UV photochemistry of carboxylic acids at the air-sea boundary: A relevant source of glyoxal and other oxygenated VOC in the marine atmosphere

Photochemistry plays an important role in marine dissolved organic carbon (DOC) degradation, but the mechanisms that convert DOC into volatile organic compounds (VOCs) remain poorly understood. We irradiated carboxylic acids (C-7-C-9) on a simulated ocean surface with UV light (<320nm) in a photochemical flow reactor and transferred the VOC products into a dark ozone reactor. Glyoxal was detected as a secondary product from heptanoic, octanoic, and nonanoic acid (NA) films, but not from octanol. Primary glyoxal emissions were not observed, nor was glyoxal formed in the absence of ozone. Addition of a photosensitizer had no noticeable effect. The concurrent detection of heptanal in the NA system suggests that the ozonolysis of 2-nonenal is the primary chemical mechanism that produces glyoxal. This source can potentially sustain tens ofparts per trillion by volume (pptv) glyoxal over oceans, and helps to explain why glyoxal fluxes in marine air are directed from the atmosphere into the ocean.