Coupled electrocoagulation–electro-Fenton for efficient domestic wastewater treatment

This article reports the first use of coupled electrocoagulation and electro-Fenton (EF-EC) to clean domestic wastewater. Domestic wastewater contains high amounts of organic, inorganic and microbial pollutants that cannot be usually treated in a single step. Here, to produce an effluent suitable for discharge in a single process step, a hybrid process combining electrocoagulation and electro-Fenton was simultaneously used to decrease chemical oxygen demand (COD), turbidity and total suspended solids (TSS) from domestic wastewater. The electrocoagulation–electro-Fenton process was firstly tested for the production of H₂O₂ using Ti–IrO₂ and vitreous carbon- or graphite electrodes arranged at the anode and the cathode, respectively. The concentration of H₂O₂ recorded at 1.5 A of current intensity during 60 min of electrolysis using vitreous carbon- and graphite electrodes at the cathode was 4.18 and 1.62 mg L^?1, respectively. By comparison, when the iron electrode was used at the anode, 2.05 and 1.06 mg L^?1 of H₂O₂ were recorded using vitreous carbon and graphite, respectively. The H₂O₂ concentration decrease was attributed to hydroxyl radical formation generated by the Fenton reaction. Electro-Fenton using iron electrode at the anode and vitreous carbon at the cathode with a current density imposed of 0.34 A dm^?2 ensures the removal efficiency of 50.1 % COD_T, 70.8 % TSS and 90.4 % turbidity. The electrocoagulation–electro-Fenton technique is therefore a promising secondary treatment to simultaneously remove organic, inorganic and microbial pollutants from domestic, municipal and industrial wastewaters.     

Free radical-assisted electrocoagulation processes for wastewater treatment

The combination of electrocoagulation with another process is a promising approach to enhance the removal efficiency of water pollutants. For instance, free radical-assisted electrocoagulation is a new combination showing higher performance. There are different combinations depending on the free radical source. This article reviews free radical-assisted electrocoagulation processes. We discuss electrocoagulation mechanisms; ozone-assisted electrocoagulation processes; advanced oxidation-assisted electrocoagulation processes; and ultrasound-assisted electrocoagulation. We present kinetic models used in free radical-assisted electrocoagulation, scale-up of free radical-assisted electrocoagulation and cost estimation. The major points are: most of the available studies have been done at laboratory scale with synthetic wastewater, and lack holistic and systematic approaches to consider the process complexity. The performance of the combined process is improved, and the removal efficiency is increased especially with ozone-assisted electrocoagulation, which gives a removal efficiency of more than 95%. The use of ultrasound energy with electrocoagulation is advantageous in reducing the problem of electrode passivation.     

Unprecedented total mineralization of atrazine and cyanuric acid by anodic oxidation and electro-Fenton with a boron-doped diamond anode

This article reports the complete mineralization of atrazine. Atrazine has been the most widely used s-triazine herbicide. Atrazine occurs in natural waters and presents a potential danger for public health because atrazine is considered as an endocrine disruptor. The use of chemical, photochemical and photocatalytic advanced oxidation processes (AOPs) to decontaminate waters containing atrazine only allowed its conversion into the cyanuric acid as ultimate end products, since it cannot be completely degraded by hydroxyl radicals (^•OH) produced by these techniques. The same behavior was previously reported for anodic oxidation and electro-Fenton with Pt anode, although better performances were found using boron-doped diamond (BDD) anode but without explaining the role of generated ^•OH. Here, the oxidative action of these radicals in such electrochemical AOPs has been clarified by studying the mineralization process and decay kinetics of atrazine and cyanuric acid in separated solutions by anodic oxidation with BDD and electro-Fenton with Pt or BDD anode using an undivided cell with a carbon-felt cathode under galvanostatic conditions. Results showed that electro-Fenton with BDD anode was the more powerful treatment to degrade both compounds. Almost total mineralization, 97% total organic carbon (COT) removal, of atrazine was only feasible by this method with a faster removal of its oxidation intermediates by ^•OH formed at the BDD surface than that formed in the bulk from Fenton reaction, although the latter process caused a more rapid decay of the herbicide. Cyanuric acid was much slowly mineralized mainly with ^•OH produced at the BDD surface, and it was not degraded by electro-Fenton with Pt anode. These results highlight that electrochemical advanced oxidation processes (EAOPs) using a BDD anode are more powerful than the classical electro-Fenton process with Pt or PbO₂ anodes.     

