Advanced oxidation process

高级氧化工艺
  • 文章类型: Journal Article
    药物和相关物品被广泛用于促进公众健康和生活质量。影响公共卫生的最严重的环境挑战之一是制药工业和医院产生的废水中持续存在抗生素。使用传统的废水处理方法不能从废水中完全去除抗生素。人类产生的未代谢抗生素可以在城市和牲畜废水中找到。废水中存在的抗生素有助于产生对抗生素的抗性和产生超级细菌的问题。最近两年,2019年冠状病毒病的大流行大大增加了医院的废物量。在这种情况下,进行了详细的文献综述,以强调未经处理的医院废物的有害影响,并概述了管理废物的最佳方法。使用传统的处理策略可以去除医院废水中普遍存在的大约50%至70%的新兴污染物。本文强调了有效消除医院废水中新兴污染物和抗生素的多种处理方法,并概述了全球医院废水立法和医院废水管理指南。当与现代氧化技术结合使用时,大约90%的EC可能会通过生物或物理处理技术消除。根据这项研究,混合方法是去除医院废水中抗生素和ECs的最佳方法。该文件概述了有效医院废物管理的许多特征,在2019年冠状病毒病爆发期间和之后可能会有所帮助。当全球所有医院的废物产生大幅增加时。
    Drugs and related goods are widely used in order to promote public health and the quality of life. One of the most serious environmental challenges affecting public health is the ongoing presence of antibiotics in the effluents generated by pharmaceutical industries and hospitals. Antibiotics cannot be entirely removed from wastewater using the traditional wastewater treatment methods. Unmetabolized antibiotics generated by humans can be found in urban and livestock effluent. The antibiotic present in effluent contributes to issues with resistance to antibiotics and the creation of superbugs. Over the recent 2 years, the coronavirus disease 2019 pandemic has substantially boosted hospital waste volume. In this situation, a detailed literature review was conducted to highlight the harmful effects of untreated hospital waste and outline the best approaches to manage it. Approximately 50 to 70% of the emerging contaminants prevalent in the hospital wastewater can be removed using traditional treatment strategies. This paper emphasizes the numerous treatment approaches for effectively eliminating emerging contaminants and antibiotics from hospital wastewater and provides an overview of global hospital wastewater legislation and guidelines on hospital wastewater administration. Around 90% of ECs might be eliminated by biological or physical treatment techniques when used in conjunction with modern oxidation techniques. According to this research, hybrid methods are the best approach for removing antibiotics and ECs from hospital wastewater. The document outlines the many features of effective hospital waste management and might be helpful during and after the coronavirus disease 2019 outbreak, when waste creation on all hospitals throughout the globe has considerably increased.
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  • 文章类型: Journal Article
    在这项研究中,制备并表征了高铁酸钾(K2FeO4)改性的生物炭(Fe-BC)。之后,Fe-BC应用于活化高碘酸盐(PI)降解四环素(TC),一种广泛用于畜牧业的抗生素。比较了不同体系对TC的降解效果,考察了影响因素。此外,确定了Fe-BC/PI系统产生的几种活性氧(ROS),并对TC降解途径进行了分析。此外,评价了Fe-BC的重复使用性能。结果表明,在[BC]=1.09g/L的最佳条件下,Fe-BC/PI体系可以去除几乎100%的TC。初始[PI]=3.29g/L,初始[TC]=20.3mg/LCl-,HCO3-,NO3-,和腐殖酸对Fe-BC/PI体系中的TC降解有不同程度的抑制作用,因为它们对ROS有猝灭作用。通过产生的ROS和BC表面上的Fe的协同作用,TC被降解为中间体甚至水和二氧化碳。Fe-BC重复使用四次,TC的去除率仍保持在80%以上,表明Fe-BC的性质稳定。
    In this study, a potassium ferrate (K2FeO4)-modified biochar (Fe-BC) was prepared and characterized. Afterwards, Fe-BC was applied to activated periodate (PI) to degrade tetracycline (TC), an antibiotic widely used in animal farming. The degradation effects of different systems on TC were compared and the influencing factors were investigated. In addition, several reactive oxygen species (ROS) generated by the Fe-BC/PI system were identified, and TC degradation pathways were analyzed. Moreover, the reuse performance of Fe-BC was evaluated. The results exhibited that the Fe-BC/PI system could remove almost 100% of TC under optimal conditions of [BC] = 1.09 g/L, initial [PI] = 3.29 g/L, and initial [TC] = 20.3 mg/L. Cl-, HCO3-, NO3-, and humic acid inhibited TC degradation to varying degrees in the Fe-BC/PI system due to their quenching effects on ROS. TC was degraded into intermediates and even water and carbon dioxide by the synergistic effect of ROS generated and Fe on the BC surface. Fe-BC was reused four times, and the removal rate of TC was still maintained above 80%, indicating the stable nature of Fe-BC.
