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.     

Enhanced removal of tetracycline via advanced oxidation of sodium persulfate and biochar adsorption

Advanced oxidation of antibiotic tetracycline (TC) is becoming an accessible and efficient technology. The removal of TC from the complex wastewater needs to be lucubrated. In this study, a TC removal system involving degradation and adsorption was established. TC degradation was accomplished by enhanced advanced oxidation via the addition of sodium persulfate (SP) and biochar into simulated wastewater containing Mn²⁺ and TC wastewater. The adsorption of TC and its derivatives was removed by biochar. The results indicate that the optimized reaction parameters were 3.0 g/L of biochar prepared at 600 °C (B600) and 400 mg/L of SP under acidic condition, and the removal percentage of TC was 87.48%, including 74.23% of degradation and 13.28% of adsorption; the anions Cl^?, NO₃^?, and H₂PO₄^? had negligible effects on the removal of TC in this Mn²⁺/B600/SP system. The system also functioned well with an aqueous solution with a high chemical oxygen demand (COD) concentration. Electron paramagnetic resonance (EPR) analysis indicated that ·OH and SO₄^? free radicals were present in the Mn²⁺/B600/SP system. Based on the testing and analysis results, a removal mechanism and potential TC degradation pathway for this system were proposed. TC can be degraded by ·OH and SO₄^? via three degradation pathways. Mn²⁺ can be precipitated as MnO₂, and a part of the TC and its derivatives can be adsorbed on the biochar surface. The Mn²⁺/B600/SP system also performed satisfactorily for a complex aqueous solution with various cations and antibiotics.

     

Vinasse-based biochar magnetic composites: adsorptive removal of tetracycline in aqueous solutions

Environmental Science and Pollution Research - Highly efficient and cost-effective adsorbents for antibiotic removal are the key to mitigate pollution by industrial wastewaters. Pyrolyzing low-cost...     

Removal of ammonia solutions used in catalytic wet oxidation processes

Ammonia (NH(3)) is an important product used in the chemical industry, and is common place in industrial wastewater. Industrial wastewater containing ammonia is generally either toxic or has concentrations or temperatures such that direct biological treatment is unfeasible. This investigation used aqueous solutions containing more of ammonia for catalytic liquid-phase oxidation in a trickle-bed reactor (TBR) based on Cu/La/Ce composite catalysts, prepared by co-precipitation of Cu(NO(3))(2), La(NO(3))(2), and Ce(NO(3))(3) at 7:2:1 molar concentrations. The experimental results indicated that the ammonia conversion of the wet oxidation in the presence of the Cu/La/Ce composite catalysts was determined by the Cu/La/Ce catalyst. Minimal ammonia was removed from the solution by the wet oxidation in the absence of any catalyst, while approximately 91% ammonia removal was achieved by wet oxidation over the Cu/La/Ce catalyst at 230 degrees C with oxygen partial pressure of 2.0 MPa. Furthermore, the effluent streams were conducted at a liquid hourly space velocity of under 9 h(-1) in the wet catalytic processes, and a reaction pathway was found linking the oxidizing ammonia to nitric oxide, nitrogen and water. The solution contained by-products, including nitrates and nitrites. Nitrite selectivity was minimized and ammonia removal maximized when the feed ammonia solution had a pH of around 12.0.     

Degradation of 1,4-dioxane using advanced oxidation processes

Introduction  

In the nuclear industry 1,4-dioxane is used as a solvent in liquid scintillation technique for measuring low-energy beta-emitters such as ³H or C¹⁴ in aqueous media. Improper disposal of 1,4-dioxane can contaminate the ground and surface waters. Conventional wastewater treatment processes like chemical treatment, air stripping, carbon adsorption, and biological treatment are ineffective for the degradation of 1,4-dioxane.     

