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

Journal metrics

Journal metrics

  • IF value: 3.248 IF 3.248
  • IF 5-year value: 3.650 IF 5-year 3.650
  • CiteScore value: 3.37 CiteScore 3.37
  • SNIP value: 1.253 SNIP 1.253
  • SJR value: 1.869 SJR 1.869
  • IPP value: 3.29 IPP 3.29
  • h5-index value: 47 h5-index 47
  • Scimago H index value: 60 Scimago H index 60
Volume 11, issue 7 | Copyright
Atmos. Meas. Tech., 11, 4413-4433, 2018
© Author(s) 2018. This work is distributed under
the Creative Commons Attribution 4.0 License.

Research article 25 Jul 2018

Research article | 25 Jul 2018

A novel semi-direct method to measure OH reactivity by chemical ionization mass spectrometry (CIMS)

Jennifer B. A. Muller, Thomas Elste, Christian Plass-Dülmer, Georg Stange, Robert Holla, Anja Claude, Jennifer Englert, Stefan Gilge, and Dagmar Kubistin Jennifer B. A. Muller et al.
  • Meteorologisches Observatorium Hohenpeissenberg, Deutscher Wetterdienst (DWD), 82383 Hohenpeissenberg, Germany

Abstract. An operational chemical ionization mass spectrometer (CIMS) for hydroxyl radical (OH) and sulfuric acid (H2SO4) concentration measurements was adapted to include observations of OH reactivity, which is the inverse of OH lifetime, for long-term monitoring at the Global Atmosphere Watch (GAW) site Hohenpeissenberg (MOHp), Germany. OH measurement using CIMS is achieved by reacting OH with SO2, leading to the production of H2SO4, which is then detected. The adaptation for OH reactivity consists of the implementation of a second SO2 injection, at a fixed point further down flow in the sample tube to detect the OH decay caused by reactions with OH reactants present in the sample.

The method can measure OH reactivity from less than 1 to 40s−1 with the upper limit due to the fixed positioning of the second SO2 injection. To determine OH reactivity from OH concentration measurements, the reaction time between the two titration zones and OH wall losses in the sample tube need to be determined accurately through OH reactivity calibration. Potential measurement artefacts as a result of HOx recycling in the presence of NO have to be considered. Therefore, NO contamination from gases used in instrument operation must be minimized and ambient NO must be measured concurrently to determine the measurement error.

This CIMS system is shown here to perform very well for OH reactivity below 15s−1 and NO concentrations below 4ppb, both values that are rarely exceeded at the MOHp site. Thus when deployed in suitable chemical environments, this method can provide valuable continuous long-term measurements of OH reactivity. The characterization utilizes results from chamber, laboratory and modelling studies and includes the discussion and quantification of sources of uncertainties.

Publications Copernicus
Short summary
The hydroxyl radical (OH) largely controls tropospheric trace gas removal and the inverse of OH lifetime, OH reactivity, is a useful measure to investigate the oxidation capacity of the atmosphere. This paper presents a novel method to measure OH reactivity using an operational chemical ionization mass spectrometer (CIMS) for OH measurements at the GAW site Hohenpeissenberg, Germany. It includes the analysis of measurement uncertainties and demonstrates its suitability for long-term monitoring.
The hydroxyl radical (OH) largely controls tropospheric trace gas removal and the inverse of OH...