Insight into Source and Evolution of Oxalic Acid: Characterization of Particulate Organic Diacids in a Mega-City, Shanghai from 2008 to 2020

Abstract

Organic acids are important aerosol compositions with significant implications on particle formation, growth, acidity, phase state, and environmental impacts. Oxalic acid was found to be the most abundant particulate organic diacid in Shanghai during the study period, accounting for ~58% of the total dicarboxylic acids (C2–C10). Biomass burning (BB) explained a small but non-negligible fraction (less than 10%) of oxalate. Significant correlations between oxalate and sulfate indicated a potentially synergistic formation mechanism of oxalate and sulfate. In addition, meteorological factors such as ambient temperature and relative humidity were found to influence the formation of oxalate. Higher oxalate relative to inorganic particulate content was found in summer. Potential source contribution function analysis suggested that most of the oxalate observed in Shanghai was produced locally. The formation of oxalate was largely impacted by atmospheric oxidation capacity as indicated by its significant correlations with both secondary organic carbon (SOC) and sulfur oxidation ratio (SOR). The evolution of oxalate, oxalate/sulfate, oxalate/organic carbon were consistent with the emission trend of volatile organic carbons (VOCs) in recent years, indicating that oxalate may be derived from secondary oxidation of VOCs, which is further confirmed by a positive relationship between Ox and oxalate/VOCs over the study period. With a detailed characterization of oxalate in Shanghai, our study highlights the importance of regulating primary emissions, such as VOCs, as well as mitigation of atmospheric oxidation capacity in controlling air pollution in a coastal megacity.