Investigation of the Acid-Mediated Photosensitized Reactions of Amphiphilic α-Keto Acids at the Air-Water Interface Using Field-Induced Droplet Ionization Mass Spectrometry

The photochemistry of alpha-keto acids has been of great interest due to its implications in atmospheric and prebiotic chemistries. alpha-Keto acids with long alkyl chains are amphiphilic in nature, and they tend to partition at the air-water interface of atmospheric water droplets and add to the complexity of the chemistries therein. The air-water interface is a unique environment that plays a vital role in overall atmospheric processes. However, existing studies mostly focus on the photochemistry of alpha-keto acids in the bulk solution and neglect the reactions that occur at the interface. In this study, using the field-induced droplet ionization mass spectrometry methodology that is capable of selectively sampling amphiphilic molecules that reside at the air-water interface, we show that the acid-mediated photochemistry of 2-oxooctanoic acid and 2-oxoheptoic acid is highly different from those of previously reported reactions in the bulk and contributes to the formation of humic-like substances (HULIS). This work emphasizes the uniqueness of the photochemistry at the air-water interface. We anticipate that studies of atmosphere-relevant photochemistry at the air-water interface will be an avenue rich with opportunities.

Automated summary

This study shows that the acid-mediated photochemistry of alpha-keto acids at the air-water interface is significantly different from those in bulk solution, contributing to the formation of HULIS. The research highlights the uniqueness of photochemistry at the air-water interface and suggests that further studies in this area could present rich opportunities.