UV-vis光照下唑类抗菌药氟康唑的光化学反应类型

以唑类抗菌药氟康唑为模型化合物,考察了其在纯水中的光降解动力学和光化学反应类型,发现模拟日光(λ>290nm)照射下氟康唑未发生光解,在UV-vis(λ>200 nm)光照下,氟康唑发生了光降解并服从准一级反应动力学.采用活性氧物种猝灭实验和竞争动力学方法,研究发现氟康唑发生了直接光解和·OH参与的自敏化光解,氟康唑与.OH的反应速率常数为(5.95±0.58)×109L·(mol·s)-1,表层水体中相应的半减期为(32.41±3.16)h·通过鉴定光解产物,得知氟康唑发生了脱氟、光致水解、光氧化等光化学反应.     

树脂负载草酸铁光助类芬顿降解水中孔雀石绿

为了强化多相类芬顿反应的速率,在可见光下采用以草酸盐为配体的三价铁草酸络合物(Fe~(3+)C_2O_4/R)为催化剂催化过氧化氢降解水中孔雀石绿.结果表明,与Fe~(3+)/R相比催化剂Fe~(3+)C_2O_4/R具有更强的催化活性,能强化羟基自由基(·OH)的产生. 过氧化氢的初始浓度越高,反应速率越快,反应遵循一级反应动力学,反应速率常数与过氧化氢浓度具有很好的相关性.在pH值3～9的范围内,催化剂Fe~(3+)C_2O_4/R都能有效地对MG进行降解,最佳pH值为6.随着催化剂投量的增加,MG的去除效率明显提高.随着MG初始浓度的增加,MG的去除也由吸附为主转化为以氧化为主,但总体影响不大.催化剂重复使用后仍然具有较好的催化活性,说明铁在树脂表面负载比较牢固,催化剂具有反复使用的能力.反应中的氧化活性物种是羟基自由基和高价态铁同时共存.     

Determination of photochemically-generated reactive oxygen species (ROS) in natural water

Reactive oxygen species (ROS) can be produced by interactions between sunlight and light-absorbing substances in natural water environment. ROS may participate in the indirect photolysis of trace organic pollutants, therefore resulting in the changing of their environmental fates and ecological risks in natural water system. Bisphenol A (BPA), an endocrine-disrupting chemical, exits widely in natural water. The photodegradation of BPA promoted by ROS (·OH, 1O2, HO2·/O2·-) which were produced on the excitation of ubiquitous constituents (such as nitrate ion, humic substances and Fe(III)-oxalate complexes) in natural water under simulated solar radiation was investigated. Both molecular probe method and electron spin resonance (ESR) test were used for the determine the characterization of generated ROS. It was found that ·OH was photochemically produced with the presence of nitrate ion, humic substances and Fe(III)-oxalate complexes and 1O2 was produced with the presence of humic substances. The steady-state concentrations of ·OH was 1.27×10-14 mol/L in nitrate ion, and the second-order rate constant of BPA with ·OH was 1.01×1010L/( mol·s).     

Determination of photochemically-generated reactive oxygen species in natural water

Reactive oxygen species(ROS) can be produced by interactions between sunlight and light-absorbing substances in natural water environment.ROS may participate in the indirect photolysis of trace organic pollutants,therefore resulting in changes in their environmental fates and ecological risks in natural water systems.Bisphenol A(BPA),an endocrine-disrupting chemical,exits widely in natural waters.The photodegradation of BPA promoted by ROS(.OH,1O2,HO2./O2·-),which were produced on the excitation of ubiquito...     

无机阴离子对CuO-H2O2氧化苯酚废水的影响

以苯酚为模型底物,研究了中性低温常压条件下无机阴离子对CuO-H₂O₂氧化苯酚废水的影响及机制.结果表明,CuO-H₂O₂能高效彻底氧化苯酚,10 min氧化率达94.7%,氧化遵循羟基自由基机制.无机阴离子对氧化效果有不同影响,浓度越高影响越显著.HCO^-₃加速H₂O₂的无效分解,当浓度从0增加到20 mmol·L^-1 时,H₂O₂分解速率常数由0.373 8 min^-1提高到0.534 7 min^-1,TOC去除速率常数由0.267 min^-1下降到0.019 4 min^-1.HPO^2-₄通过抑制H₂O₂分解实现对苯酚的氧化抑制,H₂O₂分解速率常数及TOC去除速率常数分别由0.373 8 min^-1、0.267 min^-1降低到0.033 8 min^-1、 0.033 8 min^-1.Cl^-能够促进H₂O₂有效分解,对苯酚氧化有利,H₂O₂分解速率常数及TOC去除速率常数分别由0.373 8 min^-1、0.267 min^-1提高到0.604 0 min^-1、0.387 9 min^-1.NO^-₃、SO^2-₄对H₂O₂的分解及苯酚的氧化影响不大.     

