Methanediol from cloud-processed formaldehyde is only a minor source of atmospheric formic acid.

Atmospheric formic acid is severely underpredicted by models. A recent study proposed that this discrepancy can be resolved by abundant formic acid production from the reaction (1) between hydroxyl radical and methanediol derived from in-cloud formaldehyde processing and provided a chamber-experiment-derived rate constant, k 1 = 7.5 × 10 -12 cm 3 s -1 . High-level accuracy coupled cluster calculations in combination with E,J -resolved two-dimensional master equation analyses yield k 1 = (2.4 ± 0.5) × 10 -12 cm 3 s -1 for relevant atmospheric conditions ( T = 260-310 K and P = 0-1 atm). We attribute this significant discrepancy to HCOOH formation from other molecules in the chamber experiments. More importantly, we show that reversible aqueous processes result indirectly in the equilibration on a 10 min. time scale of the gas-phase reaction [Formula: see text] (2) with a HOCH 2 OH to HCHO ratio of only ca . 2%. Although HOCH 2 OH outgassing upon cloud evaporation typically increases this ratio by a factor of 1.5-5, as determined by numerical simulations, its in-cloud reprocessing is shown using a global model to strongly limit the gas-phase sink and the resulting production of formic acid. Based on the combined findings in this work, we derive a range of 1.2-8.5 Tg/y for the global HCOOH production from cloud-derived HOCH 2 OH reacting with OH. The best estimate, 3.3 Tg/y, is about 30 times less than recently reported. The theoretical equilibrium constant K eq (2) determined in this work also allows us to estimate the Henry's law constant of methanediol (8.1 × 10 5 M atm -1 at 280 K).