Intercomparison of nitrogen monoxide and nitrogen dioxide measurements in the atmosphere simulation chamber SAPHIR during the MetNO2 campaign

Nitrogen dioxide (NO₂) and nitrogen monoxide (NO) govern the photochemical processes in the troposphere. Although nitrogen oxides have been measured for decades, their quantification remains challenging. The MetNO2 (Metrology for Nitrogen Dioxide) project of the European Metrology Programme for Innovation and Research (EMPIR) aims to improve the accuracy of NO₂ measurements.

In total 15 instruments were intercompared at the World Calibration Centre for nitrogen oxides (WCC-NOx) in Jülich in autumn 2019 within the project. In addition to chemiluminescence detectors (CLD), the instruments encompassed Quantum Cascade Laser Absorption Spectrometers (QCLAS), Iterative CAvity-enhanced Differential optical absorption spectrometers (ICAD) and Cavity Attenuated Phase Shift (CAPS) spectrometers.

During the campaign, air from a gas phase titration unit, air from the environmental chamber SAPHIR or outside air was provided to the instruments via a common inlet line. The participants calibrated their instruments prior and after the campaign with their own calibration procedures. During the campaign, the common inlet line was used for daily calibration to compare standards, calibration techniques and sensitivity drifts of the instruments. NO₂ for calibration was provided either by gas phase titration from NO, from permeation tubes or from gas mixtures produced within the MetNO2 project.

It was observed that measurements by chemiluminescence or CAPS instruments are prone to interferences from humidity and ozone. However, in most cases data can be corrected. Alkyl nitrates and reactive alkenes were also observed to cause interferences in some instruments, while isobutyl nitrite was found to be photolyzed by photolytic converters.

Finally, measurements in ambient air were compared. The nitrogen oxide observations were accompanied with measurements of hydroxyl radical (OH) reactivity and reactive nitrogen species as nitrous acid (HONO), dinitrogen pentoxide (N₂O₅), and chloryl nitrate (ClNO₂). Detailed results of the intercomparison will be presented.