Use of filter radiometer measurements to derive local photolysis rates and for future monitoring network application

Abstract

Production of hydroxyl (OH) radicals is frequently dominated by the photolysis of tropospheric ozone (O 3). However , photolysis of nocturnal radical reservoirs, such as nitrous acid (HONO) and nitryl chloride (ClNO 2), also produces radicals (OH and Cl atoms) that contribute to the oxidising capacity of the local atmosphere, and initiate many radical-chain reactions that lead to the formation of harmful secondary pollutants. Photolysis of nitric acid (HNO 3) is also a minor radical production mechanism. In this paper, locally representative photolysis rate constants (j-values) for these molecules are shown 5 to be critical for quantifying and understanding the rate of radical production in a local atmosphere. The first long-term 4-π filter radiometer dataset in the UK (21 November 2018-20 November 2019) available for direct atmospheric model validation is reported. Measurements were made at Auchencorth Moss, a Scottish rural background site, and j(NO 2) is used to generate a measurement-driven adjustment factor (MDAF) for calculated j-values that accounts for local changes in meteorological variables without significantly increasing computational cost. 10 Modelled clear-sky j-values and actinic flux for Auchencorth Moss were generated using the Tropospheric Ultraviolet and Visible radiation model (TUV; v.5.3.1). Applying the MDAF metric resulted in the calculated photolytic production rate of OH radicals, from all sources considered, being ∼ 40% lower over the year. Photolysis of HONO resulted in an increased rate of OH production compared to that from O 3 in low-light conditions, such as sunrise and sunset (Solar Zenith Angle >80 •). Hydroxyl radical production from HONO photolysis exceeded that from O 3 consistently throughout the day during 15 the winter and autumn (by a factor of 5 and 2.1, respectively). Radical production rates from HONO and ClNO 2 reached maximum values during the early morning hours of summer (06:00-09:00 UTC), with OH produced at a rate of 1.03 × 10 6 OH radicals cm −3 s −1 , and Cl radicals at 3.20 × 10 4 Cl radicals cm −3 s −1 , with the MDAF metric applied. This first application of the MDAF j-values demonstrates an efficient measurement and computational approach to improve modelling of the local atmospheric photochemistry that drives NO 2 , O 3 and PM pollution levels. The incorporation 20 of local radiation measurements in measurement networks, and the consequent greater spatial resolution of locally-relevant photolysis coefficients in model photolysis parameterisations, will improve the accuracy of assessment of air pollution and policy-intervention impacts.