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.     

Direct degradation of methylene blue by unactivated peroxymonosulfate: reaction parameters,kinetics, and mechanism

Environmental Science and Pollution Research - Advanced oxidation processes (AOPs) are efficient methods for water purification. However, there are few studies on using peroxymonosulfate (PMS) to...     

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.     

Comparison of various advanced oxidation processes and chemical treatment methods for COD and color removal from a polyester and acetate fiber dyeing effluent

In this paper, a comparison of various advanced oxidation processes (O3, O3/UV, H2O2/UV, O3/H2O2/UV, Fe2+/H2O2) and chemical treatment methods using Al2(SO4)3.18H2O, FeCl3 and FeSO4 for the chemical oxygen demand (COD) and color removal from a polyester and acetate fiber dyeing effluent is undertaken. Advanced oxidation processes (AOPs) showed a superior performance compared to conventional chemical treatment, which maximum achievable color and COD removal for the textile effluent used in this study was 50% and 60%, respectively. Although O3/H2O2/UV combination among other AOPs methods studied in this paper was found to give the best result (99% removal for COD and 96% removal for color), use of Fe2+/H2O2 seems to show a satisfactory COD and color removal performance and to be economically more viable choice for the acetate and polyester fiber dyeing effluent on the basis of 90% removal.     

O3、H2O2／O3及UV／O3在焦化废水深度处理中的应用

采用O3、H2O2／O3及UV／O3等高级氧化技术（AOPs）对某焦化公司的生化出水进行深度处理，考察了O3与废水的接触时间、溶液pH、反应温度等因素对废水COD去除率的影响，确定出O3氧化反应的最佳工艺参数为：接触时间40min，溶液pH8．5，反应温度25℃，此条件下废水COD及UV254的去除率最高可达47．14％和73．47％；H2O2／O3及UV／O3两种组合工艺对焦化废水COD及UV254的去除率均有一定程度的提高，但H2O2／O3系统的运行效果取决于H2O2的投加量。研究结论表明，单纯采用COD作为评价指标，并不能准确反映出O3系列AOPs对焦化废水中有机污染物的降解作用。     

Hydroxyl radical-mediated degradation of diclofenac revisited: a computational approach to assessment of reaction mechanisms and by-products

Environmental Science and Pollution Research - Advanced oxidation processes (AOPs) are based on the in situ production of hydroxyl radicals (•OH) and reactive oxygen species (ROS) in water...     

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...     

Studies on degradation of glyphosate by several oxidative chemical processes: Ozonation,photolysis and heterogeneous photocatalysis

Several different Advanced Oxidation Processes (AOPs) including ozonation at pH 6.5 and 10, photolysis and heterogeneous photocatalysis using TiO₂ as semiconductor and dissolved oxygen as electron acceptor were applied to study the degradation of glyphosate (N-phosphonomethyl glycine) in water. The degree of glyphosate degradation, the reactions kinetic and the formation of the major metabolite, aminomethyl phosphonic acid (AMPA), were evaluated. Ozonation at pH 10 resulted in the maximum mineralization of glyphosate. It was observed that under the experimental conditions used in this study the degradation of glyphosate followed the first-order kinetics. The half-life obtained for glyphosate degradation in the O₃/pH 10 process was 1.8 minutes.     

Analytical tools employed to determine pharmaceutical compounds in wastewaters after application of advanced oxidation processes

Today, the presence of contaminants in the environment is a topic of interest for society in general and for the scientific community in particular. A very large amount of different chemical substances reaches the environment after passing through wastewater treatment plants without being eliminated. This is due to the inefficiency of conventional removal processes and the lack of government regulations. The list of compounds entering treatment plants is gradually becoming longer and more varied because most of these compounds come from pharmaceuticals, hormones or personal care products, which are increasingly used by modern society. As a result of this increase in compound variety, to address these emerging pollutants, the development of new and more efficient removal technologies is needed. Different advanced oxidation processes (AOPs), especially photochemical AOPs, have been proposed as supplements to traditional treatments for the elimination of pollutants, showing significant advantages over the use of conventional methods alone. This work aims to review the analytical methodologies employed for the analysis of pharmaceutical compounds from wastewater in studies in which advanced oxidation processes are applied. Due to the low concentrations of these substances in wastewater, mass spectrometry detectors are usually chosen to meet the low detection limits and identification power required. Specifically, time-of-flight detectors are required to analyse the by-products.     

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.     

真空紫外光臭氧降解偏二甲肼的研究

研究比较了臭氧氧化（O₃）、紫外臭氧（O₃/UV）和真空紫外臭氧（O₃/VUV）对推进剂——偏二甲肼的处理效果，O₃/VUV最为有效，反应速率常数分别比O₃/UV和O₃高39.8%和65.6%，中间产物——甲醛去除得更迅速，反应50 min即无法检出。初始pH 9时，O₃/VUV降解偏二甲肼的速率最快，达到0.4461 min^-1；反应速率常数随臭氧投加量的增加而线性增大；随偏二甲肼初始浓度从100 mg/L增加到2 000 mg/L，反应动力学由一级转为零级。碳酸盐浓度在0～2 mmol/L范围内对O₃/VUV降解偏二甲肼没有明显的抑制作用。偏二甲肼的无机氮产物以氨离子为主，无机氮只占总氮的40%～60%，说明仍有相当比例的氮以有机氮形式存在。     

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.     

