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.     

环境水体微污染有机物及其去除技术研究进展

水体有机污染物因其生物毒性对人体健康和生态环境造成了严重的危害。随着环保技术的发展,高浓度有机污染物已得到很好的去除。检测水平的不断提高使微量有机污染物日益受到广泛关注。为了深入地研究微污染有机物及其去除技术,对微污染有机物的种类、性质和危害进行了详细阐述,并综述了国内外生物法、膜处理技术、高级氧化技术、吸附技术对微污染有机物的去除效果,总结了各种技术的优缺点。     

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.     

Endocrine disruptors compounds, pharmaceuticals and personal care products in urban wastewater: implications for agricultural reuse and their removal by adsorption process

In the last years, a lot of emerging contaminants, such as, endocrine disruptors compounds (EDCs), pharmaceuticals, and personal care products (PPCPs) have been detected in wastewater. Because of their toxicity and possible adverse effects on the environment and humans, their release from urban wastewater treatment plants (UWWTPs) effluents should be minimized, particularly when a wastewater reuse for crops irrigation is expected. Many processes have been investigated for advanced treatment of UWWTP effluents as well as for emerging contaminant degradation; among these, adsorption process was successfully used to remove EDCs and PPCPs from wastewater. This article shortly reviews EDCs and PPCPs removal from UWWTP effluents by adsorption process using conventional and non-conventional adsorbents. The fate of EDCs and PPCPs in UWWTPs and the implications for agricultural wastewater reuse has been addressed too. In spite of the adsorption process looking to be a valuable alternative to other advanced technologies for the removal of emerging contaminants from wastewater, some gaps still remain to evaluate the actual feasibility at full scale. However, according to a few studies available in scientific literature on the use of both powdered activated carbon and granular activated carbon at full scale, adsorption process by activated carbon is a promising, potentially effective, and economically feasible solution for producing safe wastewater for agricultural reuse.     

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。     

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     

Biofiltration vs conventional activated sludge plants: what about priority and emerging pollutants removal?

This paper compares the removal performances of two complete wastewater treatment plants (WWTPs) for all priority substances listed in the Water Framework Directive and additional compounds of interest including flame retardants, surfactants, pesticides, and personal care products (PCPs) (n?=?104). First, primary treatments such as physicochemical lamellar settling (PCLS) and primary settling (PS) are compared. Similarly, biofiltration (BF) and conventional activated sludge (CAS) are then examined. Finally, the removal efficiency per unit of nitrogen removed of both WWTPs for micropollutants is discussed, as nitrogenous pollution treatment results in a special design of processes and operational conditions. For primary treatments, hydrophobic pollutants (log K _ow?>?4) are well removed (>70 %) for both systems despite high variations of removal. PCLS allows an obvious gain of about 20 % regarding pollutant removals, as a result of better suspended solids elimination and possible coagulant impact on soluble compounds. For biological treatments, variations of removal are much weaker, and the majority of pollutants are comparably removed within both systems. Hydrophobic and volatile compounds are well (>60 %) or very well removed (>80 %) by sorption and volatilization. Some readily biodegradable molecules are better removed by CAS, indicating a better biodegradation. A better sorption of pollutants on activated sludge could be also expected considering the differences of characteristics between a biofilm and flocs. Finally, comparison of global processes efficiency using removals of micropollutants load normalized to nitrogen shows that PCLS?+?BF is as efficient as PS?+?CAS despite a higher compactness and a shorter hydraulic retention time (HRT). Only some groups of pollutants seem better removed by PS?+?CAS like alkylphenols, flame retardants, or di-2-ethylhexyl phthalate (DEHP), thanks to better biodegradation and sorption resulting from HRT and biomass characteristics. For both processes, and out of the 68 molecules found in raw water, only half of them are still detected in the water discharged, most of the time close to their detection limit. However, some of them are detected at higher concentrations (>1 μg/L and/or lower than environmental quality standards), which is problematic as they represent a threat for aquatic environment.     

