Abstract
It was recently proposed (Franco et al., Nature 2021) that methanediol
(MD, HOCH2OH ) formed by hydration of formaldehyde in liquid cloud
droplets is outgassed to a larger extent than previously estimated, and
reacts in the gas phase with the hydroxyl radical (OH), leading to
formic acid (HCOOH). Whereas the resulting global production of formic
acid is greatly dependent on poorly constrained parameters, such as the
Henry’s law constant (HLC) of methanediol and the rate constant of its
reaction with OH, Franco et al. suggest, based on global model
calculations and on newly conducted chamber experiments (for the rate
constant) and on statistical prediction methods (for the HLC), that this
mechanism explains the large “missing source” of HCOOH in the
atmosphere (e.g. Stavrakou et al. 2012). If true, this finding would be
of tremendous importance for our understanding of the biogeochemical
cycling of oxygenated organic compounds. For this reason, it is of
utmost importance to double check the validity of thehypotheses and
parameterizations behind this assessment. Here we examine two critical
aspects of this determination: the HLC (taken equal to either 10^4 or
10^6 M atm^-1 in model simulations by Franco et al.) and the rate
of the MD+OH reaction (taken equal to 7.5 × 10^12 cm^3 s^-1 ).
The representation of chemical processing in liquid clouds in global
models is also briefly discussed. Plausible ranges for those parameters
are proposed , and causes of uncertainty are discussed . The potential
consequences for the resulting production of formic acid are briefly
explored.