城市污水二级处理出水中不同种类PPCPs的臭氧氧化效果与机制研究

研究了臭氧氧化对城市污水二级处理出水中15种典型药品和个人护理品（PPCPs）的去除效果及O₃分子氧化和·OH自由基氧化的贡献.结果表明,PPCPs的臭氧氧化去除效果与其亲核官能结构特性相关,芳香胺结构为主的PPCPs易降解,烷基胺结构为主的PPCPs可部分降解,亲核特性较弱的双键为主的PPCPs难降解;在臭氧投加量为5.5 mg·L^-1条件下,这3类PPCPs的去除率为分别为大于95%、57%~68%和39%~57%.臭氧氧化过程中,O₃分子氧化和·OH自由基氧化均起重要作用.易降解PPCPs的氧化机制以O₃分子氧化为主,贡献率为82%~91%;可降解和难降解PPCPs的氧化机制以·OH自由基氧化为主,贡献率分别为48%~71%和66%~94%.二级出水中臭氧氧化过程中,UVA₂₅₄去除率可呈单线性或分段线性指示PPCPs的去除效率.     

碳纳米管负载纳米四氧化三铁多相类芬顿降解亚甲基蓝

在课题组前期研究的基础上,以碳纳米管(MWCNTs)为载体制备了Fe3O4/MWCNTs复合物并作为催化剂,以染料亚甲基蓝(MB)为降解对象,研究了该催化剂催化H2O2对亚甲基蓝溶液的降解特性及其影响因素,并考察了催化剂的重复使用效果,探讨了催化反应的机理.结果表明,在pH值3~8的范围内,催化反应体系都能有效降解MB,最佳pH值为3.5.随着催化剂投量的增加,MB的降解率明显提高,500 mg·L-1催化剂投量条件下,MB的降解率最高.随着H2O2初始浓度的增加,MB的降解率增加,10 mmol·L-1时MB的降解率最高.溶液中共存的阴离子会降低MB的降解率.在最佳条件,即温度25℃、H2O2浓度10 mmol·L-1、催化剂浓度500 mg·L-1的条件下,0.20 mmol·L-1MB在30 min内的降解率达到99.1%.催化剂重复使用后仍然具有较好的催化活性,说明Fe3O4在MWCNTs表面负载比较牢固,催化剂具有反复使用的能力.催化反应机理是催化剂催化H2O2产生羟基自由基,高活性的羟基自由基氧化MB.     

Heterogeneous Fenton-like degradation of 4-chlorophenol using iron/ordered mesoporous carbon catalyst

Ordered mesoporous carbon supported iron catalysts(Fe/OMC) were prepared by the incipient wetness impregnation method and investigated in Fenton-like degradation of 4-chlorophenol(4CP) in this work. XRD and TEM characterization showed that the iron oxides were well dispersed on the OMC support and grew bigger with the increasing calcination temperature. The catalyst prepared with a lower calcination temperature showed higher decomposition efficiency towards 4CP and H2O2, but more metals were leached. The effect of different operational parameters such as initial pH, H2O2 dosage, and reaction temperature on the catalytic activity was evaluated. The results showed that 96.1% of 4CP and 47.4% of TOC was removed after 270 min at 30°C, initial pH of 3 and 6.6 mmol/L H2O2. 88% of 4CP removal efficiency was retained after three successive runs, indicating Fe/OMC a stable catalyst for Fenton reaction. 4CP was degraded predominately by the attack of hydroxyl radical formed on the catalyst surface and in the bulk solution due to iron leaching. Based on the degradation intermediates detected by high performance liquid chromatography, possible oxidation pathways were proposed during the 4CP degradation.     

