Indirect Photolysis Promoted by Natural and Engineered Wetland Water Constituents:  Processes Leading to Alachlor Degradation

Wetland surface waters that received drainage from agricultural fields were probed for constituents that would promote the photodegradation of agriculture herbicides. Alachlor proved to be a good chemical probe for examining indirect photolysis due to its lack of reactivity by either direct photolysis or dark reaction pathways and its ubiquity as an agricultural herbicide. Water samples were taken from natural (Old Woman Creek) and engineered wetlands in Ohio that receive copious amounts of agricultural runoff. Possible photosensitizers including dissolved organic matter (DOM), iron, and nitrate were measured in the samples. In alkaline waters (pH >7.8), the photochemical degradation of alachlor became important only in the presence of high nitrate levels (≈1 mM). In pH-adjusted (∼4) samples, the observed degradation rate coefficient increased 3−18 times of that measured at the natural pH. Methanol quenching experiments and kinetics modeling suggest that hydroxyl radical is the principal reactant. The promotion of the reaction at the lower pH was apparently related to the activation of the photochemical pathways associated with the DOM and possibly iron−DOM complexes. The rate coefficients measured for the photodegradation of alachlor in reconstituted DOM isolates (cation-exchanged material with very low iron levels) were similar in magnitude to those measured in natural waters containing low amounts of nitrate and high amounts of DOM. Moreover, these reactions also exhibited a pH dependency. Thus, these results suggest that DOM plays a role in promoting an indirect photolytic mechanism that is highly pH dependent.