Mechanisms by which different polar fractions of dissolved organic matter affect sorption of the herbicide MCPA in ferralsol

ABSTRACT Exogenous dissolved organic matter (DOM) modifies the sorption of 4-chloro- 2-methylphenoxyacetic acid (MCPA, a polar herbicide) in soil. However, how the chemodiversity and diverse fractions of DOM affect MCPA sorption is still unknown. Here, DOM was extracted from compost and rice straw; the structure–activity correlations between DOM chemodiversity and theirs effects on MCPA sorption were investigated by redundancy analysis. Moreover, the mechanism involved was explored by spectroscopic techniques, microbeam and modeling. DOM mainly affected MCPA sorption by altering soil surface properties and MCPA complexed form. Hydrophobic neutral (HON) and acid insoluble matter (AIM) were the fractions of DOM that most inhibited MCPA sorption through soil pore blockage, and were related to the humic-like substances with high aromaticity and large molecular weight. The hydrophobic acid fraction (HOA) only showed an intermediate inhibition on the sorption, although the largest competitive sorption occurred. This was because HOA contained abundant aromatic acid and polar groups with moderate polarity. Thus, the reduced effect caused by competitive sorption was partly compensated by the greatest co-sorption by HOA. The hydrophilic matter (HIM) had the weakest inhibition on MCPA sorption, because this fraction was rich in simple sugars, poly- and oligosaccharides, but lacked aryl groups. The results will aid in the risk assessments and prevention of MCPA in DOM-introduced soil.