Mehmet A. Oturan

Electro-Fenton Process and Related Electrochemical Technologies Based on Fenton’s Reaction Chemistry

2.2. Fenton’s Chemistry 6575 2.2.1. Origins 6575 2.2.2. Fenton Process 6575 2.3. Photo-Fenton Process 6577 3. H2O2 Electrogeneration for Water Treatment 6577 3.1. Fundamentals 6578 3.2. Cathode Materials 6579 3.3. Divided Cells 6580 3.4. Undivided Cells 6583 4. Electro-Fenton (EF) Process 6585 4.1. Origins 6585 4.2. Fundamentals of EF for Water Remediation 6586 4.2.1. Cell Configuration 6586 4.2.2. Cathodic Fe2+ Regeneration 6586 4.2.3. Anodic Generation of Heterogeneous Hydroxyl Radical 6587

Electrochemical advanced oxidation processes: today and tomorrow. A review.

In recent years, new advanced oxidation processes based on the electrochemical technology, the so-called electrochemical advanced oxidation processes (EAOPs), have been developed for the prevention and remediation of environmental pollution, especially focusing on water streams. These methods are based on the electrochemical generation of a very powerful oxidizing agent, such as the hydroxyl radical (•OH) in solution, which is then able to destroy organics up to their mineralization. EAOPs include heterogeneous processes like anodic oxidation and photoelectrocatalysis methods, in which •OH are generated at the anode surface either electrochemically or photochemically, and homogeneous processes like electro-Fenton, photoelectro-Fenton, and sonoelectrolysis, in which •OH are produced in the bulk solution. This paper presents a general overview of the application of EAOPs on the removal of aqueous organic pollutants, first reviewing the most recent works and then looking to the future. A global perspective on the fundamentals and experimental setups is offered, and laboratory-scale and pilot-scale experiments are examined and discussed.

Advanced Oxidation Processes in Water/Wastewater Treatment: Principles and Applications. A Review

Advanced oxidation processes (AOPs) constitute important, promising, efficient, and environmental-friendly methods developed to principally remove persistent organic pollutants (POPs) from waters and wastewaters. Generally, AOPs are based on the in situ generation of a powerful oxidizing agent, such as hydroxyl radicals (•OH), obtained at a sufficient concentration to effectively decontaminate waters. This critical review presents a precise and overall description of the recent literature (period 1990–2012) concerning the main types of AOPs, based on chemical, photochemical, sonochemical, and electrochemical reactions. The principles, performances, advantages, drawbacks, and applications of these AOPs to the degradation and destruction of POPs in aquatic media and to the treatment of waters and waste waters have been reported and compared.

AN ECOLOGICALLY EFFECTIVE WATER TREATMENT TECHNIQUE USING ELECTROCHEMICALLY GENERATED HYDROXYL RADICALS FOR IN SITU DESTRUCTION OF ORGANIC POLLUTANTS: APPLICATION TO HERBICIDE 2,4-D

The electrochemical production of Fentons reagent by simultaneous reduction of dioxygen and ferric ions on a carbon felt electrode, permits a controlled, in situ generation of hydroxyl (OH·) radicals. The possibility of using electrochemically produced OH⋅ radicals for solving environmental problems is investigated. Continuous and controlled production of hydroxyl radicals was achieved by electrochemical reduction of O2 in the presence of a catalytic amount of ferric or ferrous ion. These radicals are used for remediation of water containing toxic-persistent-bioaccumulative organic pollutants through their transformation into biodegradable compounds or through their mineralization into H2O and CO2. A widely used herbicide, 2,4-dichlorophenoxyacetic acid (2,4-D), was selected as a model for a toxic organic pollutant. High pressure liquid chromatography (HPLC) was used to quantify the distribution of the hydroxylated products obtained. Rate constants for the hydroxylation reactions of 2,4-D, 2,4-dichlorophenol (2,4-DCP), 2,4-dichlororesorcinol (2,4-DCR) and 4,6-dichlororesorcinol (4,6-DCR) were determined. The mineralization of 2,4-D and its derivatives was followed by total organic carbon (TOC) measurements. More than 95% of 2,4-D and the intermediates generated during the electrolysis can be mineralized.

