Molecular linkages between chemodiversity and MCPA complexation behavior of dissolved organic matter in paddy soil: Effects of land conversion

Complexation of dissolved organic matter (DOM) plays a crucial role in regulating the fate and risk of agrochemicals. Here, taking a toxic herbicide MCPA (4-chloro-2- methylphenoxyacetic acid) as the target, the effect of land conversion on complexation behavior of DOM to agrochemicals was investigated in paddy soil. Furthermore, the mechanisms were explored in a new perspective of DOM chemodiversity. Soil DOMs were selected from four long-term cropping systems, including paddy field (PF), vegetable field (VF), rice-vegetable rotation (RV) and abandoned land (AL). The results showed that the DOMs in PF and AL were rich in hydrophilic substances (e.g., carbohydrates or protein-like molecules) with low aromaticity. However, after converting PF to VF and RV, abundant aromatic macromolecules and aliphatic alkanes were observed in DOM. Due to those changes in DOM chemodiversity, the binding site and capability of DOM were highest in VF and RV, and were positively correlated with DOM aromaticity, MW, humus and polar groups (e.g., amino). This was because the complexation of "DOM-MCPA" was static binding via ligand exchange and H-bonding among polar groups and hydrophobic interaction among aromatic skeletons. The EEM-PARAFAC confirmed that microbial humic-like substances dominated the complexation of DOM rather than terrestrial humic-like and tryptophan-like matters. The 2D-COS analysis further revealed that the complexation of DOM preferentially occurred in amino, polysaccharide C-O and aliphatic C-H for PF and AL, but in aromatic C=C, amide C=N for RV and VF. In summary, these findings provide molecular insight into the effect of land conversion on DOM complexation activity, which highlight the importance of DOM chemodiversity. These results will contribute to the risk assessments of agrochemicals in paddy soil.