Photoenhanced heterogeneous reaction of O3 with humic acid: Focus on O3 uptake and changes in the composition and optical property.

Abstract

Heterogeneous photochemical reaction of O3 with humic acid (HA) under simulated sunlight was performed using a flow tube reactor coupled to an O3 analyzer at ambient pressure. It was confirmed that light significantly enhanced the uptake of O3 on HA. The initial uptake coefficient (γi) and the steady-state uptake coefficient (γss) of O3 under irradiation increased by 1.6 and 3.8 times compared to those in the dark, respectively. The γi and γss on HA varied in the range of 0.76-2.77×10-5 and 1.50-9.55×10-6, respectively, which were dependent on various environmental factors including HA mass, total irradiance, initial O3 concentration, O2 content, temperature, relative humidity (RH) and HA solution pH. Both γi and γss showed linear dependence on the total irradiance (0-2.07×1016 photons/(cm2⋅s)) of the light source, and increased with the HA mass (0-3.2μg/cm2), temperature (278-298K) and HA solution pH (4.0-9.6). However, they showed negative correlations with the initial O3 concentration and O2 content. The γi remained constant in the RH range of 7%-60%, while γss exhibited the maximum value at RH=20%. During the ozonization of HA under irradiation, some functional groups were consumed, including CH2, CH3, aromatic CC, OH, CO, COOH and COO-. HA aged by O3 exhibited a decrease in the mass absorption efficiency (MAE) and a small increase in the absorption Ångström exponent between 300 and 600nm wavelength (AAE300,600), which was ascribed to changes in the composition of HA during the photochemical ozonization process.