Treatment of organic pollutants by homogeneous and heterogeneous Fenton reaction processes

Nowadays, the water ecosystem is being polluted due to the rapid industrialization and massive use of antibiotics, fertilizers, cosmetics, paints, and other chemicals. Chemical oxidation is one of the most applied processes to degrade contaminants in water. However, chemicals are often unable to completely mineralize the pollutants. Enhanced pollutant degradation can be achieved by Fenton reaction and related processes. As a consequence, Fenton reactions have received great attention in the treatment of domestic and industrial wastewater effluents. Currently, homogeneous and heterogeneous Fenton processes are being investigated intensively and optimized for applications, either alone or in a combination of other processes. This review presents fundamental chemistry involved in various kinds of homogeneous Fenton reactions, which include classical Fenton, electro-Fenton, photo-Fenton, electro-Fenton, sono-electro-Fenton, and solar photoelectron-Fenton. In the homogeneous Fenton reaction process, the molar ratio of iron(II) and hydrogen peroxide, and the pH usually determine the effectiveness of removing target pollutants and subsequently their mineralization, monitored by a decrease in levels of total organic carbon or chemical oxygen demand. We present catalysts used in heterogeneous Fenton or Fenton-like reactions, such as H₂O₂–Fe³⁺(solid)/nano-zero-valent iron/immobilized iron and electro-Fenton-pyrite. Surface properties of heterogeneous catalysts generally control the efficiency to degrade pollutants. Examples of Fenton reactions are demonstrated to degrade and mineralize a wide range of water pollutants in real industrial wastewaters, such as dyes and phenols. Removal of various antibiotics by homogeneous and heterogeneous Fenton reactions is exemplified.     

Removal of boron by electrocoagulation

Boron compounds are used in many manufacturing products and may be introduced into the environment in the form of hazardous materials. Here the feasibility of removal of boron from aqueous solutions by electrocoagulation was investigated. The process was examined under various factors in order to assess optimal operating conditions. The results showed that electrocoagulation for boron removal depends on current density, initial concentration and time. Under a current density of 30 mA/cm² the percentage of boron removal from aqueous solutions is in the range of 92–96%.     

Electrocoagulation process for the treatment of metal-plating wastewater: Kinetic modeling and energy consumption

The wastewater from industrial area was treated by EC via Fe and Al electrodes. Cu, Ni, Cr and Zn were highly removed at the first minutes, simultaneously. Pseudo-2nd-order was found to be more suitable for kinetics. Adsorption capacities based on kinetic modeling were observed as Cr>Cu>Ni>Zn. The chemical cost in the case of pH adjustment after EC was less as 3.83 $/m³. It is known that wastewater produced by the metal-plating industry contains several heavy metals, which are acidic in nature and therefore toxic for the environment and for living creatures. In particular, heavy metals enter the food chain and accumulate in vital organs and cause serious illness. The precipitation of these metals is mostly achieved by pH adjustment, but as an alternative to this method, the electrocoagulation process has investigated in this study using iron and aluminum electrodes. The effects of the pH adjustment on removal before and after the electrocoagulation process were investigated, and cost analyses were also compared. It was observed that a high proportion of removal was obtained during the first minutes of the electrocoagulation process; thus, the current density did not have a great effect. In addition, the pH adjustment after the electrocoagulation process using iron electrodes, which are 10% more effective than aluminum electrodes, was found to be much more efficient than before the electrocoagulation process. In the process where kinetic modeling was applied, it was observed that the heavy metal removal mechanism was not solely due to the collapse of heavy metals at high pH values, and with this modeling, it was seen that this mechanism involved adsorption by iron and aluminum hydroxides formed during the electrocoagulation process. When comparing the ability of heavy metals to be adsorbed, the sequence was observed to be Cr>Cu>Ni>Zn, respectively.     

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.     