Treatment of landfill leachate by ozone-based advanced oxidation processes

In this study, laboratory experiments are conducted to compare the efficacy using several ozone-based advanced oxidation processes (AOPs), such as O3, O3/H2O2, and O3/UV, to treat landfill leachate. Raw leachate was initially coagulated by ferric chloride (FeCl3) at the experimental-determined optimal dosage of 900 mgl(-1), and the ozone-based AOPs were subsequently applied. Results indicate that all AOPs would result in a significant increase on the ratio of BOD5/COD from 0.06 to 0.5 at the applied ozone dosage of 1.2 gl(-1). The increase on biodegradability for ozonated leachate indicates that these AOPs would be beneficial to the subsequent biological treatment process. To better explain the alteration of high organic molecules after oxidation, ultrafiltration was used to separate the leachate by several molecular weight cutoffs (MWCO). The COD distribution for coagulated leachate is 34% for MWCO>10 kDa, 7% for MWCO between 5 and 10 kDa, 22% for MWCO between 1 and 5 kDa, and 37% for MWCO<1 kDa. Following ozonation or AOPs, the predominant distribution of COD would be obviously shifted to the MWCO less than 1000 gmol(-1) (72-85%) over the other MWCO ranges. In addition, Gel Permeation Chromatograph (GPC) analysis has showed a substantial agreement on the cleavage of larger organic compounds into smaller ones. O3/UV was found to be the most effective approach among these ozone-based AOPs to enhancing the biodegradability and eliminating the color of leachate.     

Oxidation of artificial sweetener sucralose by advanced oxidation processes: a review

Sucralose, a chlorinated carbohydrate, has shown its increased use as an artificial sweetener and persistently exists in wastewater treatment plant effluents and aquatic environment. This paper aims to review possible degradation of sucralose and related carbohydrates by biological, electrochemical, chemical, and advanced oxidation processes. Biodegradation of sucralose in waterworks did not occur significantly. Electrochemical oxidation of carbohydrates may be applied to seek degradation of sucralose. The kinetics of the oxidation of sucralose and the related carbohydrates by different oxidative species is compared. Free chlorine, ozone, and ferrate did not show any potential to degrade sucralose in water. Advanced oxidation processes, generating highly strong oxidizing agent hydroxyl radicals (^?OH), have demonstrated effectiveness in transforming sucralose in water. The mechanism of oxidation of sucralose by ^?OH is briefly discussed.     

Stability of 6:2 fluorotelomer sulfonate in advanced oxidation processes: degradation kinetics and pathway

Perfluorooctane sulfonate (PFOS), a widely used mist suppressant in hard chrome electroplating industry, has been listed in the Stockholm Convention for global ban. 6:2 Fluorotelomer sulfonate (6:2 FTS) acid and salts have been adopted as alternative products in the market, but no data about their abiotic degradation has been reported. In the present study, the degradability of 6:2 FTS potassium salt (6:2 FTS-K) was evaluated under various advanced oxidation processes, including ultraviolet (UV) irradiation, UV with hydrogen peroxide (H₂O₂), alkaline ozonation (O₃, pH = 11), peroxone (O₃/H₂O₂), and Fenton reagent oxidation (Fe²⁺/H₂O₂). UV/H₂O₂ was found to be the most effective approach, where the degradation of 6:2 FTS-K followed the pseudo-first-order kinetics. The intermediates were mainly shorter chain perfluoroalkyl carboxylic acid (C₇ to C₂), while sulfate (SO₄ ^2?) and fluoride (F^?) were found to be the final products. The high yields of SO₄ ^2? and F^? indicate that 6:2 FTS-K can be nearly completely desulfonated and defluorinated under UV/H₂O₂ condition. The degradation should firstly begin with the substitution of hydrogen atom by hydroxyl radicals, followed by desulfonation, carboxylation, and sequential “flake off” of CF₂ unit. Compared with PFOS which is inert in most advanced oxidation processes, 6:2 FTS-K is more degradable as the alternative.     

Degradation of atrazine using solar driven fenton-like advanced oxidation processes

Atrazine (2-chloro-4-ethylamino-6-isopropylamino-s-triazine) was degraded using cobalt-peroximonosulfate (Co/PMS) advanced oxidation process (AOP). Three Co concentrations (0.00, 0.25 and 0.50 mM) and five peroximonosulfate (PMS) concentrations (0, 5, 8, 16 and 32 mM) were tested. Maximum degradation reached was 88% using dark Co/PMS in 126 minutes when 0.25 mM of cobalt and 32 mM of PMS were used. Complete atrazine degradation was achieved when the samples were irradiated by the sun under the same experimental conditions described. Tests for identification of intermediate products allowed identification and quantification of deethylatrazine in both dark and radiated conditions. Kinetic data for both processes was calculated fitting a pseudo-first order reaction rate approach to the experimental data. Having kinetic parameters enabled comparison between both conditions. It was found that the kinetic approach describes data behavior appropriately (R² ≥ 0.95). Pseudo-kinetic constants determined for both Co/PMS processes, show k value of 10^?4 for Co/PMS and a k value of 10^?3 for Co/PMS/ultraviolet (UV). This means, that, with the same Co/PMS concentrations, UV light increases the reaction rate by around one order of magnitude than performing the reaction under dark conditions.     

