Diuron herbicide degradation catalyzed by low molecular weight humic acid-like compounds

Phenylureas such as diuron are major herbicides used worldwide to control undesirable weeds. The environmental fate of phenylureas is of great interest because massive amounts of those herbicides are used. It is known that abiotic degradation of phenylureas in soil-water systems is catalyzed by humic acids. However, due to the chemical heterogeneity and large molecular sizes of humic acids, the specific effects of functional groups during catalysis have not been elucidated. Therefore, we studied here for the first time the kinetics of diuron degradation in the presence of low molecular weight humic acid-like compounds such as benzoic acid derivatives. Experiments were carried out at various pH and temperature, and monitored by high-performance liquid chromatography. Results show that all benzoic acid derivatives efficiently catalyzed diuron hydrolysis. The catalytic efficiency decreased in the following order: 0.88 M-1 day-1 for 3,4-dihydroxybenzoic acid, 0.72 M-1 day-1 for 4-hydroxybenzoic acid, 0.23 M-1 day-1 for phthalic acid, 0.11 M-1 day-1 for 2-hydroxybenzoic acid, and 0.09 M-1 day-1 for 2,4-dihydroxybenzoic acid. These differences in the catalytic efficiency are explained by steric hindrance affecting the accessibility of reactive sites and hence influencing the rate of the overall process. Steric factors are therefore expected to control the catalytic activity of humic acids because of the chemical similarities between humic acids and low molecular weight humic acid-like compound. Our results should help predict more accurately the fate and abiotic degradation mechanism of phenylureas in the environment. © 2013 Springer-Verlag Berlin Heidelberg.