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  • 文章类型: Journal Article
    近年来,关于硫酸盐自由基(SO4-·)为基础的高级氧化过程(SR-AOPs)降解新兴有机污染物的研究引起了越来越多的关注。负载金属的生物炭(Me-BC)可以有效防止过渡金属的团聚和浸出,其良好的理化性质和丰富的活性位点在活化过硫酸盐(PS)降解污染物方面表现突出,在高级氧化领域具有重要意义。在本文中,综述了Me-BC的制备方法和稳定性,金属负载对生物炭理化性质的影响,Me-BC活化PS降解污染物的途径(包括自由基途径:SO4-·,羟基自由基(·OH),超氧自由基(O2-·);非自由基途径:单线态氧(1O2),直接电子转移),并讨论了不同活性位点(包括金属离子,持久性自由基,含氧官能团,有缺陷的结构,等。)在SR-AOPs系统中。最后,对Me-BC在SR-AOPs技术中的研究进展进行了展望。
    In recent years, studies on the degradation of emerging organic contaminants by sulfate radical (SO4-·) based advanced oxidation processes (SR-AOPs) have triggered increasing attention. Metal-loaded biochar (Me-BC) can effectively prevent the agglomeration and leaching of transition metals, and its good physicochemical properties and abundant active sites induce outstanding in activating persulfate (PS) for pollutant degradation, which is of great significance in the field of advanced oxidation. In this paper, we reviewed the preparation method and stability of Me-BC, the effect of metal loading on the physicochemical properties of biochar, the pathways of pollutant degradation by Me-BC-activated PS (including free radical pathways: SO4-·, hydroxyl radical (·OH), superoxide radicals (O2-·); non-free radical pathways: singlet oxygen (1O2), direct electron transfer), and discussed the activation of different active sites (including metal ions, persistent free radicals, oxygen-containing functional groups, defective structures, etc.) in the SR-AOPs system. Finally, the prospect was presented for the current research progress of Me-BC in SR-AOPs technology.
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  • 文章类型: Journal Article
    探索高级氧化催化剂,研究了Co-Ni-Mo/碳纳米管(CNT)复合催化剂对过氧单硫酸盐(PMS)的活化作用。使用简单的一锅法成功地制备了NiCo2S4,MoS2和CNTs的化合物。结果表明,Co-Ni-Mo/CNT对PMS的活化在20分钟内对罗丹明B溶液的脱色效率为99%。Co-Ni-Mo/CNT的降解速率是Ni-Mo/CNT或Co-Mo/CNT的4.5倍,是Co-Ni/CNT的1.9倍。此外,自由基猝灭实验表明,主要活性基团是1O2,表面结合的SO4·-,和•OH自由基。此外,催化剂表现出低的金属离子浸出和良好的稳定性。机理研究表明,MoS2表面的Mo4参与了PMS的氧化以及Co3/Co2和Ni3/Ni2的转化。MoS2和NiCo2S4之间的协同作用降低了催化剂和溶液界面之间的电荷转移电阻,从而加快反应速率。由金属硫化物和CNT组成的互连结构还可以增强电子转移过程并提供足够的活性反应位点。我们的工作提供了对用于废水处理的多金属硫化物设计的进一步理解。
    To explore advanced oxidation catalysts, peroxymonosulfate (PMS) activation by Co-Ni-Mo/carbon nanotube (CNT) composite catalysts was investigated. A compound of NiCo2S4, MoS2, and CNTs was successfully prepared using a simple one-pot hydrothermal method. The results revealed that the activation of PMS by Co-Ni-Mo/CNT yielded an exceptional Rhodamine B decolorization efficiency of 99% within 20 min for the Rhodamine B solution. The degradation rate of Co-Ni-Mo/CNT was 4.5 times higher than that of Ni-Mo/CNT or Co-Mo/CNT, and 1.9 times as much than that of Co-Ni/CNT. Additionally, radical quenching experiments revealed that the principal active groups were 1O2, surface-bound SO4•-, and •OH radicals. Furthermore, the catalyst exhibited low metal ion leaching and favorable stability. Mechanism studies revealed that Mo4+ on the surface of MoS2 participated in the oxidation of PMS and the transformation of Co3+/Co2+ and Ni3+/Ni2+. The synergism between MoS2 and NiCo2S4 reduces the charge transfer resistance between the catalyst and solution interface, thus accelerating the reaction rate. Interconnected structures composed of metal sulfides and CNTs can also enhance the electron transfer process and afford sufficient active reaction sites. Our work provides a further understanding of the design of multi-metal sulfides for wastewater treatment.
