利用UVC去除低浓度苯的实验研究

探讨了不同实验参数对苯的UVC去除效果的影响,获得了苯的去除率与苯的初始浓度、气体流量、相对湿度和氧气含量等参数之间的关系。数据表明,在实验条件范围内,苯的去除率的倒数与苯初始浓度、气体流量之间为线性关系;苯的去除率随相对湿度的增加呈现先升高后缓慢降低的关系,最佳相对湿度值在30%～50%之间;苯的去除率随氧气量的增加而缓慢增加;波长为185+254 nm的UV与254 nm的UV相比净化效果更为理想。还分析了苯降解产生的中间产物,探讨了苯的降解机理。     

Evaluation of photolysis and hydrolysis of pyraclostrobin in aqueous solutions and its degradation products in paddy water

This study evaluated the hydrolysis and photolysis kinetics of pyraclostrobin in an aqueous solution using ultra-high-performance liquid chromatography–photodiode array detection and identified the resulting metabolites of pyraclostrobin by hydrolysis and photolysis in paddy water using high-resolution mass spectrometry coupled with liquid chromatography. The effect of solution pH, metal ions and surfactants on the hydrolysis of pyraclostrobin was explored. The hydrolysis half-lives of pyraclostrobin were 23.1–115.5?days and were stable in buffer solution at pH 5.0. The degradation rate of pyraclostrobin in an aqueous solution under sunlight was slower than that under UV photolysis reaction. The half-lives of pyraclostrobin in a buffer solution at pH 5.0, 7.0, 9.0 and in paddy water were less than 12?h under the two light irradiation types. The metabolites of the two processes were identified and compared to further understand the mechanisms underlying hydrolysis and photolysis of pyraclostrobin in natural water. The extracted ions obtained from paddy water were automatically annotated by Compound Discoverer software with manual confirmation of their fragments. Two metabolites were detected and identified in the pyraclostrobin hydrolysis, whereas three metabolites were detected and identified in the photolysis in paddy water.     

A study of the atmospheric reaction of CH3S with O3 as a function of temperature

The atmospheric reaction of the methylthiyl radical (CH₃S) with O₃ was investigated as a function of temperature (259–381 K), in the pressure range of 25–300 Torr, using the technique of laser photolysis/laser-induced fluorescence. The resulting Arrhenius expression, with an uncertainty of ±2σ, was k₁(T=259–381 K)=(1.02±0.30)×10⁻¹² exp[(432±77) K/T] cm³ molecule⁻¹ s⁻¹. The obtained rate constant k₁ was independent of pressure over the limited range employed. Our results are compared with the previous studies carried out, at single temperature and as a function of temperature, by different techniques.     

助溶剂甲醇对化学物质紫外光解的影响

在研究微量有机化学污染物的光化学行为时,为了增加难溶于水的药品溶解度,往往采用甲醇作助溶剂.但对反应体系中助溶剂甲醇对光化学反应的影响缺乏系统研究.以高压汞灯为光源,以萘普生(NP)及其光解产物NP1和NP2为研究对象,通过对比纯水、1%甲醇和1%异丙醇反应体系中的实验结果发现,少量助溶剂甲醇在紫外光照下对羟基自由基的淬灭效果接近于异丙醇.结合检测到的中间产物,推导了NP的光解路径主要为光致脱羧、羟基自由基夺氢、自由基耦合等反应过程.在助溶剂甲醇存在的体系中,甲醇能与萘普生发生酯化反应,并通过淬灭羟基自由基,影响萘普生的光解反应,从而导致实验结果误读.因此,在光化学实验研究中,应该排除助溶剂甲醇对实验结果的影响.     

乙烯菌核利在水溶液中的光解动力学

以高压汞灯和太阳光为光源,研究乙烯菌核利在重蒸水、自来水、湖水及pH缓冲液中的光解动力学。高压汞灯下,乙烯菌核利在重蒸水中的光解半衰期约为28 m in,而在太阳光下为3.86 h。自来水和湖水中溶解性物质对乙烯菌核利在高压汞灯下的光解动力学仅有微弱的淬灭效应,但在太阳光下表现出显著的敏化效应,照光3 h的敏化效率分别为138%和126%。2种光源下,pH 5.0和pH 7.0缓冲液对乙烯菌核利的光解均表现为光淬灭效应,高压汞灯照光60 m in的淬灭效率分别为69%和57%,太阳光照光7 h的淬灭效率分别为77%和33%;pH 9.0缓冲液则表现出显著的敏化效应,高压汞灯照光20 m in的敏化效率为58%,而太阳光照光1 h的敏化效率则达到了415%。     

