The OH-initiated atmospheric reaction mechanism and kinetics for levoglucosan emitted in biomass burning

- The OH-initiated reaction of levoglucosan is one of the main eliminating ways.
- The rate constant with the OH radical at 298 K is 2.21 × 10−13 cm3 molecule−1 s−1.
- The atmospheric reaction mechanism of levoglucosan varies with temperature.
- Once the reaction initiates, the subsequent reactions tend to occur spontaneously.

Levoglucosan is a typical molecular tracer of biomass-burning aerosols in the atmosphere. The mechanism for OH-initiated reaction with levoglucosan is studied at the level of MPWB1K/6-311+G(3df,2p)//MPWB1K/6-31+G(d,p). The possible subsequent reactions in the presence of O2, NO and H2O are also taken into consideration. The study shows that the H atom abstraction from the C4-position by the OH radical is an energetically favorable pathway, and that the OH-initiated products contribute to the formation of SOA and atmospheric acidity. The kinetic calculation is performed and the rate constants are calculated over the temperature range of 200-1500 K, using the Rice-Ramsperger-Kassel-Marcus (RRKM) theory. The rate constant of levoglucosan reacting with the OH radical at 298 K is 2.21 × 10−13 cm3 molecule−1 s−1 and the atmospheric lifetime is 26 days ([OH] = 2.0 × 106 molecule cm−3). The equilibrium constants both in gas phase and aqueous are computed. The free energy ΔG indicates that, the subsequent reactions tend to take place more spontaneously once the reaction occurs. This work provides a comprehensive investigation about OH-initiated atmospheric reactions with levoglucosan, which is helpful for experiment and risk assessment.