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The impact of heterogeneous uptake of HO2 on aerosol surfaces on radical concentrations and the O3 production regime in Beijing in summertime was investigated. The uptake coefficient of HO2 onto aerosol surfaces, γHO2, was calculated for the AIRPRO campaign in Beijing, in summer 2017, as a function of measured aerosol soluble copper concentration, [Cu2+]eff, aerosol liquid water content, [ALWC], and particulate matter concentration, [PM]. An average γHO2 across the entire campaign of 0.070±0.035 was calculated, with values ranging from 0.002 to 0.15, and found to be significantly lower than the value of γHO2=0.2, commonly used in modelling studies. Using the calculated γHO2 values for the summer AIRPRO campaign, OH, HO2 and RO2 radical concentrations were modelled using a box model incorporating the Master Chemical Mechanism (v3.3.1), with and without the addition of γHO2, and compared to the measured radical concentrations. The rate of destruction analysis showed the dominant HO2 loss pathway to be HO2 + NO for all NO concentrations across the summer Beijing campaign, with HO2 uptake contributing % to the total loss of HO2 on average. This result for Beijing summertime would suggest that under most conditions encountered, HO2 uptake onto aerosol surfaces is not important to consider when investigating increasing O3 production with decreasing [PM] across the North China Plain. At low [NO], however, i.e. ppb, which was often encountered in the afternoons, up to 29 % of modelled HO2 loss was due to HO2 uptake on aerosols when calculated γHO2 was included, even with the much lower γHO2 values compared to γHO2= 0.2, a result which agrees with the aerosol-inhibited O3 regime recently proposed by Ivatt et al. (2022). As such it can be concluded that in cleaner environments, away from polluted urban centres where HO2 loss chemistry is not dominated by NO but where aerosol surface area is high still, changes in PM concentration and hence aerosol surface area could still have a significant effect on both overall HO2 concentration and the O3 production regime. Using modelled radical concentrations, the absolute O3 sensitivity to NOx and volatile organic compounds (VOCs) showed that, on average across the summer AIRPRO campaign, the O3 production regime remained VOC-limited, with the exception of a few days in the afternoon when the NO mixing ratio dropped low enough for the O3 regime to shift towards being NOx-limited. The O3 sensitivity to VOCs, the dominant regime during the summer AIRPRO campaign, was observed to decrease and shift towards a NOx-sensitive regime both when NO mixing ratio decreased and with the addition of aerosol uptake. This suggests that if [NOx] continues to decrease in the future, ozone reduction policies focussing solely on NOx reductions may not be as efficient as expected if [PM] and, hence, HO2 uptake to aerosol surfaces continue to decrease. The addition of aerosol uptake into the model, for both the γHO2 calculated from measured data and when using a fixed value of γHO2=0.2, did not have a significant effect on the overall O3 production regime across the campaign. While not important for this campaign, aerosol uptake could be important for areas of lower NO concentration that are already in a NOx-sensitive regime.

The photostationary state (PSS) equilibrium between NO and NO2 is reached within minutes in the atmosphere and can be described by the PSS parameter, φ. Deviations from expected values of φ have previously been used to infer missing oxidants in diverse locations, from highly polluted regions to the extremely clean conditions observed in the remote marine boundary layer (MBL), and have been interpreted as missing understanding of fundamental photochemistry. Here, contrary to these previous observations, we observe good agreement between PSS-derived NO2 ([NO2]PSS ext.), calculated from measured NO, O3, and jNO2 and photochemical box model predictions of peroxy radicals (RO2 and HO2), and observed NO2 ([NO2]Obs.) in extremely clean air containing low levels of CO ( ppbV) and VOCs (volatile organic compounds). However, in clean air containing small amounts of aged pollution (CO > 100 ppbV), we observed higher levels of NO2 than inferred from the PSS, with [NO2]Obs. / [NO2]PSS ext. of 1.12–1.68 (25th–75th percentile), implying underestimation of RO2 radicals by 18.5–104 pptV. Potential NO2 measurement artefacts have to be carefully considered when comparing PSS-derived NO2 to observed NO2, but we show that the NO2 artefact required to explain the deviation would have to be ∼ 4 times greater than the maximum calculated from known interferences. If the additional RO2 radicals inferred from the PSS convert NO to NO2 with a reaction rate equivalent to that of methyl peroxy radicals (CH3O2), then the calculated net ozone production rate (NOPR, ppbV h−1) including these additional oxidants is similar to the average change in O3 observed, within estimated uncertainties, once halogen oxide chemistry is accounted for. This implies that such additional peroxy radicals cannot be excluded as a missing oxidant in clean marine air containing aged pollution and that modelled RO2 concentrations are significantly underestimated under these conditions.