Degradation of atrazine using solar driven fenton-like advanced oxidation processes

Atrazine (2-chloro-4-ethylamino-6-isopropylamino-s-triazine) was degraded using cobalt-peroximonosulfate (Co/PMS) advanced oxidation process (AOP). Three Co concentrations (0.00, 0.25 and 0.50 mM) and five peroximonosulfate (PMS) concentrations (0, 5, 8, 16 and 32 mM) were tested. Maximum degradation reached was 88% using dark Co/PMS in 126 minutes when 0.25 mM of cobalt and 32 mM of PMS were used. Complete atrazine degradation was achieved when the samples were irradiated by the sun under the same experimental conditions described. Tests for identification of intermediate products allowed identification and quantification of deethylatrazine in both dark and radiated conditions. Kinetic data for both processes was calculated fitting a pseudo-first order reaction rate approach to the experimental data. Having kinetic parameters enabled comparison between both conditions. It was found that the kinetic approach describes data behavior appropriately (R2 > or = 0.95). Pseudo-kinetic constants determined for both Co/PMS processes, show k value of 10(-4) for Co/PMS and a k value of 10(-3) for Co/PMS/ultraviolet (UV). This means, that, with the same Co/PMS concentrations, UV light increases the reaction rate by around one order of magnitude than performing the reaction under dark conditions.     

Mineralization of the biocide chloroxylenol by electrochemical advanced oxidation processes

Electrochemical advanced oxidation processes (EAOPs) are environmentally friendly methods based on the destruction of organic pollutants in wastewaters with in situ electrogenerated hydroxyl radical. This species is formed in anodic oxidation (AO) from water oxidation at the anode and in indirect electro-oxidation methods like electro-Fenton (EF) and photoelectro-Fenton (PEF) also from reaction between catalytic Fe2+ and H2O2 continuously produced at the O2-diffusion cathode. The PEF method involves the irradiation of the treated solution with UVA light to enhance the photolysis of organics including Fe(III) complexes. In this work, the oxidation power of such EAOPs to decontaminate synthetic wastewaters of the biocide chloroxylenol (4-chloro-3,5-dimethylphenol) at pH 3.0 is comparatively examined with an undivided electrolytic cell containing a Pt or boron-doped diamond (BDD) anode and a stainless steel or O2-diffusion cathode. The initial chlorine is released as Cl(-) ion, which remains stable in the medium using Pt or is oxidized to Cl2 on BDD. The biocide solutions can be completely decontaminated using AO with a BDD anode, as well as PEF with a Pt or BDD anode. The PEF procedure with a BDD anode is the most powerful method leading to total mineralization in about 300 min, practically independent of current density. When current density rises, the degradation rate of processes increases, but they become less efficient due to the larger enhancement of waste reactions of oxidants. Chloroxylenol is much more rapidly removed in EF and PEF than in AO. 2,6-dimethylhydroquinone, 2,6-dimethyl-p-benzoquinone and 3,5-dimethyl-2-hydroxy-p-benzoquinone are identified as aromatic by-products, and maleic, malonic, pyruvic, acetic and oxalic acids are found as generated carboxylic acids. A general pathway for chloroxylenol mineralization by all EAOPs including the above by-products is proposed.     

Developments in advanced oxidation processes for removal of microplastics from aqueous matrices

Environmental Science and Pollution Research - Continuous incorporation of microplastics (MPs) and their fragmented residues into the ecosystem has sparked significant scientific apprehensions...     

