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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 25 Nov 2019

Submitted as: research article | 25 Nov 2019

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

Simultaneous Detection of Ozone and Nitrogen Dioxide by Oxygen Anion Chemical Ionization Mass Spectrometry: A Fast Time Response Sensor Suitable for Eddy Covariance Measurements

Gordon A. Novak, Michael P. Vermeuel, and Timothy H. Bertram Gordon A. Novak et al.
  • Department of Chemistry, University of Wisconsin – Madison, Madison, WI, USA

Abstract. We report on the development, characterization, and field deployment of a fast time response sensor for measuring ozone (O3) and nitrogen dioxide (NO2) concentrations utilizing chemical ionization time-of-flight mass spectrometry (CI-ToFMS) with oxygen anion (O2) reagent ion chemistry. We demonstrate that the oxygen anion chemical ionization mass spectrometer (Ox-CIMS) is highly sensitive to both O3 (180 ions s−1 pptv−1 pptv−1) and NO2 (97 ions s−1 pptv−1), corresponding to detection limits (3σ, 1 s averages) of 13 and 9.9 pptv, respectively. In both cases, the detection threshold is limited by the magnitude and variability in the background determination. The short-term precision (1 s averages) is better than 0.3% at 10 ppbv O3 and 4% at 10 pptv NO2. We demonstrate that the sensitivity of the O3 measurement to fluctuations in ambient water vapor and carbon dioxide is negligible for typical conditions encountered in the troposphere. The application of the Ox-CIMS to the measurement of O3 vertical fluxes over the coastal ocean, via eddy covariance (EC), was tested during summer 2018 at Scripps Pier, La Jolla CA. The observed mean ozone deposition velocity (vd(O3)) was 0.011 cm s−1 pptv−1 with a campaign ensemble limit of detection (LOD) of 0.0042 cm s−1 pptv−1 at the 95% confidence level, from each 27-minute sampling period LOD. The campaign mean and one standard deviation range of O3 mixing ratios were 38.9 ± 12.3 ppbv. Several fast ozone titration events from local NO emissions were sampled where unit conversion of O3 to NO2 was observed, highlighting instrument utility as a total odd oxygen (Ox = O3 + NO2) sensor. The demonstrated precision, sensitivity, and time resolution of this instrument highlight its potential for direct measurements of O3 ocean–atmosphere and biosphere–atmosphere exchange from both stationary and mobile sampling platforms.

Gordon A. Novak et al.
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Gordon A. Novak et al.
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Short summary
We present the development of a new sensor capable of fast and high sensitivity measurements of ozone and nitrogen dioxide. Ozone and nitrogen dioxide are regulated air pollutants and play a central role in the cycling of atmospheric oxidants. We provide a full characterization of our sensor that will allow other researchers to adapt similar instruments for this purpose. We also demonstrate the successful application of this sensor for field measurements of ozone deposition to the ocean surface.
We present the development of a new sensor capable of fast and high sensitivity measurements of...