焦化废水泡沫分离液的Fenton催化氧化预处理

以焦化废水处理过程产生的泡沫分离液为研究对象,对其进行Fenton催化氧化处理实验,考察H₂O₂用量、Fe²⁺浓度、pH和反应时间4个因素对处理效果的影响,并结合GC/MS方法比较处理前后泡沫分离液中有机物的种类及其生物降解性的变化。结果表明,采用［H₂O₂］=100 mmol/L、［Fe²⁺］=100 mg/L、pH=3、反应时间为30 min的Fenton催化氧化反应条件,可以使分离液的COD去除率达到68%以上;经Fenton处理后,分离液的B/C值由0.12提高至0.38,生物降解性明显改善;通过GC/MS的分析,基本明确分离液中含有的有机物主要为酚、胺、腈、酯类有机物及喹啉、吡啶等杂环化合物,大多数属于难降解且生物毒性较强的有机物。针对这些复杂组分共存的泡沫分离液,利用Fenton试剂较强的氧化能力能够将其含有的有毒/难降解有机物转化为低毒或无毒的小分子有机物,为其后续的生物处理创造良好的条件。     

Applicability of Fenton and H2O2/UV reactions in the treatment of tannery wastewaters

In this paper we evaluated the H2O2/UV and the Fenton's oxidation processes for the treatment of tannery wastewater under different experimental conditions. Efficiencies were judged by the amounts of organic substances degraded or eliminated under these treatment techniques. Daphnia magna and Vibrio fischeri were used to monitor toxicity. Organic compounds contained in the untreated and treated tannery wastewater were determined and identified using substance specific techniques. Gas chromatography-mass spectrometry (GC-MS) in positive electron impact (EI(+)) mode was applied to determine volatile organics. Atmospheric pressure ionization (API) mass (MS) and tandem mass spectrometry (MS-MS) coupled with flow injection analysis (FIA) or liquid chromatography (LC) were used to detect or identify polar organic pollutants. The experimental results indicated that both oxidation processes--H2O2/UV at pH 3 and Fenton at pH 3.5--are able to reduce TOC content by mineralisation of the organic compounds.     

污水处理中几种去除药物及个人护理用品方法的机理及效果比较

目前广泛分布在环境中的药物及个人护理品（pharmaceuticals and personal care products, PPCPs）在环境中的迁移、转化和处理已成为环境科学与工程研究的一个新的领域。污水处理厂排水是PPCPs进入环境中的主要途径。介绍了污水处理过程中传统活性污泥法、膜处理技术以及氧化处理等主要工艺对PPCPs的去除机理,并对去除效果进行了比较。以传统活性污泥法及在其改进后的膜处理技术为基础的大部分现有污水处理厂只能够去除一部分PPCPs,并且主要通过吸附（如对于吐纳麝香、佳乐麝香、萨利麝香等脂溶性较高的有机物）和生物降解作用（如对于布洛芬,17β-雌二醇,雌酮等易反应的有机物）。然而,吸附了PPCPs的污泥通过土壤施肥又将PPCPs带入土壤中,进而会渗滤到地下水,或随径流水进入地表水中。因此,PPCPs并没有从根本上得以去除。相比之下氧化处理工艺（如氯化、臭氧氧化、紫外辐射）或这些工艺的组合能够将大部分的PPCPs进行氧化,去除效果明显优于以上2种技术。然而,氧化后产物的种类和毒理性需要更深入的研究。     

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.     