Production of hydroxyl radicals by electrochemically assisted Fenton's reagent : Application to the mineralization of an organic micropollutant, pentachlorophenol

Abstract Hydroxyl radicals are very powerful oxidizing agents. They are involved in hydroxylation reactions, in biological and atmospheric phenomena. A recent application of these radicals is their use in decontamination of water polluted by toxic organic substances like pesticides. Chemically, these radicals are produced by the use of a mixture of (H 2 O 2 +Fe 2+ ), the so called Fentons reagent. In this work Fentons reagent is generated by electrochemistry in a catalytic way. The reaction of the hydroxyl radicals with pentachlorophenol (PCP) was studied. These radicals generated in situ in aqueous solution react with PCP and thus lead to its degradation. The evolution of the composition of the solution was followed by chromatographic analysis, COD analysis and the measurement of the total organic carbon (TOC) of the studied aqueous solution. Tetrachloro- o -benzoquinone and tetrachloro- p -benzoquinone (TCBQ) are the only aromatic intermediates identified. They result from the oxidation of the corresponding tetrachlorohydroquinones (TCHQ). Just like PCP, the TCBQs are degraded and disappear in their turn. The mineralization of the initial toxic substrate is confirmed on the one hand, by the regular decrease in quantity of the total organic carbon of the solution (TOC analysis) and on the other hand, by the quantitative release of chloride ions according to the electrical charge passed during electrolysis. The degradation of PCP appears relatively slow compared to that of the other organic pollutants studied by the electro-Fenton process and also to the degradation of other less substituted chlorophenols. The kinetic rate of the appearance of chloride ions is slower than that in the degradation of PCP. This phenomenon highlights the formation of chlorated aliphatic intermediates.

Electrochemical Treatment of the Antibiotic Sulfachloropyridazine: Kinetics, Reaction Pathways, and Toxicity Evolution

The electro-Fenton treatment of sulfachloropyridazine (SCP), a model for sulfonamide antibiotics that are widespread in waters, was performed using cells with a carbon-felt cathode and Pt or boron-doped diamond (BDD) anode, aiming to present an integral assessment of the kinetics, electrodegradation byproducts, and toxicity evolution. H(2)O(2) electrogeneration in the presence of Fe(2+) yielded (•)OH in the solution bulk, which acted concomitantly with (•)OH adsorbed at the anode (BDD((•)OH)) to promote the oxidative degradation of SCP (k(abs,SCP) = (1.58 ± 0.02) × 10(9) M(-1) s(-1)) and its byproducts. A detailed scheme for the complete mineralization was elucidated. On the basis of the action of (•)OH onto four different SCP sites, the pathways leading to total decontamination includes fifteen cyclic byproducts identified by HPLC and GC-MS, five aliphatic carboxylic acids, and a mixture of Cl(-), SO(4)(2-), NH(4)(+), and NO(3)(-) that accounted for 90-100% of initial Cl, S, and N. The time course of byproducts was satisfactorily correlated with the toxicity profiles determined from inhibition of Vibrio fischeri luminescence. 3-Amino-6-chloropyridazine and p-benzoquinone were responsible for the increased toxicity during the first stages. Independent electrolyses revealed that their toxicity trends were close to those of SCP. The formation of the carboxylic acids involved a sharp toxicity decrease, thus ensuring overall detoxification.

Removal of Acid Orange 7 from water by electrochemically generated Fenton's reagent.

The removal of azo dye Acid Orange 7 (AO7) from water was investigated by the electro-Fenton technology using electrogenerated hydroxyl radicals (OH) which leads to the oxidative degradation of AO7 up to its complete mineralization. H(2)O(2) and Fe (II) ions are electrogenerated in a catalytic way at the carbon-felt cathode. AO7 decay kinetics and evolution of its oxidation intermediates were monitored by high-performance liquid chromatography. The absolute rate constant of AO7 hydroxylation reaction has been determined as (1.20+/-0.17)x10(10)M(-1)s(-1). The optimal current value for the degradation of AO7 was found as 300 mA. AO7 degradation rate was found to decrease by increase in Fe(3+) concentration beyond 0.1mM. Mineralization of AO7 aqueous solutions was followed by total organic carbon (TOC) measurements and found to be 92%. Based on TOC evolution and identification of aromatic intermediates, short-chain carboxylic acids and inorganic ions released during treatment, a plausible mineralization pathway was proposed.