Fast and complete removal of the 5-fluorouracil drug from water by electro-Fenton oxidation

Cytostatic drugs are a troublesome class of emerging pollutants in water owing to their potential effects on DNA. Here we studied the removal of 5-fluorouracil from water using the electro-Fenton process. Galvanostatic electrolyses were performed with an undivided laboratory-scale cell equipped with a boron-doped diamond anode and a carbon felt cathode. Results show that the fastest degradation and almost complete mineralization was obtained at a Fe²⁺ catalyst concentration of 0.2 mM. The absolute rate constant for oxidation of 5-fluorouracil by hydroxyl radicals was 1.52 × 10⁹ M^?1 s^?1. Oxalic and acetic acids were initially formed as main short-chain aliphatic by-products, then were completely degraded. After 6 h the final solution mainly contained inorganic ions (NH₄ ⁺, NO₃ ^? and F^?) and less than 10% of residual organic carbon. Hence, electro-Fenton constitutes an interesting alternative to degrade biorefractory drugs.     

Removal of textile dyes from water by the electro-Fenton process

An environmentally friendly electrochemical treatment, electro-Fenton process, was applied to the depollution of a synthetic dismissal composed of three dyes, yellow drimaren, congo red and methylene blue, frequently used in textile and dyehouses. Here, we show that those dyes and their mixture are quickly degraded under current controlled electrolysis conditions, leading to an almost complete mineralization. The results show the efficiency of electro-Fenton process to quickly degrade aqueous effluents polluted by synthetic organic dyes.     

Performance and mechanistic study on electrocoagulation process for municipal wastewater treatment based on horizontal bipolar electrodes

• EC modified with BPEs enhances pollutant removal and reduce energy consumption. • Increasing BPE number cannot increase flocculants yield exponentially. • Simulations help to predict the distribution of electrochemical reactions on BPEs. The design of electrodes is crucial to electrocoagulation process (EC), specifically, with respect to pollutant removal and energy consumption. During EC, the mechanisms for interaction between different electrode arrangement and electrode reactions remain unclear. This work presents an integrated EC process based on horizontal bipolar electrodes (BPEs). In the electrochemical cell, the graphite plates are used as driving cathode while either Fe or Al plates serves as driving anode and BPEs. The BPEs are placed horizontally between the driving electrodes. For municipal wastewater treatment, the pollutant removal efficiency and energy consumption in different configurations of two-dimension electrocoagulation (2D-EC) system with horizontal BPEs were investigated. The removal efficiency of turbidity, total phosphorus and total organic carbon increased significantly with the number of BPEs. Noted that the energy consumption for TP removal decreased by 75.2% with Fe driving anode and 81.5% with Al driving anode than those of 2D-EC, respectively. In addition, the physical field simulation suggested the distributions of potential and current in electrolyte and that of induced charge density on BPE surface. This work provides a visual theoretical guidance to predict the distribution of reactions on BPEs for enhanced pollutant removal and energy saving based on electrocoagulation process for municipal wastewater treatment.     

土壤还原过程对氯代有机污染物还原脱氯的影响与机制

自然环境中,大多数氯代有机污染物厌氧还原脱氯反应是与土壤环境中一些生源要素的生物化学还原过程相伴生。有机污染物的种类、生物有效性以及毒性能够显著影响这些生源要素的转化,反过来,土壤中活跃的氧化还原反应也可以显著影响有机污染物的动力学转化过程。本文从氧化还原顺序上综述了反硝化过程、铁还原过程、硫酸盐还原过程和产甲烷过程对氯代有机污染物厌氧还原脱氯过程的影响与作用机制,旨在为氯代有机污染物在厌氧环境中还原脱氯的过程与机理的进一步研究、以及还原脱氯与微生物介导的生源要素氧化还原过程的耦合作用机制的揭示提供参考。     

Degradation of biopolymeric pigments in distillery spentwash by electrocoagulation using copper anodes: statistical and canonical analysis

The electrocoagulation studies of distillery spentwash using copper anodes were utilized to demonstrate the usefulness of Box–Behnken experimental design of response surface analysis to derive a statistical model and the optimum parameters for color removal. The current intensity (1.5 A), dilution (10%) and time of electrolysis (5 h) had been found to be the optimum conditions for maximum 77.11% color removal. The actual color removal at optimized conditions was found to be 78.26%, which is to the predicted response using response surface methodology. The energy consumption and current efficiency were determined from reduction in chemical oxygen demand.     