Comparison of advanced oxidation processes and identification of monuron photodegradation products in aqueous solution

The photodegradation of monuron (3-(4-chlorophenyl)-1,1-dimethylurea) in aqueous solutions under simulated solar irradiation has been conducted by different advanced oxidation processes (UV/H(2)O(2), UV/H(2)O(2)/Fe(2+), UV/H(2)O(2)/TiO(2), UV/TiO(2), dark H(2)O(2)/Fe(3+)). The degradation rates were always higher for the homogeneous catalysis in photo-Fenton reactions (UV/H(2)O(2)/Fe(2+)) compared to the heterogeneous photocatalytic systems (TiO(2)/UV and UV/H(2)O(2)/TiO(2)). Optimal concentrations of Fe(2+) and H(2)O(2) for the abatement of the herbicide in the photo-Fenton system were found to be 1 mM Fe(II) and 10 mM H(2)O(2). Several intermediary products were identified using large volume injection micro-liquid chromatography with UV detection (mu-LC-UV), mu-LC-MS and GC-MS techniques and a degradation mechanism has been proposed.     

Degradation of 4-chlorophenol by microwave irradiation enhanced advanced oxidation processes

In this work the synergistic effects of several microwave assisted advanced oxidation processes (MW/AOPs) were studied for the degradation of 4-chlorophenol (4-CP). The efficiencies of the degradation of 4-CP in dilute aqueous solution for a variety of AOPs with or without MW irradiation were compared. The results showed that the synergistic effects between MW and H2O2, UV/H2O2, TiO2 photocatalytic oxidation (PCO) resulted in a high degradation efficiency for 4-CP. The potential of MW/AOPs for treatment of industrial wastewater is discussed.     

臭氧高级氧化法降解生化尾水中喹啉

采用O_3、O_3/UV、O_3/H_2O_23种工艺对喹啉的去除、矿化效果,生化性提高及降解规律等方面进行了对比分析,结果表明,单独H_2O_2、单独UV不能有效地降解喹啉;单独O_3、O_3/H_2O_2对喹啉有一定的去除效果,但两者差别不大;反应时间为6 min时,喹啉去除率分别为78.7%和79%,反应30 min时,喹啉的矿化率为33.4%和38.2%;O_3/UV工艺明显优于前2种,在6 min内,喹啉基本降解完全,30 min矿化率超过90%;3种工艺的降解过程都很好地满足伪一级动力学规律,O_3/UV的表观反应速率常数(0.7204 min~(-1))大于单独O_3(0.2832 min~(-1))和O_3/H_2O_2(0.29 min~(-1))工艺的表观反应速率常数;采用O_3/UV工艺处理实际工业园区生化尾水,6 min内喹啉降解完全,30 min时,COD去除率为88%,TOC的去除率达到89%,UV254的去除率为96%,出水指标达到《城镇污水处理厂污染物综合排放标准》一级A标准。     

Electrochemical advanced oxidation and biological processes for wastewater treatment: a review of the combined approaches

As pollution becomes one of the biggest environmental challenges of the twenty-first century, pollution of water threatens the very existence of humanity, making immediate action a priority. The most persistent and hazardous pollutants come from industrial and agricultural activities; therefore, effective treatment of this wastewater prior to discharge into the natural environment is the solution. Advanced oxidation processes (AOPs) have caused increased interest due to their ability to degrade hazardous substances in contrast to other methods, which mainly only transfer pollution from wastewater to sludge, a membrane filter, or an adsorbent. Among a great variety of different AOPs, a group of electrochemical advanced oxidation processes (EAOPs), including electro-Fenton, is emerging as an environmental-friendly and effective treatment process for the destruction of persistent hazardous contaminants. The only concern that slows down a large-scale implementation is energy consumption and related investment and operational costs. A combination of EAOPs with biological treatment is an interesting solution. In such a synergetic way, removal efficiency is maximized, while minimizing operational costs. The goal of this review is to present cutting-edge research for treatment of three common and problematic pollutants and effluents: dyes and textile wastewater, olive processing wastewater, and pharmaceuticals and hospital wastewater. Each of these types is regarded in terms of recent scientific research on individual electrochemical, individual biological and a combined synergetic treatment.     

