Analysis of the relationship between ambient levels of O3, NO2 and NO as a function of NOx in the UK

Monitoring data from the UK Automatic Urban and Rural Network are used to investigate the relationships between ambient levels of ozone (O3), nitric oxide (NO) and nitrogen dioxide (NO2) as a function of NOx, for levels ranging from those typical of UK rural sites to those observed at polluted urban kerbside sites. Particular emphasis is placed on establishing how the level of ‘oxidant’, OX (taken to be the sum of O3 and NO2) varies with the level of NOx, and therefore to gain some insight into the atmospheric sources of OX, particularly at polluted urban locations. The analyses indicate that the level of OX at a given location is made up of NOx-independent and NOx-dependent contributions. The former is effectively a regional contribution which equates to the regional background O3 level, whereas the latter is effectively a local contribution which correlates with the level of primary pollution. The local oxidant source has probable contributions from (i) direct NO2 emissions, (ii) the thermal reaction of NO with O2 at high NOx, and (iii) common-source emission of species which promote NO to NO2 conversion. The final category may include nitrous acid (HONO), which appears to be emitted directly in vehicle exhaust, and is potentially photolysed to generate HOx radicals on a short timescale throughout the year at southern UK latitudes. The analyses also show that the local oxidant source has significant site-to-site variations, and possible reasons for these variations are discussed. Relationships between OX and NOx, based on annual mean data, and fitted functions describing the relative contributions to OX made by NO2 and O3, are used to define expressions which describe the likely variation of annual mean NO2 as a function of NOx at 14 urban and suburban sites, and which can take account of possible changes in the regional background of O3.