Formaldehyde content of atmospheric aerosol

Formaldehyde (HCHO) is a highly soluble polar molecule with a large sticking coefficient and thus likely exists in both gaseous and particulate forms. Few studies, however, address particulate HCHO (HCHO(p)). Some report that HCHO(p) concentrations (obtained only with long duration sampling) are very low. The lack of data partly reflects the difficulty of specifically measuring HCHO(p). Long duration filter sampling may not produce meaningful results for a variety of reasons. In this work, gaseous HCHO (HCHO(g)) and (HCHO(p)) were, respectively, collected with a parallel plate wet denuder (PPWD) followed by a mist chamber/hydrophilic filter particle collector (PC). The PPWD quantitatively removed HCHO(g) and the PC then collected the transmitted aerosol. The collected HCHO from either device was alternately analyzed by Hantzsch reaction-based continuous flow fluorometry. Each gas and particle phase measurement took 5 min each, with a 10 min cycle. The limits of detection were 0.048 and 0.0033 μg m(-3), respectively, for HCHO(g) and HCHO(p). The instrument was deployed in three separate campaigns in a forest station in western Japan in March, May, and July of 2013. Based on 1296 data pairs, HCHO(p), was on the average, 5% of the total HCHO. Strong diurnal patterns were observed, with the HCHO(p) fraction peaking in the morning. The relative humidity dependence of the partition strongly suggests that it is driven by the liquid water content of the aerosol phase. However, HCHO(p) was 100× greater than that expected from Henry's law. We propose that the low water activity in the highly saline droplets lead to HCHO oligomerization.