节球藻毒素的紫外光降解研究

为优化节球藻毒素(NOD)光解处理的最佳光源及反应条件,利用自制光反应装置研究了NOD在暗反应、可见光、暗反应+TiO_2、可见光+TiO_2及单独紫外光(UVA、UVB、UVC)处理下的去除效果,继而选择UVC作为最佳光源进行后续实验,探讨NOD初始浓度、温度、p H和光强对NOD去除效果的影响及反应动力学.结果表明:暗反应、可见光、可见光+TiO_2的组合、UVA和UVB均对NOD无显著去除作用,最高去除率约为20%;UVC处理可以快速去除水中NOD,其去除过程符合二级动力学.UVC处理时,pH对NOD的去除无显著影响;温度升高,NOD去除率缓慢增大,但组间差异并不显著;初始浓度越大,NOD去除率越低;光强增大,NOD去除率快速升高,但到达一定临界值后保持稳定状态.3种因素对UVC去除NOD的影响程度由大到小分别为:光强时间温度.光强318μW·cm~(-2)、p H=7、温度30℃、反应时间4 h为最佳处理条件,此时NOD去除率最高,初始浓度为0.1μg·m L~(-1)的NOD几乎被完全去除,残留浓度低于WHO及我国规定的藻毒素含量限值.研究表明,UVC光解NOD安全高效,是一种非常理想的NOD去除方法.     

Photochemical degradation of methylparathion in the presence of humic acid

Photochemical degradation of methylparathion (O,O,-dimethyl O-4 nitrophenylphosphorothioate) in the presence of humic acid between pH 2 and 7 was monitored by differential pulse polarography. Humic acid was not electro-active under the experimental conditions used in this study. Only the pesticide and its main degradation product at pH 2 exhibited polarographic signals. Photolysis of methylparathion in acid media was sensitized by humic acid since the pesticide did not degrade in the absence of this compound. Methylparathion degradation in the presence of humic acid was observed at each of the studied pHs. The reaction was first-order with rate constant values ranging from 2 × 10^?3 to 6.3 × 10^?3 min^?1.     

水中普萘洛尔的紫外光降解机制及其产物毒性

以高压汞灯为光源,研究了紫外光照条件下水中普萘洛尔(PRO)的光解行为、机制及安全性.PRO光解机制通过活性氧物种(ROS)猝灭实验来确定,光解产物安全性通过发光菌毒性实验来评价.结果表明,PRO的光解速率常数(k)随初始浓度的增加而下降,两者呈显著负相关关系(r2>0.95).随着溶液初始pH的升高,PRO的光解加快,pH 5~9的PRO溶液的k值为0.0953~0.267 min-1.ROS猝灭实验表明,PRO的紫外光解过程包括了激发三重态PRO(3PRO*)参与的直接光解,以及羟基自由基(·OH)和单线态氧(1O2)参与的自敏化光解,直接光解速率常数大于自敏化光解速率常数.采用FFA探针方法测定了不同实验条件下1O2的浓度,其总体变化规律与猝灭实验所得结论一致.发光菌毒性实验表明,PRO光解生成了比母体化合物毒性更强的中间产物.     

Photo-oxidation and Photo-toxicity of Crude and Refined Oils

The fate and effects of an oil spill are effected by solar radiation through the action of photo-oxidation and photo-toxicity. Photo-oxidation, an important process in the weathering of oil, produces a variety of oxidized compounds, including aliphatic and aromatic ketones, aldehydes, carboxylic acids, fatty acids, esters, epoxides, sulfoxides, sulfones, phenols, anhydrides, quinones and aliphatic and aromatic alcohols. Some of these compounds contribute to the marine biota toxicity observed after an oil spill. Photo-toxicity occurs when uptake of certain petroleum compounds, e.g. certain polycyclic aromatic hydrocarbons and benzothiophenes, is followed by solar exposure which results in much greater toxicity than after dark uptake. The mechanism of PAH photo-toxicity includes absorbance of solar radiation by the PAH which produces a free radical and this free radical in turn reacts with oxygen to produce reactive oxygen species that can damage DNA and other cellular macromolecules. While most studies on photo-toxicity have been carried out in the laboratory, there are studies showing that water from an oil spill is photo-toxic to bivalve embryos for at least a few days after the spill. Other studies have found that oil contaminated sediments are photo-toxic to several marine invertebrates. More studies are required to determine if marine fauna at an oil spill site are effected by the action of photo-toxicity and photo-oxidation.     

