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."