DOM-Flocculation: A suitable approach for separating free and DOM-bound herbicides?

Dissolved organic matter (DOM) in soil solution is considered to interact with herbicides enhancing their mobility and promoting subsequent leaching.Batch experiments were conducted to test if free and DOM-bound herbicides can be separated by a DOM-flocculation technique with Cu as a coagulant.DOM was extracted from the H and A horizons of two soils (Terric Histosol, Cumuli-Calcaric Cambisol) and from the O horizon of a forest soil (Humic Cambisol). DOM-solutions (100 mL) were fortified with the herbicides terbuthylazine and pendimethalin (100 microg active ingredient each) and equilibrated for 14 hours. After DOM-flocculation with Cu (addition of 0.5 mM CuCl(2)) herbicide recovery was determined in the supernatant solutions and in the precipitate of Humic Cambisol-DOM, respectively.Recovery of the herbicides from pure water was 85-99% and was not influenced by the addition of Cu. At low pH (4.8-5.3) DOM-flocculation of different DOM-extracts was insufficient and varied in a range of 18 - 90%. Herbicide recovery from DOM-solutions decreased moderately for terbuthylazine (60-90%) and strongly for pendimethalin (5 - 30%). In general, the addition of Cu caused no further reduction of herbicide recovery from supernatant solutions, except for Humic Cambisol-DOM. The effects of Cu-addition were most evident for pendimethalin (strongly reduced concentration in the supernatant solutions) and were considered to be caused by a flocculation of DOM-bound moieties. Flocculation of Humic Cambisol-DOM increased from 18 - 24% at pH 5 to > 95% at pH 8. However, at this pH the formation of Cu(OH)(2) as a sorbing subcomponent of the flocculated matter lead to an overestimation of DOM-bound pendimethalin. Calculating this side effect 6% of pendimethalin added was DOM-bound. Only traces of terbuthylazine (< 1%) were found in the solid matter of flocculated Humic Cambisol-DOM.To sum up, the new approach to separate freely dissolved herbicides from DOM-bound moieties not fully corresponded to our expectations. DOM-flocculation was found to depend strongly on pH-environment influencing not only DOM-herbicide interactions but also the clear separation of DOM-bound herbicides from herbicides in solutions.