·OH的形成机理及在水处理中的应用

以产生大量·OH为特点的高级氧化水处理技术已逐渐成为各国水处理技术研究的热点。在讨论·OH氧化能力的同时 ,重点讨论了Fenton法、纳米光催化氧化法、电化学催化降解法以及超声降解法·OH的形成机理 ,介绍了它们在水处理中的工业化应用及进展情况 ,展望了今后在该领域中多种氧化降解方法协同作用的发展方向     

投加粉末活性炭对一体式膜-生物反应器膜污染的影响研究

通过试验考察了粉末活性炭（PAC）对一体式膜-生物反应器中膜污染的影响．在2种类型的污泥（膨胀污泥和非膨胀）中，投加适量PAC可以减轻膜污染，表现为临界膜通量的提高和连续运行中膜污染增长速率的降低．当污泥性质和浓度不同时，最佳PAC投加范围亦不同．PAC投量过大会引起临界通量下降．PAC的投加显著降低了混合液中溶解性物质的浓度，减轻了溶解性物质的吸附和膜孔堵塞污染，并改善了絮体结构．污泥比阻与污泥混合液膜过滤性能之间有很好的相关性，可作为污泥混合液膜过滤性能的快速评价指标．     

羟基自由基杀灭压载水赤潮入侵生物试验研究

采用羟基自由基对斯式根管藻、日本星杆藻、裸甲藻和细菌进行杀灭实验，确定杀灭入侵赤潮生物的所需OH^-比值浓度为0.68mg／L。当OH^-比值浓度达到0．68mg／L时，致死多甲藻(Peri.Spp)等10种赤潮生物效率达到99.8％，致死膝沟孢子、多甲藻孢子效率达到100％。试验数据表明，强电离先进氧化OH^-是治理赤潮有效、可行的绿色新方法。     

Isomer distribution of nitrotriphenylenes in airborne particles, diesel exhaust particles, and the products of gas-phase radical-initiated nitration of triphenylene

The formation of mutagenic nitro-polycyclic aromatic hydrocarbons (NPAHs) 1- and 2-nitrotriphenylene (1- and 2-NTP) via gas-phase OH or NO₃ radical-initiated reactions of triphenylene was demonstrated for the first time using a flow reaction system. In contrast with the results of conventional electrophilic nitration, 2-NTP was formed in larger yield than 1-NTP, but this is consistent with the mechanism proposed for gas-phase radical-initiated nitration of PAH. In diesel exhaust particle (DEP) samples, both 1- and 2-NTP were identified and their concentrations determined, as well as 1-nitropyrene (1-NP), which is a representative combustion-derived NPAH: the mean concentrations of 1-NTP, 2-NTP, and 1-NP were 4.7, 1.9, and 32 pmol mg_DEP^–1, respectively. The mean 2-NTP/1-NTP, 1-NTP/1-NP, and 2-NTP/1-NP ratios in samples of airborne particles collected in a residential area in Osaka, Japan, were>1.55,<0.25, and 0.37, respectively; these values are much higher than those of the DEP samples. This finding indicates that there is another source for airborne NTPs, especially 2-NTP, apart from diesel exhaust. These results strongly suggest that airborne NTPs originate from atmospheric processes such as radical-initiated reactions of triphenylene, and this has a significant influence on the atmospheric occurrence of NTPs.     

Modelling the environmental degradation of water contaminants. Kinetics and mechanism of the riboflavin-sensitised-photooxidation of phenolic compounds

The aerobic visible-light-photosensitised irradiation of methanolic solutions of either of the phenolic-type contaminants model compounds (ArOH) p-phenylphenol (PP), p-nitrophenol (NP) and phenol (Ph), and for two additional phenolic derivatives, namely p-chlorophenol (ClP) and p-methoxyphenol (MeOP), used in some experiments, was carried out. Employing the natural pigment riboflavin (Rf) as a sensitiser, the degradation of both the ArOH and the very sensitiser was observed. A complex mechanism, common for all the ArOH studied, operates. It involves superoxide radical anion (O₂^√−) and singlet molecular oxygen (O₂(¹Δ_g)) reactions. Maintaining Rf in sensitising concentrations levels (≈0.02 mM), the mechanism is highly dependent on the concentration of the ArOH. Kinetic experiments of oxygen and substrate consumption, static fluorescence, laser flash photolysis and time-resolved phosophorescence detection of O₂(¹Δ_g) demonstrate that at ArOH concentrations in the order of 10 mM, no chemical transformation occurs due to the complete quenching of Rf singlet excited state. When ArOH is present in concentrations in the order of mM or lower, O₂^√− is generated from the corresponding Rf radical anion, which is produced by electron transfer reaction from the ArOH to triplet excited Rf. The determined reaction rate constants for this step show a fairly good correlation with the electron-donor capabilities for Ph, PP, NP, ClP and MeOP. In this context, the main oxidative species is O₂^√−, since O₂(¹Δ_g) is quenched in an exclusive physical fashion by the ArOH. The production of O₂^√− regenerates Rf impeding the total degradation of the sensitiser. This kinetic scheme could partially model the fate of ArOH in aquatic media containing natural photosensitisers, under environmental conditions.     

