Photochemical effect of humic acid components separated using molecular imprinting method applying porphyrin-like...

To elucidate the relationship between photochemical functions with the structure of humic acids (HA), we developed a molecular imprinting method to separate the substances with given structure and investigated their photochemical behavior in aqueous solution. The substances with porphyrin-like core structure, such as chlorophyll or heme, were employed as template substances for preparing molecular imprinting polymers (MIP). The polymers were used to separate the substances with porphyrin-like structure from HA. Photochemical experiments were conducted to evaluate effects of the separated HA fractions on the photodegradation of coexisting organic pollutant. The results showed that all fractions bound by MIP accelerated photochemical degradation of coexisting 2,4-dichlorophenoxyacetic acid (2,4-D) under simulated sunlight (lambda>290 nm) irradiation, indicating that HA with porphyrin-like structure possesses better photoactivity than ones without the structure. The photochemical degradation of 2,4-D was enhanced when Fe(III), the ubiquitous element in natural aquatic systems, was added owing to the formation of Fe(III) complex with the HA. Electron paramagnetic resonance (EPR) spectra indicated that OH* and 1O2 radicals were generated in the solutions of HA fractions bound by MIP under simulated sunlight irradiation, implying that 2,4-D degradation could be related to oxidation reactions caused by reactive oxygen species (ROS).