含酚废水的无害化处理技术进展

概述了含酚废水的无害化处理技术现状及其进展。着重介绍了传统生物处理工艺的改良、高效菌种的选育、酶及固定化细胞等技术在含酚废水生物处理中的研究与应用 ,分析了先进氧化技术与焚烧技术的特点和存在的主要问题及应用前景 ,并探讨了含酚废水无害化处理技术的发展趋势     

Photodegradation of 4-tert octylphenol in aqueous solution promoted by Fe(III)

4-Tert-octylphenol (4-t-OP), a kind of endocrine-disrupting compounds, is widely distributed in natural water surroundings but can hardly be biodegraded. The advanced oxidation processes (AOPs) have been proved to be an efficient method to degrade 4-t-OP. In this study, the photodegradation of 4-t-OP in aqueous solution promoted by Fe(III) and the photooxidation mechanism were investigated. The ferric perchlorate was added into the aqueous solution for the production of hydroxyl radical. The efficiency of mineralization was monitored by total organic carbon analyzer, and photooxidation products were determined by high-performance liquid chromatography and liquid chromatography-mass spectrometer. 4-t-OP (2.4?×?10^?5 M) in aqueous solution was completely degraded after 45 min in the presence of Fe(III) (1.2?×?10^?3 M) under UV irradiation (λ?=?365 nm). The optimal pH was 3.5. Higher Fe(III) concentration or lower initial 4-t-OP concentration led to increased photodegradation efficiency of 4-t-OP. The reaction was almost completely inhibited in the presence of 2-propanol. About 70 % mineralization of the solution was obtained after 50 h. The photooxidation product was supposed to be 4-tert-octyl catechol. 4-t-OP in aqueous solution can be degraded in the presence of Fe(III) under the solar irradiation. The photoinduced degradation is due to the reaction with hydroxyl radicals. It shows that the 4-t-OP is mineralized by the inducement of Fe(III) aquacomplexes, which exposes to solar light. Therefore, the results would provide useful information for the potential application of the AOPs to remove 4-t-OP in water surroundings.     

Advanced oxidation of a pulp mill bleaching wastewater.

The degradation, by several advanced oxidation reactions, of a pulp mill ECF bleaching effluent, was studied. The initial biodegradability of the organic matter present in the effluent, estimated as the BOD5/COD, was low (0.3). When the effluent was submitted to ozonation and to five different advanced oxidation systems (O3/UV, O3/UV/ZnO, O3/UV/TiO2, O2/UV/ZnO, O2/UV/TiO2), the biodegradability increase significantly. After five minutes of reaction, the O3/UV system appears as the most efficient in to transform the organic matter to more biodegradable forms. A similar effect was observed when the effluent was submitted to an activated sludge treatment. The COD, TOC and toxicity reduction correlated well with the biodegradability enhancement after AOPs treatments.     

Application of Fenton, photo-Fenton, solar photo-Fenton, and UV/H2O2 to degradation of the antineoplastic agent mitoxantrone and toxicological evaluation

In the present study, selected advanced oxidation processes (AOPs)—namely, photo-Fenton (with Fe²⁺, Fe³⁺, and potassium ferrioxalate—FeOx—as iron sources), solar photo-Fenton, Fenton, and UV/H₂O₂—were investigated for degradation of the antineoplastic drug mitoxantrone (MTX), frequently used to treat metastatic breast cancer, skin cancer, and acute leukemia. The results showed that photo-Fenton processes employing Fe(III) and FeOx and the UV/H₂O₂ process were most efficient for mineralizing MTX, with 77, 82, and 90 % of total organic carbon removal, respectively. MTX probably forms a complex with Fe(III), as demonstrated by voltammetric and spectrophotometric measurements. Spectrophotometric titrations suggested that the complex has a 2:1 Fe³⁺:MTX stoichiometric ratio and a complexation constant (K) of 1.47 × 10⁴ M^–1, indicating high MTX affinity for Fe³⁺. Complexation partially inhibits the involvement of iron ions and hence the degradation of MTX during photo-Fenton. The UV/H₂O₂ process is usually slower than the photo-Fenton process, but, in this study, the UV/H₂O₂ process proved to be more efficient due to complexing of MTX with Fe(III). The drug exhibited no cytotoxicity against NIH/3T3 mouse embryonic fibroblast cells when oxidized by UV/H₂O₂ or by UV/H₂O₂/FeOx at the concentrations tested.     

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.     