Emerging trends in photodegradation of petrochemical wastes: a review

Various human activities like mining and extraction of mineral oils have been used for the modernization of society and well-beings. However, the by-products such as petrochemical wastes generated from such industries are carcinogenic and toxic, which had increased environmental pollution and risks to human health several folds. Various methods such as physical, chemical and biological methods have been used to degrade these pollutants from wastewater. Advance oxidation processes (AOPs) are evolving techniques for efficient sequestration of chemically stable and less biodegradable organic pollutants. In the present review, photocatalytic degradation of petrochemical wastes containing monoaromatic and poly-aromatic hydrocarbons has been studied using various heterogeneous photocatalysts (such as TiO₂, ZnO and CdS. The present article seeks to offer a scientific and technical overview of the current trend in the use of the photocatalyst for remediation and degradation of petrochemical waste depending upon the recent advances in photodegradation of petrochemical research using bibliometric analysis. We further outlined the effect of various heterogeneous catalysts and their ecotoxicity, various degradation pathways of petrochemical wastes, the key regulatory parameters and the reactors used. A critical analysis of the available literature revealed that TiO₂ is widely reported in the degradation processes along with other semiconductors/nanomaterials in visible and UV light irradiation. Further, various degradation studies have been carried out at laboratory scale in the presence of UV light. However, further elaborative research is needed for successful application of the laboratory scale techniques to pilot-scale operation and to develop environmental friendly catalysts which support the sustainable treatment technology with the “zero concept” of industrial wastewater. Nevertheless, there is a need to develop more effective methods which consume less energy and are more efficient in pilot scale for the demineralization of pollutant.     

Sulphonated aromatic pollutants

Many synthetic sulphonated aromatic compounds are used as starting material to produce dyes and pigments, or are released as by-products in the effluents of the textile and dye industry. A large number of these chemicals are poorly biodegradable and cannot be eliminated by classical wastewater treatment plants. To limit the impact of these pollutants on the environment, new processes, based on the use of higher plants (constructed wetlands or hydroponic systems), are under development. Detergents and surfactants are essential for both industrial and domestic applications, the most important family being the alkylbenzene sulphonates. Originally, the alkyl side chains were branched and thus recalcitrant to biodegradation. Therefore, they have been replaced by linear alkylbenzene sulphonates. Although more acceptable, present formulations still have adverse environmental and toxic effects. In this context, phytoremediation appears to be a promising approach to remove these compounds from contaminated soils and waters.     

Long-term comparison of trace organics removal performances between conventional and membrane activated sludge processes.

The removal of trace organic compounds through membrane bioreactors (MBR) compared with a conventional wastewater treatment plant (WWTP) in a long-term study was investigated. Two MBR pilot plants were operated in parallel to a full-scale WWTP fed with the same municipal raw wastewater. Polar compounds (phenazone-type pharmaceuticals, their metabolites, and carbamazepine) and less polar estrogenic steroids (estradiol, estrone, and ethinylestradiol) were quantified. The removal rate of phenazone, propyphenazone, and formylaminoantipyrine by the conventional WWTP was less than 15%. Significantly higher removal rates (60 to 70%) started to be clearly monitored in the pilot plants after approximately 5 months. Higher removal rates coincided with higher temperatures in the summer. The conventional WWTP removed, on average, more than 90% of the natural steroids estrone and estradiol and approximately 80% of the synthetic ethinylestradiol. Approximately 99% of estradiol and estrone and approximately 95% of ethinylestradiol was eliminated by the MBR processes.     

Biodegradation of organic pollutants in saline wastewater by halophilic microorganisms: a review

Agro-food, petroleum, textile, and leather industries generate saline wastewater with a high content of organic pollutants such as aromatic hydrocarbons, phenols, nitroaromatics, and azo dyes. Halophilic microorganisms are of increasing interest in industrial waste treatment, due to their ability to degrade hazardous substances efficiently under high salt conditions. However, their full potential remains unexplored. The isolation and identification of halophilic and halotolerant microorganisms from geographically unrelated and geologically diverse hypersaline sites supports their application in bioremediation processes. Past investigations in this field have mainly focused on the elimination of polycyclic aromatic hydrocarbons and phenols, whereas few studies have investigated N-aromatic compounds, such as nitro-substituted compounds, amines, and azo dyes, in saline wastewater. Information regarding the growth conditions and degradation mechanisms of halophilic microorganisms is also limited. In this review, we discuss recent research on the removal of organic pollutants such as organic matter, in terms of chemical oxygen demand (COD), dyes, hydrocarbons, N-aliphatic and N-aromatic compounds, and phenols, in conditions of high salinity. In addition, some proposal pathways for the degradation of aromatic compounds are presented.     

