Impacts of updated reaction kinetics on the global GEOS-Chem simulation of atmospheric chemistry.

Abstract

We updated the chemical mechanism of the GEOS-Chem global 3-D model of atmospheric chemistry to include new recommendations from the NASA Jet Propulsion Laboratory (JPL) chemical kinetics Data Evaluation 19-5 and from the International Union of Pure and Applied Chemistry (IUPAC) and to balance carbon and nitrogen. We examined the impact of these updates on the GEOS-Chem version 14.0.1 simulation. Notable changes include 11 updates to reactions of reactive nitrogen species, resulting in a 7% net increase in the stratospheric NO_x (NO + NO₂) burden; an updated CO + OH rate formula leading to a 2.7% reduction in total tropospheric CO; adjustments to the rate coefficient and branching ratios of propane + OH, leading to reduced tropospheric propane (-17%) and increased acetone (+3.5%) burdens; a 41% increase in the tropospheric burden of peroxyacetic acid due to a decrease in the rate coefficient for its reaction with OH, further contributing to reductions in peroxyacetyl nitrate (PAN; -3.8%) and acetic acid (-3.4%); and a number of minor adjustments to halogen radical cycling. Changes to the global tropospheric burdens of other species include -0.7% for ozone, +0.3% for OH (-0.4% for methane lifetime against oxidation by tropospheric OH), +0.8% for formaldehyde, and -1.7% for NO_x. The updated mechanism reflects the current state of the science, including complex chemical dependencies of key atmospheric species on temperature, pressure, and concentrations of other compounds. The improved conservation of carbon and nitrogen will facilitate future studies of their overall atmospheric budgets.