羟基自由基检测技术方法概述

高级氧化技术（ AOP）是一种新兴的氧化处理技术,而羟基自由基（·OH）是高级氧化技术中一种重要的中间体,具有很强的氧化能力,是一种高效环保的氧化剂,近年将其用于烟气中有害气体氧化脱除的技术方法多有研究。列举了羟基自由基的检测方法,包括：电子自旋捕集法（ ESR）、高效液相色谱法（ HPLC）、分光光度法、荧光光度法（ FD）等方法,这些方法对科研工作者检测羟基自由基提供了一定的技术支持,并对今后的研究方向起到一定的指导作用。     

羟基自由基抑制剂对臭氧氧化降解苯酚的影响

采用臭氧氧化法处理模拟苯酚废水,考察了废水pH以及HCO₃^-、CO₃^2-、HPO₄^2-、H₂PO₄^-和叔丁醇等·OH抑制剂对苯酚降解效果的影响。实验结果表明：苯酚降解率随废水pH的增大而增大;当废水pH=11时,降解25 min后苯酚降解率达到99.55%,比废水pH=5时提高了50.12百分点;CO₃^2-和H₂PO₄^-对·OH的抑制作用分别强于HCO₃^-和HPO₄^2-;当叔丁醇质量浓度由0增至50 mg/L时,苯酚降解率由99.55%降至69.19%。     

城市大气颗粒物表面半醌自由基的测定方法

采集上海市城区和郊区2个典型站位的大气颗粒物样品,以二氯甲烷作萃取溶剂,采用索氏抽提法萃取分离吸附在颗粒物表面的稳定自由基,并利用电子自旋共振波谱技术(ESR)分析测定其种类和浓度。结果表明,测试样品的波谱特征表现为显著的三重信号峰,且g因子值均为2.002 7~2.004 7,通过与醌类物质的碱性饱和溶液ESR图谱比对,可以推断颗粒物表面至少吸附一种邻位半醌自由基。同时,通过锰标定量的方式估算了闵行和普陀2个采样点颗粒物样品表面的半醌自由基浓度,闵行采样点TSP、PM10和PM2.5表面半醌自由基的平均浓度分别为5.02×105、5.54×105、9.43×105g-1,而普陀采样点的平均浓度分别为2.02×105、3.50×105、7.16×105g-1。     

静电场和聚乙二醇等处理对大豆种子抗吸胀冷害的促进作用的比较

用正、负高压静电场（HVEF）,聚乙二醇（PEG）,氯化钙（CaCl2）和二甲基亚矾（DMSO）等方法预处理大豆种子,比较种子抗低温吸胀冷害的能力结果表明：负高压静电场处理能促进膜相转变或损伤修复,并能在低温吸胀时减少无机离子,有机大分子物质的外渗;还能提高种子内自由基清除酶系的活性,促进糖原和贮存蛋白的代谢及生长调节物质的水平比较几种处理方法的效果表明：高压静电场处理主要提高自由基清除酶系和基础代谢酶的活性,而对吸胀时的膜损伤修复的促进效果较小;聚乙二醇和氯化钙则在促进种子吸胀时的睦相转变和膜损伤修复方面有显著作用所有的处理方法均在不同程度上抑制羟自由基（HO）的产生,从而减轻膜脂质过氧化的伤害.     

对氯苯甲酸用于测量OH#方法探讨1.机理研究

对氯苯甲酸被用于臭氧氧化过程中羟基自由基的测量,为了检验对氯苯甲酸是否在测量过程中出现误差,进行了臭氧氧化对氯苯甲酸的间歇实验和半连续实验.结果表明,中性条件下间歇试验中,对氯苯甲酸可以强烈促进臭氧分解,它促进臭氧分解的能力比典型的促进剂甲酸和甲醇高10倍.半连续试验的结果进一步表明,臭氧氧化对氯苯甲酸时,可以形成中间产物过氧化氢,过氧化氢能和臭氧反应,形成大量的OH.,从而改变O3/OH.的链式反应,导致采用对氯苯甲酸测量OH.时出现误差.     

