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Atmospheric Measurement Techniques An interactive open-access journal of the European Geosciences Union
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Discussion papers
© Author(s) 2019. This work is distributed under
the Creative Commons Attribution 4.0 License.
© Author(s) 2019. This work is distributed under
the Creative Commons Attribution 4.0 License.

Submitted as: research article 16 Jul 2019

Submitted as: research article | 16 Jul 2019

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

Measurement of ammonia, amines and iodine species using protonated water cluster chemical ionization mass spectrometry

Joschka Pfeifer1,2, Mario Simon2, Martin Heinritzi2, Felix Piel2,a, Lena Weitz2,b, Dongyu Wang3, Manuel Granzin2, Tatjana Müller2, Steffen Bräkling4, Jasper Kirkby1,2, Joachim Curtius2, and Andreas Kürten2 Joschka Pfeifer et al.
  • 1CERN, Geneva, 1211, Switzerland
  • 2Institute for Atmospheric and Environmental Sciences, Frankfurt Am Main, 60438, Germany
  • 3Paul Scherrer Institute, Villigen, 5232, Switzerland
  • 4TOFWERK AG, Thun, 3600, Switzerland
  • anow at: Ionicon Analytik GmbH, 6020 Innsbruck, Austria
  • bnow at: GSI Helmholtzzentrum für Schwerionenforschung GmbH, Darmstadt, 64291, Germany

Abstract. A new water cluster Chemical Ionization-Atmospheric Pressure interface-Time Of Flight mass spectrometer (CI-APi-TOF) is introduced. The instrument is designed for the selective measurement of trace gases with high proton affinity, such as ammonia, amines, and diamines that are, for example, relevant for atmospheric new particle formation. Following the instrument description and characterization, we demonstrate successful measurements at the CLOUD (Cosmics Leaving OUtdoor Droplets) chamber where very low ammonia background levels of ~ 4 pptv were achieved (at 278 K and 80 % RH). The estimated level of detection of the water cluster CI-APi-TOF can be estimated as ~ 0.5 pptv for ammonia and it is significantly lower for amines. Due to a short reaction time (< 1 ms) and high primary ion concentrations in the cross-flow ion source even high ammonia mixing ratios of ca. 10 ppbv can be measured without significant reagent ion depletion. Besides the application to measure compounds like ammonia and amines, the technique is also suitable for the measurement of iodine oxides. During experimental runs exploring the nucleation capabilities of iodine-containing species in the CLOUD chamber, many different iodine-containing species were identified with the water cluster CI-APi-TOF. These compounds involved iodic acid and neutral clusters containing as many as four iodine atoms. However, the molecular structures of the measured iodine-containing species are not explicitly known, due to the difficulty in separating potential water molecules from the clusters. In addition to the description of the results obtained at the CLOUD chamber, we discuss the applicability of the technique for atmospheric measurements.

Joschka Pfeifer et al.
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Status: final response (author comments only)
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Joschka Pfeifer et al.
Joschka Pfeifer et al.
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Publications Copernicus
Short summary
Ammonia is an important atmospheric trace gas that affects secondary aerosol formation and, together with sulfuric acid, the formation of new particles. A measurement technique is presented that uses high-resolution mass spectrometry and protonated water clusters for the ultra-sensitive detection of ammonia at single-digit pptv levels. The instrument is further capable of measuring amines and a suite of iodine species at sub-pptv levels.
Ammonia is an important atmospheric trace gas that affects secondary aerosol formation and,...