Seasonal variability of formaldehyde production from photolysis of rainwater dissolved organic carbon

Photochemical production of formaldehyde (HCHO) was measured in rainwater from 13 precipitation events in Wilmington, North Carolina, USA under conditions of simulated sunlight. HCHO concentrations increased in all samples irradiated with no changes observed in dark controls. HCHO photoproduction rates were strongly correlated with dissolved organic carbon (DOC) suggesting HCHO was derived from direct or indirect photolysis of rainwater DOC. The higher photoproduction rates (0.03–2.9 μM h−1) relative to those reported for surface waters suggests that rainwater DOC is more photolabile in terms of HCHO production than surface waters. HCHO photoproduction rates were higher in growing season (1.0 ± 1.0 μM h−1) compared to non-growing season (0.08 ± 0.05 μM h−1) even when rates were normalized for DOC (6.8 ± 3.6 μM h−1 mM C−1 versus 1.8 ± 1.0 μM h−1 mM C−1). The higher growing season rate may be related to seasonal differences in the composition of DOC as evidenced by differences in fluorescence per unit carbon of rainwater samples. Irradiation of C18 extracts of rainwater also produced HCHO, but at lower rates compared to corresponding whole rain samples, suggesting that hydrophyllic components of rainwater play a role in HCHO photoproduction. Our results indicate that photolysis of rainwater DOC produces significant amounts of HCHO, and possibly other low molecular weight organic compounds, likely increasing its reactivity and bioavailability.