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  • 文章类型: Journal Article
    季铵化合物(QAC)在大流行期间广泛用于各种抗菌产品中,因此在水生环境中被广泛检测到。在目前的研究中,用UV/一氯胺(UV/NH2Cl)降解三种典型的QAC,即苯扎氯铵化合物(BAC),二烷基二甲基铵化合物(DADMACs),和烷基三甲基铵化合物(ATMAC)。该方法实现了从水样中去除BAC的高效率。用UV/NH2Cl处理的QAC的转化产物使用高分辨率质谱仪进行鉴定和表征,并提出了转化途径。在QAC降解过程中观察到N-亚硝基-N-甲基-N-烷基胺(NMA)和N-亚硝基二甲胺(NDMA)的形成。来自C12-BAC的NDMA的摩尔形成产率为0.04%,而NMA的收益率达到1.05%。使用ECOSAR软件预测了QAC衍生的NMA的生态毒性。增加的毒性可归因于具有较长烷基链的NMA的形成;这些NMA,与它们的母体QAC相比,毒性增加了一个数量级。这项研究提供了证据,证明QAC是NMA的特异性和重要前体。应更加关注NMA的形成及其对生态系统的潜在威胁,包括人类。
    Quaternary ammonium compounds (QACs) are widely detected in the aquatic environment due to their extensive use in a wide array of antibacterial products during the pandemic. In the current study, UV/monochloramine (UV/NH2Cl) was used to degrade three typical QACs, namely benzalkonium compounds (BACs), dialkyl dimethyl ammonium compounds (DADMACs), and alkyl trimethyl ammonium compounds (ATMACs). This process achieved high efficiency in removing BACs from water samples. The transformation products of QACs treated with UV/NH2Cl were identified and characterized using a high-resolution mass spectrometer, and transformation pathways were proposed. The formation of N-nitroso-N-methyl-N-alkylamines (NMAs) and N-nitrosodimethylamine (NDMA) were observed during QAC degradation. The molar formation yield of NDMA from C12-BAC was 0.04 %, while yields of NMAs reached 1.05 %. The ecotoxicity of NMAs derived from QACs was predicted using ECOSAR software. The increased toxicity could be attributed to the formation of NMAs with longer alkyl chains; these NMAs, exhibited a one order of magnitude increase in toxicity compared to their parent QACs. This study provides evidence that QACs are the specific and significant precursors of NMAs. Greater attention should be given to NMA formation and its potential threat to the ecosystem, including humans.
