Reaction Mechanism and Kinetic Modeling of DEET Degradation by Flow-Through Anodic Fenton Treatment (FAFT)

Cornell University, Итак, New York, United States
Environmental Science and Technology (Impact Factor: 5.33). 08/2006; 40(14):4488-94. DOI: 10.1021/es060515b
Source: PubMed


The previously developed batch anodic Fenton treatment (AFT) technology has been successfully applied to degrade various pesticides in aqueous solution. The goal of this work is the development of a flow-through AFT system (FAFT) which is critical to bringing this technology into practical general use in the field. For this purpose, the degradation of DEET (N,N-diethyl-3-methylbenzamide), an insect repellent, and nine model amides was studied. Oxidation products of these compounds in FAFT were identified by GC/MS, and the results revealed that various -OH additions (most likely on the aromatic ring), quinone/keto product formation, and dimerization/bimolecular disproportionation are the major reaction pathways. This proposed overall reaction mechanism was then combined with the basic Fenton's mechanism to model the kinetics of various active species in FAFT including DEET, Fe2+, H2O2, and total iron under different reaction conditions. In addition, both initial and steady-state hydroxyl radical concentrations were measured in FAFT using benzoic acid as a chemical probe; the measured *OH concentrations were best-fitted exponentially. On the basis of the obtained [*OH] trend and the mass balance of the FAFT system, a simple FAFT model was developed to fit all of the degradation data of DEET and the model amides.

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    ABSTRACT: A flow-through anodic Fenton treatment (FAFT) system based on the batch AFT technology was previously developed to degrade pesticides in aqueous solution. As one of a series of benchtop and pilot-scale studies in process optimization, the goal of the reported work is to evaluate the performance of the FAFT system under various operating conditions, which is critical to bringing this technology into practical general use in the field. For this purpose, the removal efficiency of the parent pesticide and the concentration of the hydroxyl radical in FAFT were calculated on the basis of a previously developed FAFT kinetic model and used for the evaluation. N,N-Diethyl-3-methylbenzamide (DEET), an insect repellent, was used as a chemical probe. Experimental data showed that the key to a high treatment efficiency is to operate the FAFT system to achieve a maximum *OH production with a minimum input of energy and chemicals. For the anodic half-cell, the system should be operated under flow-through conditions with a self-developed optimum pH of 3.0, a relatively high flow rate, and the initial effluent recycled within 6-10 min to the FAFT system for further treatment; for the cathodic half-cell, it should have a fixed volume and be entirely replaced by another batch of cathodic solution only when the pH reaches a very high value. The delivery rate of the ferrous iron should be maintained at an electrolytic current between 0.01 and 0.02 A; the ratio of H2O2/Fe2+ should be between 5:1 and 10:1. NaCl was found to be the best electrolyte, with concentrations of 0.01-0.02 and 0.08 M in the anodic and cathodic half-cells, respectively. The FAFT system was successfully applied to degrade various model amide compounds and DEET formulations, which suggests the likelihood of extending this approach to other pesticide-containing wastewaters.
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