Optimizing electron spin resonance detection of hydroxyl radical in water

The parameters affecting the electron spin resonance (ESR) detection of hydroxyl free radical in water are studied and optimized. The hydroxyl radical is generated by the Fenton reaction with iron (II) ammonium sulfate and hydrogen peroxide reacting in a phosphate buffer using N-tert-butyl-alpha-phenylnitron as the spin trap. The concentrations of Fe²⁺, H₂O₂, and phosphate buffer are the parameters studied. The Taguchi method and the orthogonal experiment design were used to evaluate the effects of these parameters on the ESR signal intensity. By the analysis of the signal-to-noise ratio and the analysis of variance, the order of importance of the various parameters on the hydroxyl radical formation is determined for optimal ESR detection of hydroxyl radical. The results will help the development of water purification technologies using hydroxyl free radical as a green oxidant.     

Comparative study of the oxidation of atrazine and acetone by H2O2/UV, Fe(III)/UV, Fe(iii)/H2O2/UV and Fe(II) or Fe(III)/H2O2

In this study, the rates of degradation of organic compounds by several AOPs (H₂O₂/UV, Fe(III)/UV, Fe(III)/H₂O₂/UV, Fe(II)/H₂O₂ and Fe(III)/H₂O₂) have been compared. Experiments were carried out at pH ≈ 3 (perchloric acid / sodium perchlorate solutions) and with UV reactors equipped with a low-pressure mercury vapour lamp (emission at 253.7 run). The data obtained with atrazine ([Atrazine]_o = 100 μg/L) showed that the rate of degradation of atrazine in very dilute aqueous solution is much more rapid with Fe(III)/UV than with H₂O₂/UV. Photo-Fenton process (Fe(III)/H₂O₂/UV) was found to be more efficient than H₂O₂/UV and Fe(II)/H₂O₂ for the mineralization of acetone ([Acetone]_o = 1 mM).     

紫外活化甲酸产二氧化碳阴离子自由基还原Cr (VI)的研究

研究高效还原技术是去除废水中Cr（VI）的有效手段,本研究提出了一种新颖有前景的基于紫外（UV）活化甲酸（HCOOH）产还原性二氧化碳阴离子自由基（CO₂^•;-）去除Cr（VI）的方法.通过对比UV、HCOOH、UV/HCOOH三种体系对Cr（VI）还原效率和电子自旋共振（EPR）对体系中自由基的检测研究了其活化原理和还原机制.结果表明UV能显著活化HCOOH产生CO₂^•-（α_H=19.08G,α_N=15.86G,g=2.0036）.此外,试验考察了主要影响因素对Cr（VI）去除效果的影响,包括初始Cr（VI）浓度、甲酸投加量、初始pH值、反应温度、有机污染物以及水中常见阴离子.结果显示当甲酸浓度为40mmol/L,Cr（VI）初始浓度为10mg/L,反应时间在60min内,UV/HCOOH体系对Cr（VI）的去除率能达到100%.在酸性条件下（pH≤3.5）能显著促进Cr（VI）的还原,且Cr（VI）去除效率随着初始HCOOH浓度和反应温度升高而增加.进一步研究表明,该体系下NO₃^-对Cr（VI）的还原有着显著的促进作用,而Cl^-、HCO₃^-和对硝基苯酚（pNP）则有抑制作用.不同温度下Cr（VI）去除率与时间关系的拟合结果表明,当反应时间t³;40min,UV/HCOOH体系去除Cr（VI）过程遵循准一级反应动力学,根据不同温度下对应的反应速率常数k,结合阿伦尼乌斯方程,计算求得准一级反应的活化能为15.9kJ/mol.     

植物配置与进水碳氮比对沉水植物塘水质净化效果的影响

将3种常见湖泊沉水植物苦草(Vallisneris spiralis)、轮叶黑藻(Hydrilla verticillata)、穗花狐尾藻(Myriophyllum spicatum)组合构建7种沉水植物稳定塘,分析植物组合对水体氮、磷、有机物去除效果;在此基础上,模拟不同碳氮比(C/N)条件下的沉水植物塘对污水的净化效果,进而探讨碳氮比对沉水植物去污效果的影响.结果表明:(1)7种沉水植物组合对氮、磷均具有一定的净化效果,其中苦草和轮叶黑藻组成的沉水植物塘净化效果最好.(2)3种C/N(1.89、5.93、12.09)条件下,苦草黑藻植物塘的去污效果有所差异,当C/N=5.93时,对污染物的综合去除效果最佳.因此对于沉水植物稳定塘而言,沉水植物组合能取得比单类植物更好的净水效果,并且通过添加适量碳源物质,调整污水的碳氮比,可以提升沉水植物塘的净水效果,研究结果对于实际工程构建稳定塘净化污水具有理论指导意义.