New Insights into Martian Atmospheric Chemistry

Abstract

HO_x radicals are produced in the Martian atmosphere by the photolysis of water vapor and subsequently participate in catalytic cycles that recycle carbon dioxide (CO_2) from its photolysis product carbon monoxide (CO), providing a qualitative explanation for the stability of its atmosphere. Balancing CO_2 production and loss based on our current understanding of Martian gas-phase chemistry has, however, proven to be difficult. The photolysis of O_3 produces O(^1D), while oxidation of CO produces HOCO radicals, a new member of the HO_x family. The O(^1D) quantum yield has recently been updated, which quantifies nonzero quantum yields in the Huggins bands. In Earth's atmosphere HOCO is considered to be unimportant since it is quickly removed by abundant oxygen molecules. The smaller amount of O_2 in the Mars' atmosphere causes HOCO's lifetime to be longer in Mars' atmosphere than Earth's (3 × 10^(-5) seconds to 1.2 days from Mars's surface to 240 km, respectively). Limited kinetic data on reactions involving HOCO prevented consideration of its reactions directly in atmospheric models. Therefore, the impact of HOCO reactions on Martian chemistry is currently unknown. Here, we incorporate new literature rate constants for HOCO chemistry and an updated representation of the O(^1D) quantum yield in the Caltech/JPL 1-D photochemical model for Mars' atmosphere. Our simulations exemplify perturbations to NO_y, HO_x, and CO_x species, ranging from 5 to 50%. The modified O(^1D) quantum yield and new HOCO chemistry cause a 10% decrease and a 50% increase in OH and H_2O_2 total column abundances, respectively. At low altitudes, HOCO production contributes 5% towards CO_2 production. Given recent experimentally-obtained branching ratios for the oxidation of CO, HOCO may contribute up to 70% toward the production of NO_y, where HO_x and NO_y species are enhanced up to a factor 3, which has implications for rethinking the fundamental understanding of NO_y, HO_x, and CO/CO_2 cycling on Mars. Two new reaction mechanisms for converting CO to CO_2 using HOCO reactions are proposed, which reveal that H_2O_2 is more intimately coupled to CO_x chemistry. Our simulations are in good agreement with satellite/spacecraft measurements of CO and H_2O_2 on Mars.

Additional details