Partitioning, sources and variability of regional and local oxidant (OX = O3 + NO 2) in a coastal rural area in the southwest of Iberian Peninsula.

The purpose of this work is to investigate the behaviour and variability of oxidant levels (OX = NO2 + O3), for the first time, in a rural coastal area in the southwest of the Iberian Peninsula, affected by several air masses types. Detailed database (built-up over the years 2008 to 2011, and containing around 500,000 data) from the Atmospheric Sounding Station "El Arenosillo" was used. The observed daily cycles of NO x and OX were influenced by air masses coming from industrial and urban area. It can be seen that the concentration of OX is made up of a NO x -independent 'regional' contribution (i.e. the O3 background), and a linearly NO x -dependent 'local' contribution from primary emissions, such as traffic. The local emission is very low in this area. Also, the regional contribution is similar to unpolluted sites and presents seasonal variation, being higher in May. However, our measurements showed that the proportion of OX in the form of NO2 increases with the increase in NO x concentration during the day. The higher proportion of NO2 observed at night must be due to the conversion of NO to NO2 by the NO + O3 reaction. With regards to the source of the local NO x -dependent contribution, it may be attributed to industrial emission, or the termolecular reaction 2NO + O2 = 2NO2, at high-NO x levels and stagnant air during several days. Finally, we estimated the photolysis rate of NO2, J NO2, an important key atmospheric reaction coupled with ozone. We also present surface plots of annual variation of the daily mean NO x and OX levels, which indicate that oxidants come from transport processes instead of local emissions associated as local photochemistry.