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  • 文章类型: Journal Article
    污水处理厂在从能源密集型系统向碳中性系统过渡方面面临重大挑战,节能系统,废水中的大量化学能仍未开发。铁在现代废水处理中应用广泛。研究表明,利用铁和碳的耦合氧化还原关系可以将这种能量(以碳的形式)重定向到资源利用。因此,重新审视铁在现有废水制碳工艺中的应用尤为重要。在这次审查中,我们探讨了铁用于废水碳流重组的最新研究进展。在铁基化学强化初级处理(CEPT)过程中,有机碳被捕获到污泥中,其生物有效性通过铁基高级氧化工艺(AOP)预处理得到提高,进一步在厌氧生物过程中回收或升级为增值产品。我们讨论了铁在CEPT中的作用和机制,AOP,厌氧生物过程,和生物精炼驱动有机碳转化。铁的用量,作为一个关键参数,显著影响污泥碳资源的回收和利用,特别是通过促进有效的电子转移。我们提出了由铁驱动的废水有机碳的有益转化途径,并详细分析了主要产品的效益。通过这次审查,我们希望为铁化学品的应用和当前的废水处理模式提供新的见解。
    Wastewater treatment plants face significant challenges in transitioning from energy-intensive systems to carbon-neutral, energy-saving systems, and a large amount of chemical energy in wastewater remains untapped. Iron is widely used in modern wastewater treatment. Research shows that leveraging the coupled redox relationship of iron and carbon can redirect this energy (in the form of carbon) towards resource utilization. Therefore, re-examining the application of iron in existing wastewater carbon processes is particularly important. In this review, we investigate the latest research progress on iron for wastewater carbon flow restructuring. During the iron-based chemically enhanced primary treatment (CEPT) process, organic carbon is captured into sludge and its bioavailability is enhanced through iron-based advanced oxidation processes (AOP) pretreatment, further being recovered or upgraded to value-added products in anaerobic biological processes. We discuss the roles and mechanisms of iron in CEPT, AOP, anaerobic biological processes, and biorefining in driving organic carbon conversion. The dosage of iron, as a critical parameter, significantly affects the recovery and utilization of sludge carbon resources, particularly by promoting effective electron transfer. We propose a pathway for beneficial conversion of wastewater organic carbon driven by iron and analyze the benefits of the main products in detail. Through this review, we hope to provide new insights into the application of iron chemicals and current wastewater treatment models.
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  • 文章类型: Journal Article
    在本研究中,我们引入共价有机三嗪骨架聚合物(COTF-P),使用3,4,9,10-茚四羧酸二酐(PTCDA)与三嗪基胺。所得的深红色COTF-P显示了在可见光下作为光催化剂的潜在行为。由于太阳能捕获不足和所得COTF-P的超快电荷复合,制备的COTF-P已经用CQDs(N-CQD和N-S-CQD)装饰,以构建Z方案CQDs/COTF-P异质结光催化剂,并用作暴露于可见光的菲(PHE)的分解光催化剂。对制备的COTF-P和CQDs/COTF-P进行了充分的表征,分析纹理(N2等温线),结构(XRD和FTIR),化学(EDX和XPS),形态学(FESEM和TEM),光学(DRS-UV-Vis和光致发光),和电化学性质(EIS阻抗,瞬态光电流,和平带电位)。制备的N-S-CQD/COTF-P异质结对水中PHE的光催化氧化表现出最佳活性,由于增强了光生电荷的分离和较低的带隙值,2.1vs.1.9eV。N-S-CQD/COTF-P异质结在5次循环再利用后在活性和结构性质方面显示出可接受的稳定性。活化机制突出了超氧自由基和羟基自由基的重要性。该项目揭示了CQDs用于聚合物装饰的潜在用途,扩大可见光区域的吸光度,促进电荷的迁移,这增强了所得材料的活性。
    In the present study, we introduce a covalent organic triazine framework polymer (COTF-P) using 3,4,9,10-perylenetetracarboxylic dianhydride (PTCDA) with triazine-based amine. The resulting dark red COTF-P illustrated potential behavior as a photocatalyst under visible light. Due to the inadequate solar energy capture and ultrafast charge recombination of the resulting COTF-P, the prepared COTF-P has been decorated with CQDs (N-CQD and N-S-CQD) to build a Z-scheme CQDs/COTF-P heterojunction photocatalyst and utilizes as photocatalyst for the breakdown of phenanthrene (PHE) exposed to visible light. The prepared COTF-P and CQDs/COTF-P were fully characterized, analyzing the textural (N2 isotherms), structural (XRD and FTIR), chemical (EDX and XPS), morphological (FESEM and TEM), optical (DRS-UV-Vis and photoluminescence), and electrochemical properties (EIS impedance, transient photocurrent, and flat band potential). The prepared N-S-CQD/COTF-P heterojunction displayed optimum activity for the photocatalytic oxidation of PHE from water, owing to an enhanced separation of the photogenerated charges and lower bandgap value, 2.1 vs. 1.9 eV. The N-S-CQD/COTF-P heterojunction showed acceptable stability in terms of activity and structural properties after 5 cycles of reuse. The mechanism of activation highlights the importance played by superoxide radicals and hydroxyl radicals. This project sheds light on the potential use of CQDs for the decoration of polymers, extending the absorbance in the visible region and boosting the migration of charge, which boosts the activity of the resulting material.
