Hygroscopic properties of oxalic acid and atmospherically relevant oxalates

Oxalic acid and oxalates represent an important fraction of atmospheric organic aerosols, however, little knowledge about the hygroscopic behavior of these particles is known. In this study, the hygroscopic behavior of oxalic acid and atmospherically relevant oxalates (H2C2O4, (NH4)2C2O4, CaC2O4, and FeC2O4) were studied by Raman spectrometry and vapor sorption analyzer. Under ambient relative humidity (RH) of 10–90%, oxalic acid and these oxalates hardly deliquesce and exhibit low hygroscopicity, however, transformation between anhydrous and hydrated particles was observed during the humidifying and dehumidifying processes. During the water adsorption process, conversion of anhydrous H2C2O4, (NH4)2C2O4, CaC2O4, and FeC2O4 to their hydrated particles (i.e., H2C2O4·2H2O, (NH4)2C2O4·H2O, CaC2O4·H2O, and FeC2O4·2H2O) occurred at about 20% RH, 55% RH, 10% RH, and 75% RH, respectively. Uptake of water on hydrated Ca-oxalate and Fe-oxalate particles can be described by a multilayer adsorption isotherm. During the dehumidifying process, dehydration of H2C2O4·2H2O and (NH4)2C2O4·H2O occurred at 5% RH while CaC2O4·H2O and FeC2O4·2H2O did not undergo dehydration. These results implied that hydrated particles represent the most stable state of oxalic acid and oxalates in the atmosphere. In addition, the assignments of Raman shift bands in the range of 1610–1650 cm−1 were discussed according to the hygroscopic behavior measurement results.