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.     

光诱导下农药的化学转化及其环境意义

农药在光诱导下进行的化学转化是重要的非生物转化途径,其过程和产物对农药药效、代谢、毒性及环境影响重大.近年来,在国外已成为十分活跃的研究领域.本文着重论述农药环境光化学基本概念,主要光化学反应类型及光诱导下农药化学转化的环境意义。     

十溴联苯醚环境修复技术的研究进展

介绍了溴代阻燃剂十溴联苯醚（BDE-209）环境修复技术的研究进展。从光降解、零价铁降解、生物降解3个方面对BDE-209的降解机理和降解后的产物进行了介绍。BDE-209经光照、厌氧微生物、零价铁的脱溴作用后,降解成低溴代联苯醚产物;好氧微生物利用低溴代联苯醚作为生长碳源,将其在酶的作用下开环降解,进入三羧酸循环或彻底分解成CO₂和H₂O。提出应采用多种方法协同作用,更有效地降解多溴联苯醚化合物。     

Phototransformation of ibuprofen and ketoprofen in aqueous solutions

The UV (254 nm) and UV/VUV (254/185 nm) photolysis of two anti-inflammatory drugs, ibuprofen and ketoprofen, have been studied in aqueous solutions as a possible process for the removal of non-biodegradable compounds.We have examined the effects of dissolved oxygen and initial target concentration. Upon irradiation at 254 nm, the decomposition rate of ketoprofen is almost forty times higher as it of ibuprofen whilst VUV irradiation only increased the ibuprofen decomposition rate. The presence of dissolved oxygen accelerated the photodegradation of ibuprofen, whereas no effect was observed on the degradation of ketoprofen. The maximum quantum yield for the phototransformation was 0.2. The rate of mineralization in both cases was ∼60%, even after 1 h of treatment and this suggests the formation of stable by-products which were identified using GC-MS and HPLC-MS, respectively.     

Photolysis of polycyclic aromatic hydrocarbons on soil surfaces under UV irradiation

Photolysis of some polycyclic aromatic hydrocarbons (PAHs) on soil surfaces may play an important role in the fate of PAHs in the environment.Photolysis of PAHs on soil surfaces under UV irradiation was investigated.The effects of oxygen,irradiation intensity and soil moisture on the degradation of the three PAHs were observed.The results showed that oxygen,soil moisture and irradiation intensity enhanced the photolysis of the three PAHs on soil surfaces.The degradation of the three PAHs on soil surfaces is related to their absorption spectra and the oxidation-half-wave potential.The photolysis of PAHs on soil surfaces in the presence of oxygen followed pseudo first-order kinetics.The photolysis half-lives ranged from 37.87 days for benzo[a]pyrene to 58.73 days for phenanthrene.The results indicate that photolysis is a successful way to remediate PAHs-contaminated soils.     

Photochemical degradation of nonylphenol in aqueous solution：The impact of pH and hydroxyl radical promoters

The degradation of nonylphenol (NP) in aqueous solution with UV, H₂O₂/UV, and Fenton/photo-Fenton processes was studied. The efficacy of direct and hydrogen peroxide photolysis proved to be dependent on the pH value. The addition of H₂O₂ to UV treatment improved NP degradation. The application of UV photolysis and the H₂O₂/UV system at pH 7 resulted in low pseudo first-order rate constants at 10^-4 sec^-1. In the experiments at elevated pH values the pseudo-first order rate constants increased to 10^-3 sec^-1. The efficacy of the Fenton process was lower in comparison with UV and hydrogen peroxide photolysis. The addition of UV irradiation to the H₂O₂/Fe²⁺ system substantially improved NP degradation efficacy. In terms of performance, the photo-Fenton process was similar to the H₂O₂/UV process. The most favourable process for complete nonylphenol degradation considering both operational cost and treatment efficacy was H₂O₂/UV at pH 11 and 250 mol/L H₂O₂.