Bacteria in clouds biodegrade atmospheric formic and acetic acids

Formic and acetic acids are major organic species in cloud water and affect precipitation acidity. In atmospheric models, their losses are limited to chemical oxidation in the gas and aqueous phases and deposition processes. Previous lab studies suggest that these acids can be efficiently biodegraded in water by atmospherically relevant bacteria. However, the importance of biodegradation as a loss process in the atmospheric multiphase system has not been fully assessed. We implemented biodegradation as a sink of formic and acetic acids in a detailed atmospheric multiphase chemistry model. In our model, biodegradation is considered in 0.1 % of cloud droplets according to atmospheric bacteria concentrations of 0.1 cminline-formula⁻³. We predict that up to 20 ppt hinline-formula⁻¹ formic acid and 5 ppt hinline-formula⁻¹ acetic acid are biodegraded. This translates into a concentration change of 20 % and 3 % in addition to that caused by chemical losses. Our sensitivity studies suggest that acetic acid is most efficiently biodegraded at pH inline-formula> 5, whereas biodegradation is least efficient for formic acid under such conditions. This trend can be explained by the fact that formic acid partitions more efficiently into the aqueous phase due to its higher Henry's law constant (inline-formula $M5inlinescrollmathml{K}_{\mathrm{normal\; H},\mathrm{normal\; eff}}\left(chem\mathrm{normal\; HCOOH}\right)=\mathrm{normal\; 2}\times {\mathrm{normal\; 10}}^{\mathrm{normal\; 5}}$ 121pt17ptsvg-formulamathimgbc99fa174a04e7379fc11bbf342eb038 acp-24-5181-2024-ie00001.svg121pt17ptacp-24-5181-2024-ie00001.png  M atminline-formula⁻¹ vs. inline-formula $M7inlinescrollmathml{K}_{\mathrm{normal\; H},\mathrm{normal\; eff}}\left(chem{\mathrm{normal\; CH}}_{\mathrm{normal\; 3}}\mathrm{normal\; COOH}\right)=\mathrm{normal\; 3}\times {\mathrm{normal\; 10}}^{\mathrm{normal\; 4}}$ 134pt17ptsvg-formulamathimgdbb1d2acb0d2a4d75ddabef796345b6e acp-24-5181-2024-ie00002.svg134pt17ptacp-24-5181-2024-ie00002.png  M atminline-formula⁻¹ at pH inline-formula= 5). Therefore, under such conditions, formic acid evaporates less efficiently from bacteria-free droplets, resulting in less formic acid in the gas phase for dissolution bacteria-containing droplets to replenish biodegraded acid. Our analysis demonstrates that previous estimates of the importance of atmospheric biodegradation were often biased high as they did not correctly account for such uptake limitation in bacteria-containing droplets. The results suggest that, under specific conditions, biological processes can significantly affect atmospheric composition and concentrations in particular volatile, moderately soluble organics.