The enhanced mixing states of oxalate with metals in single particles in Guangzhou, China

Highlights: • 55% of oxalate-containing particles were internally mixed with metals. • Enhanced oxalate production might be due to increased aqueous phase reactions. • The complexation with metals also contributed to the enrichment of oxalate. • The efficient photolysis of oxalate was observed in the metal particles. Recently, internal mixing states of oxalate with metals in single particles have been reported from field studies, yet the role of metals in the formation processes of oxalate remains unclear due to the diversity of chemical components and complex atmospheric environment. In this study, the mixing states of oxalate with five metals, including zinc (Zn), copper (Cu), lead (Pb), vanadium (V) and iron (Fe) were investigated in Guangzhou, China. It was found that 55% of oxalate-containing particles were internally mixed with these metals. The number fraction of oxalate in the metal-containing particles ranged from 5.4–26%, which is much higher than that in the total detected particles (4.0%), indicating significant enrichment of oxalate in the metal-containing particles. Enhanced oxalate production was found in the Fe- and V-containing particles based on distinctly higher relative peak area (RPA) ratios of oxalate to its precursors compared to the total particles, possibly due to enhanced aqueous phase reactions in the Fe- and V-containing particles. However, enrichment of oxalate in the Zn-, Pb-, and Cu-containing particles was possibly associated with complexation of gas phase oxalic acid with the metals, as indicated by the small increase in RPA ratios in these particles. On the other hand, the internal mixing of oxalate with metals was found to provide a way of efficient photolysis of oxalate-metal complexes, which led to a decrease in oxalate after sunrise in the metal-containing particles. In this study, the enhanced mixing states of oxalate with metals have revealed the important role of metals in the production and degradation of oxalate, providing insights for the evaluation of metals in the formation processes of organic aerosol in field studies, which is beneficial to the further study of air pollution in metal emission areas.