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  • 文章类型: Journal Article
    光电催化高级氧化过程(PEAOP)需要高性能和稳定的光阳极来有效氧化工业废水中的复杂污染物。本研究提出了2DWO3/MXene异壬基结构的构建,用于开发高效稳定的光阳极。WO3/MXene异质结构具有固定在微米大小的MXene片上的有序WO3光敏位点,为污染物氧化提供增加的可见光活性催化表面积和增强的电催化活性。苯酚,一种剧毒的化合物,在0.8V的施加电位下完全氧化可见光照射下的RHE。对苯酚光电催化氧化的操作条件进行了系统优化。通过高效液相色谱(HPLC)分析和中间体化合物的鉴定阐明了苯酚的氧化机理。此外,污染水中苯酚和砷(III)的混合模型证明了WO3/MXene光电阳极同时氧化有机和无机污染物的能力,实现苯酚和As(III)向无毒As(V)的完全转化。WO3/MXene光阳极促进水氧化,产生大量的O2·-和·OH氧化物质,这对于苯酚和砷的同时氧化至关重要。可回收性测试表明,性能保持了99%,确认WO3/MXene光电阳极在PEAOPs中长期运行的适用性。研究结果表明,将WO3/MXene光阳极集成到水净化系统中可以提高经济可行性,降低能耗,提高效率。该PEAOP为各种水体中重金属和有机化学污染的关键问题提供了可行的解决方案,鉴于其可扩展性和在保护清洁水资源的同时保护生态系统的能力。
    The photoelectrocatalytic advanced oxidation process (PEAOP) necessitates high-performing and stable photoanodes for the effective oxidation of complex pollutants in industrial wastewater. This study presents the construction of 2D WO3/MXene heteronanostructures for the development of efficient and stable photoanode. The WO3/MXene heterostructure features well-ordered WO3 photoactive sites anchored on micron-sized MXene sheets, providing an increased visible light active catalytic surface area and enhanced electrocatalytic activities for pollutant oxidation. Phenol, a highly toxic compound, was completely oxidized at an applied potential of 0.8 V vs. RHE under visible light irradiation. Systematic optimization of operational conditions for the photoelectrocatalytic oxidation of phenol was conducted. The phenol oxidation mechanism was elucidated via high-performance liquid chromatography (HPLC) analysis and the identification of intermediate compounds. Additionally, a mixed model of phenol and arsenic (III) in polluted water demonstrated the capability of WO3/MXene photoanode for the simultaneous oxidation of both organic and inorganic pollutants, achieving complete conversion of phenol and As(III) to non-toxic As(V). The WO3/MXene photoanode facilitated water oxidation, generating a substantial amount of O2•- and •OH oxidative species, which are crucial for the concurrent oxidation of phenol and arsenic. Recyclability tests demonstrated a 99% retention of performance, confirming the WO3/MXene photoanode\'s suitability for long-term operation in PEAOPs. The findings suggest that integrating WO3/MXene photoanodes into water purification systems can enhance economic feasibility, reduce energy consumption, and improve efficiency. This PEAOP offers a viable solution to the critical issue of heavy metal and organic chemical pollution in various water bodies, given its scalability and ability to preserve ecosystems while conserving clean water resources.