Particulate nitrate ( pNO 3 − ) has long been considered a permanent sink for NO x (NO and NO 2 ), removing a gaseous pollutant that is central to air quality and that influences the global self-cleansing capacity of the atmosphere. Evidence is emerging that photolysis of pNO 3 − can recycle HONO and NO x back to the gas phase with potentially important implications for tropospheric ozone and OH budgets; however, there are substantial discrepancies in “renoxification” photolysis rate constants. Using aircraft and ground-based HONO observations in the remote Atlantic troposphere, we show evidence for renoxification occurring on mixed marine aerosols with an efficiency that increases with relative humidity and decreases with the concentration of pNO 3 − , thus largely reconciling the very large discrepancies in renoxification photolysis rate constants found across multiple laboratory and field studies. Active release of HONO from aerosol has important implications for atmospheric oxidants such as OH and O 3 in both polluted and clean environments.

Photolysis rate constants (j-values) play a crucial role in atmospheric chemistry modelling, but capturing the variability in local conditions needed for their accurate simulation is computationally challenging. One approach is to adjust modelled clear-sky estimates using ratios of measured-to-modelled j-values of a reference photolysis, typically j(NO2) or j(O1D). However, application of such adjustments to other photolysis reactions introduces uncertainty. Using spectral radiometer data from the UK, this study examines how hourly measurement driven adjustment factors (MDAF) across a set of 12 photolysis reactions group together using cluster analysis, and evaluates the uncertainties in using j(NO2) and j(O1D)-derived MDAF values to adjust modelled j-values of other photolysis reactions. The NO2-MDAF reference is suitable for adjusting photolysis reactions that absorb at λ > 360 nm (HONO, methylglyoxal, ClNO2, ClONO2 → Cl), which are largely independent of solar zenith angle and total ozone column (

Volatile organic compounds (VOCs) are important precursors to the formation of ozone (O3) and secondary organic aero-sols (SOA) and can also have direct human health impacts. Generally, given the range and number of VOC species, their emissions are poorly characterised. The VOC levels in Beijing during two campaigns (APHH) were investigated using a dispersion model (NAME), and a chemical box model (AtChem2) in order to understand how chemistry and transport affect the VOC concentrations in Beijing. Emissions of VOCs in Beijing and contributions from outside Beijing were modelled using the NAME dispersion model combined with the emission inventories and were used to initialize the AtChem2 box model. The modelled concentrations of VOCs from the NAME-AtChem2 combination were then compared to the output of a chemical transport model (GEOS-Chem). The results from the emission inventories and the NAME air mass pathways suggest that industrial sources to the south of Beijing and within Beijing both in summer and winter are very important in con-trolling the VOC levels in Beijing. A number of scenarios with different nitrogen oxides to ozone ratios (NOx / O3) and hydroxyl (OH) levels were simulated to determine the changes in VOC levels. In Beijing over 80 % of VOC are emitted locally during winter, while during summer about 35 % of VOC concentrations (greater for some individual species) are transported into Beijing from the surrounding regions. Most winter scenarios are in good agreement with daily GEOS-Chem simulations, with the best agreements seen for the modelled concentrations of ethanol, benzene and propane with correlation coefficients of 0.67, 0.63 and 0.64 respectively. Furthermore, the production of formaldehyde within 24 hours air travel from Beijing was investigated, and it was determined that 90 % of formaldehyde in the winter and 83 % in the summer in Beijing is secondary, produced from oxidation of non-methane volatile organic compounds (NMVOCs). The benzene / CO and toluene / CO ratios during the campaign is very similar to the ratio derived from literature for 2014 in Beijing, however more data are needed to enable investigation of more species over longer timeframes to determine whether this ratio can be applied to predicting VOCs in Beijing. The results suggest that VOC concentrations in Beijing are driven predominantly by sources within Beijing and by local atmospheric chemistry during the winter, and by a combination of transport and chemistry during the summer. Moreover, the relationship of the NOx / VOC and O3 during winter and summer shows the need for season-specific policy measures.