Development of an instrument for direct ozone production rate measurements: measurement reliability and current limitations

Sofia Sklaveniti,Nadine Locoge,Shuvashish Kundu,Ezra Wood,Sébastien Dusanter,Philip S. Stevens

doi:10.5194/amt-11-741-2018

Abstract

Abstract. Ground-level ozone (O3) is an important pollutant that affects both global climate change and regional air quality, with the latter linked to detrimental effects on both human health and ecosystems. Ozone is not directly emitted in the atmosphere but is formed from chemical reactions involving volatile organic compounds (VOCs), nitrogen oxides (NOx= NO + NO2) and sunlight. The photochemical nature of ozone makes the implementation of reduction strategies challenging and a good understanding of its formation chemistry is fundamental in order to develop efficient strategies of ozone reduction from mitigation measures of primary VOCs and NOx emissions. An instrument for direct measurements of ozone production rates (OPRs) was developed and deployed in the field as part of the IRRONIC (Indiana Radical, Reactivity and Ozone Production Intercomparison) field campaign. The OPR instrument is based on the principle of the previously published MOPS instrument (Measurement of Ozone Production Sensor) but using a different sampling design made of quartz flow tubes and a different Ox (O3 and NO2) conversion–detection scheme composed of an O3-to-NO2 conversion unit and a cavity attenuated phase shift spectroscopy (CAPS) NO2 monitor. Tests performed in the laboratory and in the field, together with model simulations of the radical chemistry occurring inside the flow tubes, were used to assess (i) the reliability of the measurement principle and (ii) potential biases associated with OPR measurements. This publication reports the first field measurements made using this instrument to illustrate its performance. The results showed that a photo-enhanced loss of ozone inside the sampling flow tubes disturbs the measurements. This issue needs to be solved to be able to perform accurate ambient measurements of ozone production rates with the instrument described in this study. However, an attempt was made to investigate the OPR sensitivity to NOx by adding NO inside the instrument. This type of investigations allows checking whether our understanding of the turnover point between NOx-limited and NOx-saturated regimes of ozone production is well understood and does not require measuring ambient OPR but instead only probing the change in ozone production when NO is added. During IRRONIC, changes in ozone production rates ranging from the limit of detection (3σ) of 6.2 ppbv h−1 up to 20 ppbv h−1 were observed when 6 ppbv of NO was added into the flow tubes.

Highlights

Ground-level ozone (O3) is a primary constituent of photochemical smog that irritates the respiratory system (WHO, 2013) and damages vegetation (Ashmore, 2005)
While plug flow conditions are not met in the flow tubes, it is interesting to note that a residence time of 4.79 min would be expected from plug flow conditions at a total flow rate of 2.25 L min−1 for a volume of 10.8 L in each flow tube.The asymmetry of the peak indicates that the flow rate at the central axis of the tube is larger, with the first molecules of toluene being sampled after approximately 2 min (Fig. 2)
The first source of errors is due to Ox production in the reference flow tube and the latency for ROx reformation in the ambient flow tube, with the extent of each depending on the fraction of ambient peroxy radicals that is transmitted into the flow tubes

Summary

Introduction

Ground-level ozone (O3) is a primary constituent of photochemical smog that irritates the respiratory system (WHO, 2013) and damages vegetation (Ashmore, 2005). S. Sklaveniti et al.: Development of an instrument for direct ozone production rate measurements formed during daytime and has an average lifetime estimated at 22 ± 2 days (Stevenson et al, 2006), which is long enough to transport it from polluted regions to remote areas and between continents. The local production of ozone on top of the amount advected from elsewhere can lead to exceedances of air quality standards in urbanized areas, making ozone pollution an issue of global concern (Akimoto, 2003)

Methods

Results

Conclusion