Degradation of Acid Orange 7 by electrochemically generated •OH radicals in acidic aqueous medium using a boron-doped diamond or platinum anode: A mechanistic study

A comparative study of the degradation of Acid Orange 7 (AO 7) aqueous solutions in acidic medium of pH 3.0 by electro-Fenton process using Pt or boron-doped diamond (BDD) anode was reported. The oxidative degradation of AO 7 by electrochemically generated hydroxyl radicals follows a pseudo-first order kinetic with a similar rate constant with BDD or Pt anode. The absolute rate constant of the AO 7 hydroxylation reaction was determined as (1.10+/-0.04)x10(10)M(-1)s(-1) by using the competition kinetic method. The comparative study of TOC measurements during electro-Fenton treatment showed a higher mineralization rate with BDD than Pt anode at the first hours of electrolysis because of the higher oxidizing power of this anode. The electro-Fenton degradation of AO 7 was followed by monitoring the formation and evolution of aromatic intermediates which are oxidized to aliphatic carboxylic acids before mineralization (transformation to CO(2) and inorganic ions, i.e. sulphate, nitrate and ammonium). The follow-up of the solution toxicity evolution shows the formation of intermediates more toxic than AO 7 and the connection between toxicity and aromaticity. A mineralization reaction pathway of AO 7 by electro-Fenton degradation involving all the intermediates identified was proposed.

Electrochemistry: as cause and cure in water pollution—an overview

This article reviews both the pollution by the electrochemical industry and the use of electrochemistry to clean water. Main pollutants include Pd, Cd, Ni, Hg and other metals and cyanide as well as organic pollutants. The cause for water pollution by electrochemistry is due to the effluents from different electrochemical industries such as mercury from chlor-alkali industry; lead, cadmium and mercury from battery industry; heavy metals and organic contaminants from electroplating wastes; contaminants from corrosion processes; and persistent organic pollutants from the synthesis and use of pesticides, dyes and pharmaceuticals. Most pollutants can be successfully eliminated or converted to non-toxic materials by methods based on the electrochemical principles. Electrochemical depolluting methods are mainly electrodialysis, electrocoagulation, electroflotation, anodic processes, cathodic processes and electrochemical advanced oxidation processes.

Electrochemical abatement of the antibiotic sulfamethoxazole from water

The electrochemical abatement of the antibiotic sulfamethoxazole (SMX) from aqueous solutions at pH 3.0 has been carried out by anodic oxidation and electro-Fenton (EF) processes with H(2)O(2) electrogeneration. The electrolyses have been performed using a small, undivided cell equipped with a Pt or thin film boron-doped diamond (BDD) anode and a carbon-felt cathode. The higher performance of the EF process with 0.2mM Fe(2+) in a BDD/carbon felt cell is demonstrated. This is due to the higher production of ()OH radicals, as well as to the simultaneous degradation at the anode surface and in the bulk solution. At low current, the oxidation at the anode was predominant; at high current, SMX was pre-eminently degraded in the bulk. SMX was quickly destroyed under all the conditions tested, following pseudo first-order kinetics; however, the almost total removal of the total organic carbon was only achieved in the BDD/carbon felt cell. The reaction by-products were quantified by chromatographic techniques and thus, the reaction pathway for the mineralization of SMX by EF has been elucidated. Hydroxylation of SMX on the sulfanilic ring is suggested as the first step, followed by the formation of p-benzoquinone and 3-amino-5-methylisoxazole. Their oxidative cleavage led to the formation of five carboxylic acids that were finally mineralized to CO(2); the release of NH(4)(+), NO(3)(-), and SO(4)(2-) accounted for almost 100% of the initial nitrogen and sulfur content. The absolute rate constants for the oxidative degradation of SMX and the detected aromatic by-products have also been determined.