Comparative time-based intermediates study of ozone oxidation of 4-chloro- and 4-nitrophenols followed by LCMS-TOF

Greater insights on the degradation pathways and intermediates formed during the oxidation of organics can be achieved by more suitable and compatible instrumentation. In our research, we sought to explore the relative advantages of the liquid chromatography coupled to a time of flight mass spectrometer (LCMS-TOF) technique for the comparative time-based degradation intermediates and pathways of 4-chlorophenol (4CP) and 4-nitrophenol (4NP). The ozonation of the analytes solution (100 mL of 2 x 10^-3 M) was done in a sintered glass reactor, with an ozone dose of 0.14 mg min^-1 (O₂/O₃ 10 mL/min). The comparative oxidation results revealed that the 4-chloro- and 4-nitrocatechol pathways via hydroxylation were the major degradation route for 4CP and 4NP. Catechol intermediate was present as a primary breakdown product for the two analytes. Hydroquinone was observed as transient degradation intermediate for 4CP, but was absent for 4NP. Rather, a novel ozonation intermediate 2, 4-dinitrophenol was identified which was further oxidized to 3,6-dinitrocatechol. Several dimer products were identified in the oxidation processes, favored by alkaline conditions with more versatility shown by 4CP. The study provided a great insight into the ozone degradation intermediates and pathways, with some intermediates scarce in literature identified.