The hydrophobic chlorocarbon mirex readily binds to aqueous humic acids (HAs). In HA solutions irradiated at sunlight wavelengths (λ g 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.
A kinetic model was developed describing the effects of hydrophobic partitioning to humics on second-order humic-mediated photoreactions in aqueous solution. Model development and evaluation were in terms of the humic-mediated dechlorination of the hydrophobic chlorocarbon, mirex. Mirex dechlorination in irradiated (λ g 290 nm) Aldrich humic acid (HA) solution was examined as a function of humic acid and scavenger concentration. Kinetic models in which HA solution is described as a homogeneous or single-phase solution were not able to describe the effects of HA and scavenger concentrations on mirex dechlorination rates. However, these effects were successfully described by including partitioning in the models to characterize the bound phase and dissolved phase mirex reactions separately. The resulting model uses homogeneous phase kinetics to describe reaction in the dissolved phase. Bound phase reaction is described as occurring within individual HA molecules with the distribution of scavengers within HA molecules following a Poisson distribution. Used to assess the relative reactivities of the bound and dissolved phases, the model indicated that the reaction of mirex in HA solution is confined to the humic phase. The general predictions and utility of the model are evaluated both in terms of experimental data and pollutant photodegradation.
The muscular function similarity of All-on-Four and dentate patients shows that this treatment concept may be considered as a good option for oral rehabilitation in edentulous patients.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.