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.     

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.     

Novel imazethapyr detoxification applying advanced oxidation processes

Different degradation methods have been applied to assess the suitability of advanced oxidation process (AOPs) to promote mineralization of imazethapyr [(RS)-5-ethyl-2-(4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl)nicotinic acid], a widely used imidazolinone class herbicide, the persistence of which has been demonstrated in surface and ground waters destined to human uses. Independent of the oxidation process assessed, the decomposition of imazethapyr always followed a pseudo-first order kinetic. The direct UV-irradiation (UV) of the herbicide as well as its oxidation with ozone (O?), and hydrogen peroxide tied to UV-irradiation (H?O?/UV) were sufficiently slow to permit the identification of intermediate products, the formation pathway of which has been proposed. Ozonation joined to UV-irradiation (O?/UV), ozonation joined to titanium dioxide photo-catalysis (TiO?/UV+O?), sole photo-catalysis (TiO?/UV), and photo-catalysis reinforced with hydrogen peroxide-oxidation (TiO?/UV+H?O?) were characterized by a faster degradation and rapid formation of a lot of small molecules, which were quickly degraded to complete mineralization. The most effective oxidation methods were those using titanium dioxide photo-catalysis enhanced either by ozonation or hydrogen peroxide. Most of all, these last processes were useful to avoid the development of dangerous by-products.     

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.     

一种新兴的高级氧化技术--超临界水氧化法

超临界水氧化法在处理废水方面具有独特的优势.从超临界水的性质,超临界水氧化法原理、工艺、应用和优越性等方面阐述了超临界水氧化法作为一种新兴的高级氧化技术具有广阔的应用前景,并且提出了解决现存问题的建议.     

Evaluation and comparison of advanced oxidation processes for the degradation of 2,4-dichlorophenoxyacetic acid (2,4-D): a review

Environmental Science and Pollution Research - Organochlorine pesticides have generated public concern worldwide because of their toxicity to human health and the environment, even at low...     

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.     

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.     

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.     

A comparative study of the removal of 3-indolebutyric acid using advanced oxidation processes

In this study, advanced oxidation technologies, namely Fenton Process (FP), Fenton-Like Process (FLP), ozonation (O3) and O3/H2O2 processes, were applied to synthetic wastewater containing 3-indolebutyric acid (IBA). The effectiveness of each process was investigated at different pH values, Fe(+2), Fe(+3), O3 and H2O2 concentrations with respect to the removal efficiencies for chemical oxygen demand (COD) and total organic carbon (TOC). The best removal efficiencies were seen at pH 3 and 2 mM Fe concentration in both FP and FLP, in which the optimum H2O2 concentrations were 6 mM for FP and 10 mM for FLP. Optimum process conditions were pH 12 for the O3 process, pH 9 for the O3/H2O2 process and 1:1 O3/H2O2 molar ratio. The highest COD removal efficiency was 86 percent, obtained in the O3/H2O2 process and the highest TOC removal efficiency was obtained at 77 percent in the FP.     

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.     

Application of biochar in advanced oxidation processes: supportive,adsorptive, and catalytic role

Environmental Science and Pollution Research - The advanced oxidation processes (AOPs), especially sulphate radical (SO4•−)–based AOPs (SR-AOPs), have been considered more...     

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。     

An investigation into reservoir NOM reduction by UV photolysis and advanced oxidation processes

A comparison of four treatment technologies for reduction of natural organic matter (NOM) in a reservoir water was made. The work presented here is a laboratory based evaluation of NOM treatment by UV-C photolysis, UV/H(2)O(2), Fenton's reagent (FR) and photo-Fenton's reagent (PFR). The work investigated ways of reducing the organic load on water treatment works (WTWs) with a view to treating 'in-reservoir' or 'in-pipe' before the water reaches the WTW. The efficiency of each process in terms of NOM removal was determined by measuring UV absorbance at 254 nm (UV(254)) and dissolved organic carbon (DOC). In terms of DOC reduction PFR was the most effective (88% removal after 1 min) however there were interferences when measuring UV(254) which was reduced to a lesser extent (31% after 1 min). In the literature, pH 3 is reported to be the optimal pH for oxidation with FR but here the reduction of UV(254) and DOC was found to be insensitive to pH in the range 3-7. The treatment that was identified as the most effective in terms of NOM reduction and cost effectiveness was PFR.     

SARS-CoV-2 pharmaceutical drugs: a critical review on the environmental impacts,chemical characteristics,and behavior of advanced oxidation processes in water

This review summarizes research data on the pharmaceutical drugs used to treat the novel SARS-CoV-2 virus, their characteristics, environmental impacts, and the advanced oxidation processes (AOP) applied to remove them. A literature survey was conducted using the electronic databases Science Direct, Scopus, Taylor & Francis, Google Scholar, PubMed, and Springer. This complete research includes and discusses relevant studies that involve the introduction, pharmaceutical drugs used in the SARS-CoV-2 pandemic: chemical characteristics and environmental impact, advanced oxidation process (AOP), future trends and discussion, and conclusions. The results show a full approach in the versatility of AOPs as a promising solution to minimize the environmental impact associated with these compounds by the fact that they offer different ways for hydroxyl radical production. Moreover, this article focuses on introducing the fundamentals of each AOP, the main parameters involved, and the concomitance with other sources and modifications over the years. Photocatalysis, sonochemical technologies, electro-oxidation, photolysis, Fenton reaction, ozone, and sulfate radical AOP have been used to mineralize SARS-CoV-2 pharmaceutical compounds, and the efficiencies are greater than 65%. According to the results, photocatalysis is the main technology currently applied to remove these pharmaceuticals. This process has garnered attention because solar energy can be directly utilized; however, low photocatalytic efficiencies and high costs in large-scale practical applications limit its use. Furthermore, pharmaceuticals in the environment are diverse and complex. Finally, the review also provides ideas for further research needs and major concerns.

Graphical abstract

     

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.     

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...