The important characteristics of soil organic matter affecting 2,4-dichlorophenoxyacetic acid sorption along a catenary sequence.

Variations in the characteristics of soil organic matter (SOM) at the field-scale are largely unknown, particularly in relation to observed variations in herbicide sorption. For the herbicide 2,4-D [2,4-dichlorophenoxyacetic acid], we found that its organic carbon-normalized sorption coefficient, Koc, varied by four-fold, from 76 to 315 L kg(-1), in the Ap-horizon along a slope transect in an undulating agricultural field in Manitoba, Canada. In order to explain the relatively large in-field variation in 2,4-D Koc values, techniques ranging from conventional chemical fractionation methods to solid state Cross Polarization and Magic-Angle Spinning (13)C-Nuclear Magnetic Resonance applied on whole soils, were used to derive SOM chemical, physical and structural parameters for correlation analyses with the measured 2,4-D Koc values on whole soils. Out of the 15 parameters considered, the 2,4-D Koc was significantly positively correlated with 1) the carbon (C) content of sodium hydroxide-extracted humic acids (r = 0.83, P < 0.01), a chemical parameter indicative of free form C in soil; 2) the molar absorptivity of humic acids at wavelength 280 nm (r = 0.81, P < 0.01), a physical parameter indicative of greater SOM aromaticity; and 3) the relatively intensity of aryl C (r = 0.92, P < 0.01) and O-aryl C (r = 0.93, P < 0.01) in whole soil, both structural parameters indicative of aromatic C. Consequently, the results suggest that in-field variations in 2,4-D Koc values are induced by variations in SOM aromaticity. Koc values are among the most sensitive parameters in herbicide fate models used in regulatory and environmental assessments. Currently, these herbicide fate models do not consider associations between SOM characteristics and Koc and hence revising model equations to include these associations may improve estimates of herbicide persistence, bioavailability and transport at the field-scale.