Combination of heterogeneous Fenton-like reaction and photocatalysis using Co-TiO2 nanocatalyst for activation of KHSO5 with visible light irradiation at ambient conditions

A novel coupled system using Co–Ti O2 was successfully designed which combined two different heterogeneous advanced oxidation processes, sulfate radical based Fenton-like reaction（SR-Fenton） and visible light photocatalysis（Vis-Photo）, for degradation of organic contaminants. The synergistic effect of SR-Fenton and Vis-Photo was observed through comparative tests of 50 mg/L Rhodamine B（Rh B） degradation and TOC removal. The Rhodamine B degradation rate and TOC removal were 100% and 68.1% using the SR-Fenton/Vis-Photo combined process under ambient conditions, respectively. Moreover, based on XRD, XPS and UV-DRS characterization, it can be deduced that tricobalt tetroxide located on the surface of the catalyst is the SR-Fenton active site, and cobalt ion implanted in the Ti O2 lattice is the reason for the visible light photocatalytic activity of Co–Ti O2. Finally, the effects of the calcination temperature and cobalt concentration on the synergistic performance were also investigated and a possible mechanism for the synergistic system was proposed. This coupled system exhibited excellent catalytic stability and reusability,and almost no dissolution of Co2＋was found.     

Herbicide Roundup® and its main constituents cause oxidative stress and inhibit acetylcholinesterase in liver of Carassius auratus

Roundup® is a glyphosate-based herbicide containing a mixture of surfactants. This paper evaluates the toxic effects of Roundup® and its main constituents on the goldfish, Carassius auratus, after 7 days exposure. Fish were exposed to 0.16, 0.032 and 0.0064 mg/L of Roundup® [containing 41% isopropylamine salt of glyphosate (G.I.S) and 18% polyoxyethylene amine (POEA)], G.I.S, and POEA. Their livers were taken for determining reactive oxygen species (ROS), superoxide dismutase (SOD) activity, malondialdehye (MDA) content and acetylcholinesterase (AChE) activity. Hydroxyl radical (·OH) could be induced by exposing Roundup® at a rate of 43%–111%, G.I.S at 90%–124% and POEA at142%–157%. A decreased SOD activity was observed in fish exposed to G.I.S and POEA. The contents of MDA significantly increased when exposed to Roundup® at all concentrations, 0.16 mg/L G.I.S and 0.032 mg/L POEA. The exposure led to an inhibition of AChE in livers overall during the experimental periods. POEA was more toxic than Roundup® or G.I.S during this experiment. AChE and ·OH are supposed to be sensitive biomarkers of the exposure of Roundup® and its main constituents to C. auratus.     

Aniline degradation by electrocatalytic oxidation

The degradation of aniline solution in alkaline medium of pH 11.0 by electrocatalytic oxidation has been studied using an electrochemical reactor containing a SnO₂–Sb₂O₃–PtO anode and a Ti cathode, both of 54 cm² area. Hydroxyl radicals (HO^√) are produced at the anode, being tested with the trace catcher salicylic acid and phenol by spectrophotometery and high performance liquid chromatography. Intermediates dianiline, 4-anilino phenol and azobenzol were detected by gas chromatography–mass spectrometry. The existence of HO^√ produced in the aniline degradation was assayed with scavenger tertiary butanol. The results showed that electrocatalytic oxidation is an effective process for the degradation of aniline. A general reaction pathway that accounts for aniline degradation to CO₂ involving those intermediates is proposed.     

高级氧化技术处理垃圾渗滤液的研究进展

本文介绍了包括化学氧化法、电化学氧化法、光催化氧化法、超声氧化法、辐照氧化法和催化湿式氧化法等在内的高级氧化技术的机理和运用于垃圾渗滤液处理的研究进展,并提出高级氧化技术与生物处理联合运用和各种高级氧化工艺之间的优化组合将是实现高级氧化技术在垃圾渗滤液处理中工程化运用的发展方向.     

水相中羟基自由基诱导二甲基硫氧化的研究

用激光闪光光解技术研究了水相中二甲基硫(DMS)与羟基自由基(·OH)的反应机理,并讨论了溶液pH值和O2对该反应的影响,进而比较了气液相DMS与·OH反应的不同,初步评估了由·OH氧化引起的海洋和大气液相中DMS的寿命.结果表明:在pH 6-9时, ·OH会与DMS反应生成·DMSOH, ·DMSOH在水相中继续与DMS反应生成(DMS) 2, (DMS) 2与氧气的反应速度很慢,其衰减受pH影响较大.