OH measurements in the coastal atmosphere of South China: Possible missing OH sinks in aged air masses

Abstract

The hydroxyl radical (OH) is the main atmospheric oxidant responsible for the removal of many reduced trace gases and the formation of secondary air pollutants. However, due to technical difficulties in measuring OH, the existing measurements of atmospheric OH concentrations are limited, and its sources and sinks are not well understood under low-nitrogen-oxide (NOx) conditions. In this study, we observed the OH concentrations using chemical ionization mass spectrometry at a coastal site in Hong Kong from October to November 2020. The average noontime OH concentration over the study period was measured at 4.9 ± 2.1 × 106 cm-3. We found that a box model with comprehensive observational constraints reproduced the observed daytime OH concentrations when air parcels originated from the continental regions. However, this model overpredicted the observed daytime OH concentrations for coastal air parcels by 142% on average. Unaccounted-for OH sinks in the model are proposed to be the cause of this overprediction. A missing OH reactivity, which is defined as the pseudo-first-order rate coefficient for OH loss by unmeasured trace gases, was estimated as 5.0 ± 2.6 s-1 (lower limit) in the coastal air, and the missing reactivity increased with decreasing concentrations of NOx and volatile organic compounds (VOCs). Further studies are needed to find out the exact cause of the model overestimation and to identify the suspected unmeasured chemical species that contribute to the OH budget, in order to better quantify the formation of secondary air pollutants.