Accelerated Indirect Photodegradation of Organic Pollutants at the Soil–Water Interface

Indirect photolysis driven by photochemically produced reactive intermediates (PPRIs) is pivotal for the transformations and fates of pollutants in nature. While well-studied in bulk water, indirect photolysis processes at environmental interfaces remain largely unexplored. This study reveals a significant acceleration of indirect photodegradation of organic pollutants at the soil-water interface of wetlands. Organic pollutants experienced ubiquitously enhanced indirect photodegradation at the soil-water interfaces, with rates 1.41 ± 0.01 to 4.27 ± 0.03-fold higher than those in bulk water. This enhancement was observed across various natural and artificial wetlands, including coastal wetlands and rice paddies. In situ mapping indicated that soil-water interfaces act as hotspots, concentrating both organic pollutants and PPRIs by 9.30- and 4.27-folds, respectively. This synchronized colocation is the primary cause of the accelerated pollutant photolysis. Additionally, the contribution of each PPRI species to pollutant photolysis and a coupled transformation pathway at the soil-water interface significantly differed from those in bulk water. For instance, the contribution of singlet oxygen to metoxuron photolysis increased from 10.1% in bulk water to 44.4% at the soil-water interface. Our study highlights the rapid indirect photolysis of organic pollutants at the soil-water interfaces, offering new insights into the natural purification processes in wetlands as "Earth's kidneys."