15 Films of biogenic compounds exposed to the atmosphere are ubiquitously found on surfaces of cloud droplets, aerosol particles, buildings, plants, soils, and the ocean. These air/water interfaces host countless amphiphilic compounds concentrated there with respect to bulk water, leading to a unique chemical environment. Here, photochemical processes at the air/water interface of biofilm-containing solutions were studied, demonstrating abiotic VOC production from authentic biogenic 20 surfactants under ambient conditions. Using a combination of online-APCI-HRMS and PTR-ToF-MS, unsaturated and functionalized VOCs were identified and quantified, giving emission fluxes comparable to previous field and laboratory observations. Interestingly, VOC fluxes increased with the decay of microbial cells in the samples, indicating that cell lysis due to cell death was the main source for surfactants, and VOC production. In particular, irradiation of samples containing solely 25 biofilm cells without matrix components exhibited the strongest VOC production upon irradiation. In agreement with previous studies, LC-MS measurements of the liquid phase suggested the presence of fatty acids and known photosensitizers, possibly inducing the observed VOC production via peroxy-radical chemistry. Up to now such VOC emissions were directly accounted to high biological activity in surface waters. However, the obtained results suggest that abiotic photochemistry can 30 lead to similar emissions into the atmosphere, especially in less biologically-active regions. Furthermore, chamber experiments suggested that oxidation (O 3 /OH-radicals) of the photochemically-produced VOCs leads to aerosol formation and growth, possibly affecting