磺酰脲类除草剂在硅胶G表面的光解

应用高效薄层析方法研究了苄嘧磺隆，甲磺隆，氯磺隆，氯嘧磺隆4种磺酰脲类除草剂在氙灯与太阳光下的光解动力学，以及8种有机色素对苄嘧磺隆光降解的影响。结果表明4种除草剂在硅胶G表面的降解呈一级动力学反应；有机色素对除草剂的降解均表现显著的猝灭效应。其中以姜黄素的猝灭作用最强，色素剂量与光解中的猝灭效应存在着显著的相关性。色素剂量加大，猝灭效应加强。     

308 nm光作用下α-Fe2O3表面HNO3的光解

采用紫外可见光谱(UV-Vis)、傅立叶变换红外光谱(FTIR)及离子色谱(IC)技术对HNO3在α-Fe2O3表面暗反应和308nm下光解反应进行了研究.考察了时间、HNO3浓度、相对湿度(RH)等条件对反应的影响.结果表明,随着HNO3浓度、光照时间的增加,HNO3在气相与α-Fe2O3表面光解产物浓度均呈指数增加;HNO3在α-Fe2O3表面光解产生的NO2、NO分别为气相产生的3.27及3.87倍,而无论气相还是表面光解的NO2浓度均约为NO的2倍.随着RH的增加,HNO3光解产生的HONO的浓度随之呈指数增大,其产率从RH 20%时的0.023增加到90%时的0.087.α-Fe2O3的表面效应在HNO3的表面光解反应中起主导作用.     

A photolysis coefficient for characterizing the response of aqueous constituents to photolysis

UV photolysis and UV based advanced oxidation processes (AOPs) are gaining more and more attention for drinking water treatment. Quantum yield (ø) and molar absorption coefficient (ε) are the two critical parameters measuring the effectiveness of photolysis of a compound. The product of the two was proposed as a fundamental measure of a constituent’s amenability to transformation by photolysis. It was shown that this product, named the photolysis coefficient, k _p , can be determined using standard bench tests and captures the properties that govern a constituent’s transformation when exposed to light. The development showed the photolysis coefficient to be equally useful for microbiological, inorganic and organic constituents. Values of k _p calculated by the authors based on quantum yield and molar absorption coefficient data from the literature were summarized. Photolysis coefficients among microorganisms ranged from 8500 to more than 600000 and are far higher than for inorganic and organic compounds, which varied over a range of approximately 10 to 1000 and are much less sensitive to UV photolysis than the microorganisms.     

Hydrolysis and photolysis of oxytetracycline in aqueous solution

Oxytetracycline ((2Z,4S,4aR,5S,5aR,6S,12aS)-2-(amino-hydroxy-methylidene)-4-dimethylamino-5,6,10,11,12a-pentahydroxy-6-methyl-4,4a,5,5a-tetrahydrotetracene-1,3,12-trione) is a member of tetracycline antibiotics family and is widely administered to farm animals for the purpose of therapeutical treatment and health protection. Increasing attention has been paid to the environmental fate of oxytetracycline and other veterinary antibiotics with the occurrence of these antibiotics in the environment. The hydrolysis and photolysis degradation of oxytetracycline was investigated in this study. Oxytetracycline hydrolysis was found to obey the first-order model and similar rate constant values ranging from 0.094 ± 0.001 to 0.106 ± 0.003 day^{? 1} were obtained at different initial concentration ranging from 10 to 230 μ M. Solution pH and temperature were shown to have remarked effects on oxytetracycline hydrolysis. The hydrolysis in pH neutral solution appeared to be much faster than in both acidic and alkaline solutions. Oxytetracycline half-life decreased from 1.2 × 10² to 0.15 day with the increasing temperature from 4 ± 0.8 to 60 ± 1°C. The presence of Ca^{2 +} made oxytetracycline hydrolytic degradation kinetics deviate from the simple first-order model to the availability-adjusted first-order model and greatly slowed down the hydrolysis. Oxytetracycline photolysis was found to be very fast with a degradation rate constant at 3.61 ± 0.06 day^{? 1}, which is comparable to that of hydrolysis at 60°C. The presence of Ca^{2 +} accelerated oxytetracycline photolysis, implying that oxytetracycline become more vulnerable to sunlight irradiation after chelating with Ca^{2 +}. The photolysis may be the dominant degradation pathway of oxytetracycline in shallow transparent water environment.     

蒽醌化合物的光解动力学及定量结构-性质关系

以高压汞灯为光源, 测定了15 种蒽醌化合物(ATQs)的光解速率常数(k), 讨论了取代基位置、数目及种类对ATQs 光解速率的影响.另外,选取9 种氨基蒽醌, 应用偏最小二乘(PLS)算法, 建立了关于k的定量结构-性质关系(QSPR)模型. 根据该模型, 决定k值大小的主要因素包括:分子生成热、H 原子所带最大正电荷、C 原子所带最大负电荷,以及分子最低未占据轨道与最高占据轨道能量差.