酵母菌处理高浓度色拉油加工废水研究

从含油土壤中筛选出适用于色拉油加工废水的酵母菌菌群,并用摇瓶试验研究了该菌群对未经预处理的高浓度含油色拉油加工废水的降解效果．采用酵母菌菌群处理总有机碳（ Ｔ Ｏ Ｃ） 含量为ρ Ｔ Ｏ Ｃ＝ ２ ５００ ｍｇ Ｌ－ １ 的色拉油加工废水,２４ ｈ 内可以去掉８５ ．２ ％ 的 Ｔ Ｏ Ｃ．酵母菌菌群在酸性条件下（ｐ Ｈ３ 左右） 表现出更好的处理效率,反应温度升高时 Ｔ Ｏ Ｃ 去除率有降低的趋势．结果表明,高浓度含油色拉油废水可以直接用酵母菌法进行处理     

高锰酸钾预氧化-混凝沉淀组合工艺处理微污染水研究

针对微污染水,就高锰酸钾预氧化技术与与饮用水常规混凝沉淀工艺组合联用开展了一些试验研究。结果表明：高锰酸钾的预氧化作用有助于PAC混凝沉淀工艺对原水中有机污染物的去除;KMnO4和聚合氯化铝（PAC）的投加方式对原水耗氧量的去除率有明显影响;KMnO4预氧化有一个最佳时间;高锰酸钾预氧化-混凝沉淀组合微污染水处理工艺,对原水pH值的波动有比较好的适应性。     

Depollution of indigo dye by anodic oxidation and electro-Fenton using B-doped diamond anode

Hazardous wastes are generated in the synthesis of dyes and pigments applied in industries. Efficient methods are thus needed to clean wastewaters. Here, we use anodic oxidation and electro-Fenton with B-doped diamond anode to degrade the synthetic dye indigo in aqueous sodium dithionite. Results show the near-complete mineralization of the dye within 80 min at 500 mA. Mineralization was faster by electro-Fenton than anodic oxidation. The second-order rate constant (k) for the reaction of indigo with ^·OH was measured as 4.03 × 10⁹ M^?1 s^?1 at pH 3.0 and was compared with the rate constants of reactions between dyes and ^·OH. The results clearly demonstrate that both electro-Fenton and anodic oxidation can be used to depollute dyes in textile effluent with high efficiency and low cost. The main oxidant, ^·OH, being a non-selective reagent, the method could be applied to degrade other organic pollutants.     

Degradation of the herbicide imazapyr by Fenton reactions

The degradation of the herbicide imazapyr has been carried out by three advanced oxidation processes involving iron ions as catalysts: Fentons reagent, photo-Fenton and electro-Fenton. We show that all processes are rapid and efficient. The kinetic rate constant was found to be k=5.4×10⁹ M^–1 s^–1. The mineralization of imazapyr is almost complete using the photo-Fenton and electro-Fenton processes.     

Removal of decabromodiphenyl ether (BDE-209) by sepiolite-supported nanoscale zerovalent iron

Nanoscale zerovalent iron (nZVI) synthesized using sepiolite as a supporter was used to investigate the removal kinetics and mechanisms of decabromodiphenyl ether (BDE-209). BDE-209 was rapidly removed by the prepared sepiolite-supported nZVI with a reaction rate that was 5 times greater than that of the conventionally prepared nZVI because of its high surface area and reactivity. The degradation of BDE-209 occurred in a stepwise debromination manner, which followed pseudo-first-order kinetics. The removal efficiency of BDE-209 increased with increasing dosage of sepiolite-supported nZVI particles and decreasing pH, and the efficiency decreased with increasing initial BDE-209 concentrations. The presence of tetrahydrofuran (THF) as a cosolvent at certain volume fractions in water influenced the degradation rate of sepiolite-supported nZVI. Debromination pathways of BDE-209 with sepiolite-supported nZVI were proposed based on the identified reaction intermediates, which ranged from nona- to mono-brominated diphenylethers (BDEs) under acidic conditions and nona- to penta-BDEs under alkaline conditions. Adsorption on sepiolite-supported nZVI particles also played a role in the removal of BDE-209. Our findings indicate that the particles have potential applications in removing environmental pollutants, such as halogenated organic contaminants.     