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  • 文章类型: Journal Article
    基于生物炭过硫酸盐活化的高级氧化工艺已广泛用于去除废水中的抗生素和抗生素抗性基因(ARGs)。在这项研究中,我们使用基于生物炭/过硫酸盐系统的普通连续固定床反应器来处理废水。在生物炭/过硫酸盐反应器中,平均表观ARG去除效率为82.38%。连续反应器活动的结果表明,生物炭中存在ARG残留物(生物炭中ARG的丰度增加了103倍),并且不稳定地去除细胞外ARG,引起人们对潜在环境负担的担忧。动力学实验表明,细胞内ARGs(iARGs)的绝对丰度在30min内迅速下降98.3%,但是细胞外ARGs(eARGs)相应增加了15倍,表明过硫酸盐将细菌细胞打开并迅速释放iARGs作为eARGs。此外,三种类型的ARG的比例表明,生物炭/过硫酸盐反应器对ARG的去除归因于约70%的降解和30%的吸附。进一步的分析表明,生物炭是ARGs的特殊庇护所。使用过的生物炭的释放实验表明,将近一半的吸收的ARGs可以释放到新环境中并引起潜在的风险。总的来说,我们的研究结果提供了在抗生素污染的废水处理过程中ARGs的命运的基本理解和对生物炭的多种作用的新见解,这可能会给生态系统和人类健康带来额外负担。
    Advanced oxidation processes based on persulfate activation by biochar have been widely used to remove antibiotics and antibiotic resistance genes (ARGs) from wastewater. In this study, we used a common continuous fixed-bed reactor based on a biochar/persulfate system to treat wastewater. The average apparent ARG-removal efficiency was 82.38% in the biochar/persulfate reactor. The results of continuous reactor activity suggested the presence of ARG residues in the biochar (the abundance of ARG in the biochar increased 103-fold) and unstable removal of extracellular ARGs, raising concerns about a potential environmental burden. Kinetic experiments showed that the absolute abundance of intracellular ARGs (iARGs) rapidly decreased 98.3% within 30 min, but extracellular ARGs (eARGs) correspondingly increased 15-fold, suggesting that persulfate broke bacterial cells open and quickly released iARGs as eARGs. Moreover, the proportions of the three types of ARGs showed that ARG removal was attributed to about 70% degradation and 30% adsorption by the biochar/persulfate reactor. Further analysis revealed that biochar acts as a special shelter for ARGs. Release experiment of used biochar indicated that nearly half of absorbed ARGs could be released into new environment and causing potential risk. Overall, our findings provide a fundamental understanding of the fate of ARGs during treatment of antibiotic-contaminated wastewater and new insights into the multiple roles of biochar, which can potentially represent an additional burden on ecosystems and human health.
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  • 文章类型: Journal Article
    利巴韦林(RBV),被广泛用于治疗病毒性疾病,如COVID-19,由于其在水环境系统中的长期存在和健康风险,被认为是主要的新兴污染物之一。然而,关于有效去除RBV的研究仍然不足。在这项研究中,我们研究了RBV在UV/氯/Fe(II)过程中的降解动力学和机理。在UV/氯/Fe(II)工艺中,RBV的降解速率常数kobs-RBV为2.52×10-4s-1,比单独的氯和UV/氯工艺增加了1.6倍和1.3倍,分别。值得注意的是,痕量Fe(II)通过Fe2+/Fe3+循环促进紫外/氯体系中RBV的降解,提高反应性物种如HO·和某些物种反应性氯自由基(RCS)的产率。HO·和RCS对RBV降解的贡献分别为53.91%和16.11%,分别。具体来说,Cl·,ClO·,和Cl2·-占8.59%,2.69%,和4.83%的RBV去除。RBV降解途径表明,反应性物种优先攻击RBV的酰胺部分,它裂解了醚键和羟基。对RBV降解产物的毒性评估表明,UV/氯/Fe(II)工艺有利于RBV的解毒。
    Ribavirin (RBV), which is extensively used to treat viral diseases such as COVID-19, is considered one of the major emerging contaminants due to its long-term existence and health risk in the aqueous environmental system. However, research on effective removal of RBV still remains insufficient. In this study, we investigated the RBV degradation kinetics and mechanism in UV/chlorine/Fe(II) process. The degradation rate constant kobs-RBV of RBV was 2.52 × 10-4 s-1 in UV/chlorine/Fe(II) process, which increased by 1.6 times and 1.3 times than that in chlorine alone and UV/chlorine process, respectively. Notably, trace amount Fe(II) promoted RBV degradation in UV/chlorine system through Fe2+/Fe3+ cycles, enhancing the yield of reactive species such as HO· and certain species reactive chlorine radicals (RCS). The contributions of HO· and RCS toward RBV degradation were 53.91% and 16.11%, respectively. Specifically, Cl·, ClO·, and Cl2·- were responsible for 8.59%, 2.69%, and 4.83% of RBV removal. The RBV degradation pathway indicated that the reactive species preferentially attacked the amide moiety of RBV, which cleaved the ether bond and the hydroxyl group. The toxicity evaluation of RBV degradation products elucidated that UV/chlorine/Fe(II) process was beneficial for RBV detoxification.
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