Effect of natural aquatic humic substances on the photodegradation of bisphenol A

The photochemical degradation of bisphenol A (BPA) was studied in the presence of natural humic substances from different origins under simulated solar irradiation. BPA underwent insignificant direct photolysis in neutral water, but rapid photosensitized degradation in four humic substances solutions via pseudo-first-order reaction occurred. The photo-degradation rate of BPA was insensitive to the different initial BPA concentrations and was inhibited in aerated solution compared with the deoxygenated medium. The reactive oxygen species (ROS) such as ·OH and ¹O₂ produced from excitation of humic substances under irradiation was determined from the quenching kinetic experiment using molecular probe. The five main intermediate photoproducts of BPA in Nordic lake fulvic acid (NOFA) were tentatively identified using gas chromatography/mass spectrometer (GC/MS). Based on the identification of ROS and the analysis of photoproduct formation, the possible phototransformation pathways of BPA were proposed, involving the direct photolysis due to the energy transfer from the triplet state humic substance (³HS*) to BPA molecules and hydroxyl radical addition and oxidation as well. Translated from Acta Scientiae Circumstantiae, 2005, 25(6): 816–820 [译自: 环境科学学报]     

Insight into phase structure-dependent soot oxidation activity of K/MnO2 catalyst

In the present study, two nanosized MnO₂ with β and δ phase structures and potassium loaded MnO₂ catalysts with varied K loading amounts (denoted as K/MnO₂) were prepared. Temperature programmed oxidation and isothermal reactions in loose contact modes were employed to examine the soot oxidation activity of the as-prepared catalysts. Characterization results show that as compared with β-MnO₂, δ-MnO₂ has larger surface area and higher content of hydroxyl groups. Upon K loading, abundant hydroxyl groups in δ-MnO₂ effectively sequestrate K cation to form bound K species and free K species are available only at K loading above 3.0 wt.%. In contrast, the majority of K species present as free state in β-MnO₂ even at a K loading of 1.0 wt.% due to its very low hydroxyl group content. The O₂ temperature-programmed desorption (O₂-TPD) demonstrates that the catalysts with free K species exhibit strong ability in activating gaseous O₂, whereas the catalysts only having bound K display minor O₂ activation capability. As a result, despite of slightly lower activity of β-MnO₂ than δ-MnO₂, the K/β-MnO₂ catalysts exhibit substantially higher activities than K/δ-MnO₂ catalysts with identical K loadings. The finding in this study clearly demonstrates that for MnO₂ based catalysts, the enhancement of catalytic activity for soot oxidation is highly K loading amount dependent and the dependency is strongly associated with the phase structure of MnO₂.     

水处理中的高级氧化技术

随着水质污染的日益严重,以产生大量自由基为主体的高级氧化技术越来越受到人们的关注.本文综述了O3/H2O2,O3/uV,H2O2/uV和催化臭氧化几种高级氧化技术在水处理中的应用及其反应机理,并对其发展前景进行了分析.     

相对速率法测OH自由基与几种低碳醇的反应速率常数

在 2 99± 2K温度下 ,以甲醇为参照物 ,采用相对速率方法得到了几种醇与OH自由基在气相中的反应速率常数 ,这些速率常数分别为 (单位为 :10 5m3·mol-1·s-1) :乙醇k1=17 6 ,正丙醇k2 =35 2 ,2 丙醇k3=31 2 ,正丁醇k4 =48 2 ,2 甲基—1 丙醇k5=6 2 0 ,2 甲基— 2 丙醇k6=5 36 ,正戊醇k7=5 1 4,3 甲基— 1 丁醇k8=6 8 6 .其中 2 甲基— 1 丙醇的速率常数在本文中是首次报道 .根据各自的反应速率常数计算得到它们在大气中的平均寿命分别为 :τ1=95 1h ,τ2 =47 5h ,τ3=5 3 6h ,τ4 =34 7h ,τ5=2 7 0h ,τ6=312h ,τ7=32 6h ,τ8=2 4 4h .     

超声活化过硫酸盐降解甲基橙的影响因素研究

利用频率为40 kHz的超声（US）活化过硫酸盐（PS）氧化降解甲基橙.系统研究了超声（US）声强、过硫酸盐（PS）浓度对US/PS组合工艺降解甲基橙的影响.采用单独超声（US）或单独过硫酸盐（PS）时，甲基橙的降解率随US声强和PS浓度的增加而增大.在PS浓度为0.5~3 mmol·L^-1和US声强为0.22~0.54 W·cm^-2条件下，60 min时甲基橙的最大降解率分别为52.22%和16.7%.采用US/PS高级氧化工艺时，甲基橙的降解率也随PS浓度和US声强的增加而增大，60 min时甲基橙的最大降解率高达87.38%，比单独US和PS提高70.68%和35.16%.同种条件下，TOC的降解率小于甲基橙的降解率.甲醇和叔丁醇（自由基抑制剂）的加入降低甲基橙的降解率，且甲醇对甲基橙降解的抑制程度更明显.US/PS高级氧化工艺对甲基橙的降解主要依靠硫酸根自由基.