Occurrence of phthalates in aquatic environment and their removal during wastewater treatment processes: a review

Phthalates are plasticizers and are concerned environmental endocrine-disrupting compounds. Due to their extensive usage in plastic manufacturing and personal care products as well as the potential to leach out from these products, phthalates have been detected in various aquatic environments including drinking water, groundwater, surface water, and wastewater. The primary source of their environmental occurrence is the discharge of phthalate-laden wastewater and sludge. This review focuses on recent knowledge on the occurrence of phthalate in different aquatic environments and their fate in conventional and advanced wastewater treatment processes. This review also summarizes recent advances in biological removal and degradation mechanisms of phthalates, identifies knowledge gaps, and suggests future research directions.     

Effect of humic substances on the Fenton treatment of wastewater at acidic and neutral pH

This paper describes results of treatability studies of the effect of humic substances (humate, HS, at the concentration 500-5000 mg l-1) on the Fenton (Fe2+/H2O2) treatment of industrial wastewater at pH 3.5 and 7.0. Without humate, the removal of all contaminants was significantly higher at pH 3.5 than at pH 7. At pH 7.0, the removal of all compounds in the presence of HS (3000 mg l-1) was comparable to that at pH 3.5 without HS. At pH 3.5, humate had no effect on the removal of arsenic, thiocyanate and cyanide, but the removal of all organic compounds (phenol, 2,4-dimethylphenol, benzene, toluene, o-xylene, m- & p-xylene and dichloromethane) was significantly inhibited. Mechanisms of the processes are discussed. It is suggested that, in the presence of HS, acidification of the treated wastewater may not only be unnecessary but it can even hinder the degradation of organic pollutants.     

污水低氧脱氮机制及其应用研究进展

阐述了污水低氧脱氮的基本原理,即抑制或去除亚硝酸盐氧化菌(NOB),同时保留氨氧化菌(AOB),并保持其活性;探讨了污水低氧脱氮实现途径;详细介绍了几种典型的污水低氧脱氮工艺(短程硝化(SHARON)工艺、厌氧氨氧化(ANAMMOX)工艺、好氧反氨化(DEMON)工艺、低氧自养硝化反硝化(OLAND)工艺、甲烷营养型硝化反硝化工艺和亚硝酸盐型完全自养脱氮(CANNON)工艺)的应用研究进展;最后对污水低氧脱氮处理工艺的工程运用进行了展望.     

Biodegradation potential of ofloxacin and its resulting transformation products during photolytic and photocatalytic treatment

The release of pharmaceuticals in the environment, as parent compounds, metabolites and transformation products, and the consequent risks posed to living organisms due to the unintended exposure of the latter to these chemicals are nowadays of increasing scientific concern. The development of advanced oxidation processes able to degrade these substances is in the core of the current research objectives, the main target being the removal of these compounds from wastewaters. Often the focus is on the removal of the parent compound only. However, these processes can form transformation products. Knowledge on the risk related to such transformation products is scarce. Among others, knowledge on their toxic effects and their biodegradability is of importance not only when they are present in the environment but also for the assessment of the advanced oxidation processes’ efficiency applied for their degradation. Photolytic (UV irradiation) and photocatalytic treatment (UV irradiation in the presence of TiO₂) of the fluoroquinolone ofloxacin were applied, and the biodegradability of the formed products was investigated using the Closed Bottle test (OECD 301 D). Various transformation products, formed both during the photo(cata)lytic treatment and the Closed Bottle test, were identified using chromatographic analysis with an ultra high-performance liquid chromatography–tandem mass spectrometry (UPLC–MS/MS) system. The transformation products formed during the phototreatments were found to be non-readily biodegradable as the biodegradation percentages were close to zero. The persistence of the various photo(cata)lytic transformation products during the Closed Bottle test may be attributed to the fluorine present in all the transformation products formed. The transformation products identified suggest that two transformation routes were present: decarboxylation and opening of the piperazinyl ring. Interestingly, it was observed that in the presence of a readily biodegradable carbon source (sodium acetate), the biodegradation percentage increased drastically for some of the photolytically treated samples. This was not the case for the photocatalytically treated samples, in which also mineralization of the parent compound was achieved faster. Further research is needed, however, in order to increase the understanding of the conditions that may lead to less potent and persistent substances during the application of such engineered or natural processes.