking advantage of recent mass spectrometric developments, we have evaluated and compared the capability of multiple state-of-the-art mass spectrometers to detect a wide variety of oxygenated VOC.
The impact of aerosol particles on climate and air quality remains poorly understood due to...
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