摘要:
The hydrophobic chlorocarbon mirex readily binds to aqueous humic acids (HAs). In HA solutions irradiated at sunlight wavelengths (lambda greater than or equal to 290 nm), mirex molecules bound to HAs are transformed to photomirex by dechlorination. The mechanism of this intrahumic dechlorination was investigated both in HA solutions and in model systems simulating select photochemical capabilities of HAs. In HA solution, the reaction was unaffected by methanol and pentanol; was accelerated by hydroxide; and was inhibited by oxygen, 2-chloroethanol, nitrate, and hydrogen ion, all four of which can scavenge hydrated electron. Additional experiments probing for involvement of hydrated electron were consistent with it as the reactant. In irradiated N,N-dimethylaniline solution, a model system for generating hydrated electron, mirex was dechlorinated to form photomirex, the same product that is found in HA solution. Relative rate experiments in HA solution, while inconsistent with the reaction with hydrated electron in homogeneous solution, were consistent with reaction with a purely intrahumic hydrated electron. However, other humic-generated reductants cannot be eliminated as possible reactants. The potential confounding influence of hydrophobic partitioning to HAs on investigations using molecular probes is evaluated in terms of current data and previous reports.