Elucidating the Effects of COVID-19 Lockdowns in the UK on the O3-NOx-VOC Relationship

The unprecedented reductions in anthropogenic emissions over the COVID-19 lockdowns were utilised to investigate the response of ozone (O3) concentrations to changes in its precursors across various UK sites. Ozone, volatile organic compounds (VOCs) and NOx (NO+NO2) data were obtained for a 3-year period encompassing the pandemic period (January 2019–December 2021), as well as a pre-pandemic year (2017), to better understand the contribution of precursor emissions to O3 fluctuations. Compared with pre-lockdown levels, NO and NO2 declined by up to 63% and 42%, respectively, over the lockdown periods, with the most significant changes in pollutant concentrations recorded across the urban traffic sites. O3 levels correspondingly increased by up to 30%, consistent with decreases in the [NO]/[NO2] ratio for O3 concentration response. Analysis of the response of O3 concentrations to the NOx reductions suggested that urban traffic, suburban background and suburban industrial sites operate under VOC-limited regimes, while urban background, urban industrial and rural background sites are NOx-limited. This was in agreement with the [VOC]/[NOx] ratios determined for the London Marylebone Road (LMR; urban traffic) site and the Chilbolton Observatory (CO; rural background) site, which produced values below and above 8, respectively. Conversely, [VOC]/[NOx] ratios for the London Eltham (LE; suburban background) site indicated NOx-sensitivity, which may suggest the [VOC]/[NOx] ratio for O3 concentration response may have had a slight NOx-sensitive bias. Furthermore, O3 concentration response with [NO]/[NO2] and [VOC]/[NOx] were also investigated to determine their relevance and accuracy in identifying O3-NOx-VOC relationships across UK sites. While the results obtained via utilisation of these metrics would suggest a shift in photochemical regime, it is likely that variation in O3 during this period was primarily driven by shifts in oxidant (OX; NO2 + O3) equilibrium as a result of decreasing NO2, with increased O3 transported from Europe likely having some influence.