Photocatalytic degradation of organic micropollutants: Inhibition mechanisms by different fractions of natural organic matter

Natural organic matter (NOM) can inhibit the photocatalytic degradation of organic micropollutants (OMPs) through inner filter effect, reactive oxygen species (ROS) scavenging, and competitive adsorption. However, previous studies have focused solely on the bulk properties of NOM and our understanding of the inhibition mechanism by NOM fractions during photocatalytic degradation of OMP is still fragmentary. In this study, five well-characterized different NOM samples (i.e., secondary treated wastewater, river water, and three standard NOM surrogates) were used to elucidate the inhibition mechanisms during photocatalytic degradation of carbamazepine (a model OMP) using TiO2 and its composites with carbon nanotubes (CNT-TiO2) under UVC and solar-light irradiation. The results indicated that terrestrially derived NOM with high aromaticity, a low oxygen/carbon atom ratio, and large molecular weight is the major fraction that participates in ROS scavenging, competitive adsorption, and inner filter effect. Furthermore, the modeling analysis suggested that inner filter effect due to NOM and ROS scavenging was the most influential inhibitory mechanism. In the case of secondary treated wastewater, the presence of high concentrations of inorganic species (e.g., PO43−, Cl−, and NO3−) together with NOM significantly reduced the photocatalytic degradation of carbamazepine. Overall, the methods and the results of this study provide a comprehensive understanding of the effects of NOM fractions on photocatalysis and highlight the need to further consider the interplay between NOM and background inorganic constituents in photocatalytic degradation of OMP.