Atmospheric behaviour of particulate oxalate at UK urban background and rural sites

Oxalic acid is widely reported in the literature as one of the major components of organic aerosol. It has been reported as both a product of primary emissions from combustion processes and as a secondary product of atmospheric chemistry. Concentrations of particulate oxalate have been measured at a UK urban site (500 daily samples) and for a more limited period simultaneously at a rural site (100 samples) in the fine (less than 2.5 μm) and coarse (2.5-10 μm) size fractions. Full size distributions have also been measured by sampling with a MOUDI cascade impactor. Average concentrations of oxalate sampled over different intervals in PM are 0.04 ± 0.03 μg m at the rural site and 0.06 ± 0.05 μg m at the urban background site, broadly comparable with measurements from other European locations. During the period of simultaneous sampling at the urban and rural site, concentrations were very similar and the inter-site correlation in the PM fraction for oxalate (r = 0.45; p <0.001) was appreciably weaker than that for sulphate and nitrate (r = 0.82 and 0.84, respectively). Nonetheless, the data clearly point to a predominantly secondary source of oxalate at these sites. Possible contributions from road traffic and woodsmoke appear to be very small. In the larger urban dataset, oxalate in PM was correlated significantly (p <0.01) with sulphate (r = 0.60), nitrate (r = 0.48) and secondary organic carbon (r = 0.25). Clustering of air mass back trajectories demonstrates the importance of advection from mainland Europe. The size distribution of oxalate at the urban site showed a major mode at around 0.55 μm and a minor mode at around 1.5 μm in the mass distribution. The former mode is similar to that for sulphate suggesting either a similar in-cloud formation mechanism, or cloud processing of oxalate and sulphate after formation in homogeneous reaction processes.