脉冲放电处理苯酚废水降解过程的分析

由于水中脉冲放电产生等离子体通道,水会发生复杂的等离子体化学反应,产生各种自由基,本文检测到放电形成的羟基自由基.对苯酚废水进行放电降解研究,利用紫外分光计、有机碳分析仪、液相质谱联用仪和气相质谱仪等仪器对降解产物进行检验.结果表明,苯酚废水在放电作用下生成的中间产物为:多羟基苯酚、酮、醛和酯等,最终产物为二氧化碳和水.此结果对苯酚废水在脉冲放电,甚至直流或交流电下的苯酚降解机理的进一步研究有参考价值.     

水体系中EDTA-Fe(Ⅱ)/Ｋ２Ｓ２Ｏ８降解敌草隆的研究

对水体系中EDTA-Fe(Ⅱ)/K2S2O8降解敌草隆的方法进行了研究.在综合考虑经济性和降解率的前提下,提出了反应的最佳条件:K2S2O8初始浓度为2.0 mmol·L-1, Fe(Ⅱ)初始浓度为1.0 mmol·L-1, EDTA初始浓度为0.5 mmol·L-1,反应时间为300 min, pH=7.0,最终0.1 mmol·L-1,敌草隆降解率可达67.6%.同时,采用分子探针竞争实验鉴定了体系中产生的硫酸根自由基和羟基自由基,并采用LC/MS法鉴定了敌草隆的主要降解产物,从而探讨了敌草隆在EDTA-Fe(Ⅱ)/K2S2O8体系中可能的降解途径.     

Determination of atmospheric hydroxyl radical by HPLC coupled with electrochemical detection

The hydroxyl radical (·OH) plays a central role in the oxidation and removal of many atmospheric compounds. Measurement of atmospheric·OH is very difficult because of its high reactivity and low atmospheric abundance. In this article, a simple and highly sensitive method, high performance liquid chromatography coupled with coulometric detection (HPLC-CD), was developed to determine·OH indirectly by determining its reaction products with salicylic acid (SAL), 2,3-dihydroxybenzoic acid (2,3-DHBA), and 2,5-dihydroxybenzoic acid (2,5-DHBA). Under the optimum conditions for its determination, 2,3-DHBA and 2,5-DHBA could be well separated and the detection limits for 2,3-DHBA were 3×10~(-10) mol/L and for 2,5-DHBA were 1.5×10~(-10) mol/L, which were lower than most previous reports. This method was also applied to measure atmospheric hydroxyl radical levels and demonstrated the feasibility in clean and polluted air.     

均相Co/PMS系统降解吡虫啉的影响因素及降解途径研究

过渡态Co^2+-催化分解KHSO₅(Co/PMS)系统是一种新型的高级氧化技术,其反应体系可以产生强氧化性的硫酸自由基(SO^·-₄).以杀虫剂吡虫啉为目标污染物,重点研究了溶液中PMS浓度、Co^2+-浓度和无机阴离子(H₂PO^-₄、HCO^-₃、NO^-₃和Cl^-)对Co/PMS系统降解吡虫啉的影响.结果表明,吡虫啉的降解遵循准一级动力学,其降解速率与氧化剂PMS浓度和催化剂Co^2+-的浓度呈正相关.吡虫啉的降解速率随着PMS和Co^2+-浓度的增加而增大,但是当PMS与吡虫啉的摩尔比大于20时,增加PMS的浓度对吡虫啉的降解速率反而有一定程度的抑制.H₂PO^-₄能促进Co/PMS系统对虫啉的降解;低浓度的HCO^-₃促进吡虫啉的降解,高浓度则为抑制作用;Cl^-抑制吡虫啉的降解,而NO^-₃则对整个降解过程影响不明显.研究中采用GC/MS分析吡虫啉降解的中间产物,得到了6-氯烟酸和6-氯烟酰胺2种主要的中间产物,并由此推测其可能的降解途径.     

西安地区PM2.5中环境持久性自由基(EPFRs)性质及来源研究

环境持久性自由基(environmental persistent free radicals, EPFRs)是一种近年来备受关注的环境风险物质,可能会危害人体健康.本研究利用溶剂萃取方法从西安市大气PM_(2.5)样品中分离出物质,运用电子顺磁共振波谱(EPR)技术分析了不同大气污染状况下大气PM_(2.5)样品及类黑碳成分中EPFRs的种类和含量,并分别测定PM_(2.5)和类黑碳成分催化H_2O_2产生羟基自由基的能力.结果表明:PM_(2.5)中的EPFRs约有85%～90%是由类黑碳成分产生的.可见光照(400～700 nm)前后,PM_(2.5)样品中EPFRs的含量增加10%～20%.此外,实验结果亦表明PM_(2.5)中能催化H_2O_2产生羟基自由基的物质主要是PM_(2.5)中水溶性物质而不是类黑碳.大气PM_(2.5)中的EPFRs没有显著催化H_2O_2产生羟基自由基的能力,也不能将O_2分子转化为活性氧物质.