Atrazine Complexation by Soil Humic Acids

Abstract

Atrazine [6-chloro-N-ethyl-N'-(1-methylethyl)-1,3,5-triazine-2,4-diamine] complexation pathways with soil humic acid remain a controversial issue, in part because of the absence of direct spectroscopic information. Recent optical and magnetic resonance spectral data indicate that proton-transfer and, to a lesser extent, hydrogen bonding are as important as electron-transfer in the mechanisms of reaction between atrazine and humic acid, whereas other s-triazines appear to react more strongly by electron transfer mechanisms. Two representative temperate-zone humic acids were selected to probe the issue of complexation mechanisms more decisively. They were reacted at pH < 7 with 140 mmol m -3 atrazine solution under exdusion of light. Infrared and electron spin resonance spectra of the resulting products gave evidence for proton-transfer and, under certain conditions, electron-transfer reactions. The spectroscopic data, and those from other published studies, were analyzed in terms of the molecular properties of humic acids and s-triazines. The analysis suggested a general guiding principle to characterize the complexation mechanisms of s-triazines with soil humic acids. Proton-transfer is favored (and electron-transfer is disfavored) for humic acids of high acidic functional group content and for s-triazines of low basicity. Electron-transfer mechanisms are favored for humic acids of low acidic functional group content and for s-triazines of high basicity. This principle illustrates the importance of specific molecular structure, as opposed to class structure, to understanding reactivity between the s-triazines and humic acids.