Theoretical investigation on atmospheric oxidation of fluorene initiated by OH radical.

Atmospheric oxidation of fluorene and its derivatives initiated by OH radicals was investigated theoretically with quantum chemical calculation methods [M06-2X/6-311++G(3df,2p)//M06-2X/6-311+G(d,p)]. It revealed that the OH addition pathways form hydroxyfluorene and ring-opening product dialdehyde while the H abstraction pathways lead to the formation of 9-fluorenone. Subsequent oxidation of 9-fluorenone has considerable potential to form dibenzo-p-dioxin and nitrofluorenone according to the present calculation results. The atmospheric lifetime of fluorene relative to the reactions with OH radicals is deduced to be 12.51 h based on the calculated overall rate constant (2.29 × 10-11 cm3 molecule-1 s-1) at 298 K and 1 atm. The oxidation products of fluorene in the atmosphere are generally more toxic and persistent. This work provides a comprehensive explanation for atmospheric oxidation processes of fluorene and facilitates clarifying its environmental risks.