Removal of PCBs in contaminated soils by means of chemical reduction and advanced oxidation processes

Although the chemical reduction and advanced oxidation processes have been widely used individually, very few studies have assessed the combined reduction/oxidation approach for soil remediation. In the present study, experiments were performed in spiked sand and historically contaminated soil by using four synthetic nanoparticles (Fe⁰, Fe/Ni, Fe₃O₄, Fe_3???x Ni _x O₄). These nanoparticles were tested firstly for reductive transformation of polychlorinated biphenyls (PCBs) and then employed as catalysts to promote chemical oxidation reactions (H₂O₂ or persulfate). Obtained results indicated that bimetallic nanoparticles Fe/Ni showed the highest efficiency in reduction of PCB28 and PCB118 in spiked sand (97 and 79 %, respectively), whereas magnetite (Fe₃O₄) exhibited a high catalytic stability during the combined reduction/oxidation approach. In chemical oxidation, persulfate showed higher PCB degradation extent than hydrogen peroxide. As expected, the degradation efficiency was found to be limited in historically contaminated soil, where only Fe⁰ and Fe/Ni particles exhibited reductive capability towards PCBs (13 and 18 %). In oxidation step, the highest degradation extents were obtained in presence of Fe⁰ and Fe/Ni (18–19 %). The increase in particle and oxidant doses improved the efficiency of treatment, but overall degradation extents did not exceed 30 %, suggesting that only a small part of PCBs in soil was available for reaction with catalyst and/or oxidant. The use of organic solvent or cyclodextrin to improve the PCB availability in soil did not enhance degradation efficiency, underscoring the strong impact of soil matrix. Moreover, a better PCB degradation was observed in sand spiked with extractable organic matter separated from contaminated soil. In contrast to fractions with higher particle size (250–500 and <500 μm), no PCB degradation was observed in the finest fraction (≤250 μm) having higher organic matter content. These findings may have important practical implications to promote successively reduction and oxidation reactions in soils and understand the impact of soil properties on remediation performance.     

Comparison of various advanced oxidation processes for the degradation of phenylurea herbicides

Various types of advanced oxidation processes (AOPs), such as UV photolysis, ozonation, heterogeneous photocatalysis and their combinations were comparatively examined at the same energy input in a home-made reactor. The oxidative transformations of the phenylurea herbicides fenuron, monuron and diuron were investigated. The initial rates of transformation demonstrated that UV photolysis was highly efficient in the cases of diuron and monuron. Ozonation proved to be much more effective in the transformation of fenuron than in those of the chlorine containing monuron and diuron. In heterogeneous photocatalysis, the rate of decomposition decreased with increase of the number of chlorine atoms in the target molecule. Addition of ozone to UV-irradiated solutions and/or TiO₂-containing suspensions markedly increased the initial rates of degradation. Dehalogenation of monuron and diuron showed that each of these procedures is suitable for the simultaneous removal of chlorinated pesticides and their chlorinated intermediates. Heterogeneous photocatalysis was found to be effective in the mineralization.     

Bibliometric analysis of advanced oxidation processes (AOPs) in wastewater treatment: global and Ibero-American research trends

Environmental Science and Pollution Research - Advanced oxidation processes (AOPs) constitute a developing area of particular interest for researchers in different fields due to their broad range...     

Contribution of free radicals to chlorophenols decomposition by several advanced oxidation processes

The chemical decomposition of aqueous solutions of various chlorophenols (4-chlorophenol (4-CP), 2,4-dichlorophenol (2-DCP), 2,4,6-trichlorophenol (2,4,6-TCP) and 2,3,4,6-tetrachlorophenol (2,3,4,6-TeCP)), which are environmental priority pollutants, is studied by means of single oxidants (hydrogen peroxide, UV radiation, Fenton's reagent and ozone at pH 2 and 9), and by the Advanced Oxidation Processes (AOPs) constituted by combinations of these oxidants (UV/H2O2 UV/Fenton's reagent and O3/UV). For all these reactions the degradation rates are evaluated by determining their first-order rate constants and the half-life times. Ozone is more reactive with higher substituted CPs while OH* radicals react faster with those chlorophenols having lower number of chlorine atoms. The improvement in the decomposition levels reached by the combined processes, due to the generation of the very reactive hydroxyl radicals. in relation to the single oxidants is clearly demonstrated and evaluated by kinetic modeling.