A pulsed switching peroxi-coagulation process to control hydroxyl radical production and to enhance 2,4-Dichlorophenoxyacetic acid degradation

• A new pulsed switching peroxi-coagulation (PSPC) system was developed. • The EC_T for 2,4-D removal in the PSPC was lower than that in the EF. • The iron consumption for 2,4-D removal in the PSPC was lower than that in the PC. The aim of this study was to develop a new pulsed switching peroxi-coagulation system to control hydroxyl radical (?OH) production and to enhance 2,4-Dichlorophenoxyacetic acid (2,4-D) degradation. The system was constructed with a sacrifice iron anode, a Pt anode, and a gas diffusion cathode. Production of H₂O₂ and Fe²⁺ was controlled separately by time delayers with different pulsed switching frequencies. Under current densities of 5.0 mA/cm² (H₂O₂) and 0.5 mA/cm² (Fe²⁺), the ?OH production was optimized with the pulsed switching frequency of 1.0 s (H₂O₂):0.3 s (Fe²⁺) and the ratio of H₂O₂ to Fe²⁺ molar concentrations of 6.6. Under the optimal condition, 2,4-D with an initial concentration of 500 mg/L was completely removed in the system within 240 min. The energy consumption for the 2,4-D removal in the system was much lower than that in the electro-Fenton process (68±6 vs. 136±10 kWh/kg TOC). The iron consumption in the system was ~20 times as low as that in the peroxi-coagulation process (196±20 vs. 3940±400 mg/L) within 240 min. The system should be a promising peroxi-coagulation method for organic pollutants removal in wastewater.     

海洋环境中多环芳烃的微生物降解研究进展

多环芳烃 (PAHs)是一类广泛分布于海洋环境中的含有两个苯环以上的有毒有害污染物 ,主要来源于人类活动和能源利用过程 ,如石油、煤、木材等的燃烧过程 ,石油及石油化工产品的生产过程 ,海上通过地面径流、污水排放及机动车辆等燃料不完全燃烧后的废气随大气颗粒的沉降进入海洋环境中 .由于多环芳烃的潜在毒性、致癌性及致畸诱变作用[1,2 ] ,通过生物累积及食物链的传递作用 ,给海洋生物、生态环境和人体健康带来极大危害 ,已引起各国环境科学家的极大重视 .美国环保局在上世纪 80年代把 16种未带分支的多环芳烃确定为环境中的优先污染物[…     

Soil washing of As-contaminated stream sediments in the vicinity of an abandoned mine in Korea

A soil washing process was applied to remediate arsenic (As)-contaminated stream sediments around an abandoned mine in Goro, Korea. Laboratory scale soil washing experiments for As-contaminated stream sediments were performed under various washing conditions in order to maximize As removal efficiency. Stream sediments were taken from two sites (S1 and S5) along the main stream connected to an abandoned mine. Stream sediments at the two sites were divided into two groups (≥0.35 and <0.35 mm in diameter), giving four types of sediments, which were thereupon used for soil washing experiments. The results of soil washing experiments involving various pH conditions suggested that As removal efficiency is very high in both strongly acidic and basic solutions (pH 1 and 13), regardless of sediment type. Removal efficiencies for fine sediments from S1 and S5 were >95% after 1 h of washing with 0.2 M citric acid (C₆H₈O₇). When using 0.2 M citric acid mixed with 0.1 M potassium phosphate (KH₂PO₄), the As removal efficiency increased to 100%. When recycled washing solution was applied, As removal efficiency was maintained at a level greater than 70%, even after eight recycling events. This suggests that the recycling of washing solution could be successfully applied as a means of decreasing the cost of the washing process. Results from the experiments suggest that soil washing is a potentially useful process for the remediation of As-contaminated stream sediments around abandoned mines.