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Atmospheric Measurement Techniques An interactive open-access journal of the European Geosciences Union

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Atmos. Meas. Tech., 9, 1449-1460, 2016
https://doi.org/10.5194/amt-9-1449-2016
© Author(s) 2016. This work is distributed under
the Creative Commons Attribution 3.0 License.
Research article
04 Apr 2016
Characterization of the mass-dependent transmission efficiency of a CIMS
Martin Heinritzi1, Mario Simon1, Gerhard Steiner2,3, Andrea C. Wagner1, Andreas Kürten1, Armin Hansel3,4, and Joachim Curtius1 1Goethe University Frankfurt, Institute for Atmospheric and Environmental Sciences, 60438 Frankfurt am Main, Germany
2University of Vienna, Faculty of Physics, 1090 Wien, Austria
3University of Innsbruck, Institute for Ion and Applied Physics, 6020 Innsbruck, Austria
4Ionicon Analytik GmbH, 6020 Innsbruck, Austria
Abstract. Knowledge about mass discrimination effects in a chemical ionization mass spectrometer (CIMS) is crucial for quantifying, e.g., the recently discovered extremely low volatile organic compounds (ELVOCs) and other compounds for which no calibration standard exists so far. Here, we present a simple way of estimating mass discrimination effects of a nitrate-based chemical ionization atmospheric pressure interface time-of-flight (CI-APi-TOF) mass spectrometer. Characterization of the mass discrimination is achieved by adding different perfluorinated acids to the mass spectrometer in amounts sufficient to deplete the primary ions significantly. The relative transmission efficiency can then be determined by comparing the decrease of signals from the primary ions and the increase of signals from the perfluorinated acids at higher masses. This method is in use already for PTR-MS; however, its application to a CI-APi-TOF brings additional difficulties, namely clustering and fragmentation of the measured compounds, which can be treated with statistical analysis of the measured data, leading to self-consistent results. We also compare this method to a transmission estimation obtained with a setup using an electrospray ion source, a high-resolution differential mobility analyzer and an electrometer, which estimates the transmission of the instrument without the CI source. Both methods give different transmission curves, indicating non-negligible mass discrimination effects of the CI source. The absolute transmission of the instrument without the CI source was estimated with the HR-DMA method to plateau between the mz range of 127 and 568 Th at around 1.5 %; however, for the CI source included, the depletion method showed a steady increase in relative transmission efficiency from the mz range of the primary ion (mainly at 62 Th) to around 550 Th by a factor of around 5. The main advantages of the depletion method are that the instrument is used in the same operation mode as during standard measurements and no knowledge of the absolute amount of the measured substance is necessary, which results in a simple setup.

Citation: Heinritzi, M., Simon, M., Steiner, G., Wagner, A. C., Kürten, A., Hansel, A., and Curtius, J.: Characterization of the mass-dependent transmission efficiency of a CIMS, Atmos. Meas. Tech., 9, 1449-1460, https://doi.org/10.5194/amt-9-1449-2016, 2016.
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Short summary
An easy-to-use method of estimating the mass-dependent transmission efficiency of a CIMS is presented. It makes use of depleting nitrate primary ions by different perfluorinated acids to obtain the transmission efficiency of these acids relative to the primary ion. Knowledge about the transmission efficiency is crucial for, e.g., quantification of extremely low volatile organic compounds.
An easy-to-use method of estimating the mass-dependent transmission efficiency of a CIMS is...
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