Sonochemical degradation of a pharmaceutical waste,atenolol, in aqueous medium

Atenolol is a β-blocker drug and an identified emerging pollutant. Advanced oxidation processes (AOPs) utilise the reaction of a highly oxidising species (hydroxyl radicals, ^?OH) for the mineralisation of emerging pollutants since conventional treatment methodologies generally fail to degrade these compounds. In the present work, degradation of atenolol was carried out using ultrasound with frequencies ranging from 200 kHz to 1 MHz as a source of hydroxyl radical. The degradation was monitored by HPLC, total organic carbon (TOC) and chemical oxygen demand (COD) reduction and ion chromatography (IC). Nearly 90 % of degradation of atenolol was observed with ultrasound having 350 kHz. Both frequency and power of ultrasound affect the efficiency of degradation. Nearly 100 % degradation was obtained at a pH of 4. Presence of various additives such as sodium dodecyl sulphate, chloride, sulphate, nitrate, phosphate and bicarbonate was found to reduce the efficiency of degradation. Although nearly 100 % degradation of atenolol was observed under various experimental conditions, only about 62 % mineralisation (from TOC and COD measurements) was obtained. Nearly eight intermediate products were identified using high-resolution mass spectrometry (LC-Q-TOF). These products were understood as the results of hydroxyl radical addition to atenolol. The degradation studies were also carried out in river water which also showed a similar degradation profile. A mechanism of degradation and mineralisation is presented.     

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.     

Photochemical degradation and mineralization of 4-chlorophenol

INTENTION, GOAL, SCOPE, BACKGROUND: Since the intermediate products of some compounds can be more toxic and/or refractory than the original compund itself, the development of innovative oxidation technologies which are capable of transforming such compounds into harmless end products, is gaining more importance every day. Advanced oxidation processes are one of these technologies. However, it is necessary to optimize the reaction conditions for these technologies in order to be cost-effective. OBJECTIVE: The main objectives of this study were to see if complete mineralization of 4-chlorophenol with AOPs was possible using low pressure mercury vapour lamps, to make a comparison of different AOPs, to observe the effect of the existence of other ions on degradation efficiency and to optimize reaction conditions. METHODS: In this study, photochemical advanced oxidation processes (AOPs) utilizing the combinations of UV, UV/H2O2 and UV/H2O2/Fe2+ (photo-Fenton process) were investigated in labscale experiments for the degradation and mineralization of 4-chlorophenol. Evaluations were based on the reduction of 4-chlorophenol and total organic carbon. The major parameters investigated were the initial 4-chlorophenol concentration, pH, hydrogen peroxide and iron doses and the effect of the presence of radical scavengers. RESULTS AND DISCUSSION: It was observed that the 4-chlorophenol degradation efficiency decreased with increasing concentration and was independent of the initial solution pH in the UV process. 4-chlorophenol oxidation efficiency for an initial concentration of 100 mgl(-1) was around 89% after 300 min of irradiation in the UV process and no mineralization was achieved. The efficiency increased to > 99% with the UV/H2O2 process in 60 min of irradiation, although mineralization efficiency was still around 75% after 300 min of reaction time. Although the H2O2/4-CP molar ratio was kept constant, increasing initial 4-chlorophenol concentration decreased the treatment efficiency. It was observed that basic pHs were favourable in the UV/H2O2 process. The results showed that the photo-Fenton process was the most effective treatment process under acidic conditions. Complete disappearance of 100 mgl(-1) of 4-chlorophenol was achieved in 2.5 min and almost complete mineralization (96%) was also possible after only 45 min of irradiation. The efficiency was negatively affected from H2O2 in the UV/H2O2 process and Fe2+ in the photo-Fenton process over a certain concentration. The highest negative effect was observed with solutions containing PO4 triple ions. Required reaction times for complete disappearance of 100 mgl(-1) 4-chlorophenol increased from 2.5 min for an ion-free solution to 30 min for solutions containing 100 mgl(-1) PO4 triple ion and from 45 min to more than 240 min for complete mineralization. The photodegradation of 4-chlorophenol was found to follow the first-order law. CONCLUSION: The results of this study showed that UV irradiation alone can degrade 4-CP, although at very slow rates, but cannot mineralize the compound. The addition of hydrogen peroxide to the system, the so-called UV/H2O2 process, significantly enhances the 4-CP degradation rate, but still requires relatively long reaction periods for complete mineralization. The photo-Fenton process, the combination of homogeneous systems of UV/H2O2/Fe2+ compounds, produces the highest photochemical elimination rate of 4-CP and complete mineralization is possible to achieve in quite shorter reaction periods when compared with the UV/H2O2 process. RECOMMENDATIONS AND OUTLOOK: It is more cost effective to use these processes for only purposes such as toxicity reduction, enhancement of biodegradability, decolorization and micropollutant removal. However the most important point is the optimization of the reaction conditions for the process of concern. In such a case, AOPs can be used in combination with a biological treatment systems as a pre- or post treatment unit providing the cheapest treatment option. The AOP applied, for instance, can be used for toxicity reduction and the biological unit for chemical oxygen demand (COD) removal.