Concentration and size distribution of particulate oxalate in marine and coastal atmospheres - Implication for the increased importance of oxalate in nanometer atmospheric particles

In literature, particulate oxalate has been widely studied in the total suspended particles (TSP), particles <10 μm or 2.5 μm (PM10 and PM2.5) and size-segregated particles >100 nm. In this article, we measured oxalate's concentrations in size-segregated atmospheric particles down to 10 nm or 56 nm during eight campaigns performed at a semi-urban coastal site, over the marginal seas of China and from the marginal seas to the northwest Pacific Ocean (NWPO) in 2012-2015. When the sum of the oxalate's concentration in particles <10 μm was used for intercomparison, the lowest average values of 0.05-0.06 μg m−3 were observed during the two campaigns performed at NWPO. The highest average value of 0.38 μg m−3 was observed at the coastal site during a heavy pollution event. Mode analysis results of particulate oxalate and the correlation between oxalate and sulfate suggested that the elevated concentrations of oxalate in PM10 were mainly related to enhanced in-cloud formation of oxalate via anthropogenic precursors. Size distribution data in the total of 136 sets of samples also showed approximately 80% of particulate oxalate's mass existing in atmospheric particles >100 nm. Consistent with previous studies, particulate oxalate in particles >100 nm was a negligible ionic component when comparing to particulate SO42− in the same size range. However, the mole ratios of oxalate/sulfate in particles <100 nm were generally increased by 1-2 orders of magnitude. In approximately 30% of the samples, the mole ratios in atmospheric particles <56 nm were larger than 0.5. Moreover, during Campaign 5, the oxalate's concentrations in <56 nm particles were substantially increased on the days in presence of new particle formation events. These results strongly imply the importance of oxalate in nanometer atmospheric particles, but not in >100 nm atmospheric particles such as PM2.5, PM10, TSP, etc.