气相化学反应中的云盖效应

本文在ＣＢＭ－Ｉ机理的基础上考虑了ＯＨ和ＨＯ２自由基对ＳＯ２的氧化作用和云对光解率的影响，定量研究了气相色化学反应中的云盖效应。结果表明，云的存在将改变整个反应体系的平衡，气态物对云的响应是非线的。     

Treatment of organic pollutants by homogeneous and heterogeneous Fenton reaction processes

Nowadays, the water ecosystem is being polluted due to the rapid industrialization and massive use of antibiotics, fertilizers, cosmetics, paints, and other chemicals. Chemical oxidation is one of the most applied processes to degrade contaminants in water. However, chemicals are often unable to completely mineralize the pollutants. Enhanced pollutant degradation can be achieved by Fenton reaction and related processes. As a consequence, Fenton reactions have received great attention in the treatment of domestic and industrial wastewater effluents. Currently, homogeneous and heterogeneous Fenton processes are being investigated intensively and optimized for applications, either alone or in a combination of other processes. This review presents fundamental chemistry involved in various kinds of homogeneous Fenton reactions, which include classical Fenton, electro-Fenton, photo-Fenton, electro-Fenton, sono-electro-Fenton, and solar photoelectron-Fenton. In the homogeneous Fenton reaction process, the molar ratio of iron(II) and hydrogen peroxide, and the pH usually determine the effectiveness of removing target pollutants and subsequently their mineralization, monitored by a decrease in levels of total organic carbon or chemical oxygen demand. We present catalysts used in heterogeneous Fenton or Fenton-like reactions, such as H₂O₂–Fe³⁺(solid)/nano-zero-valent iron/immobilized iron and electro-Fenton-pyrite. Surface properties of heterogeneous catalysts generally control the efficiency to degrade pollutants. Examples of Fenton reactions are demonstrated to degrade and mineralize a wide range of water pollutants in real industrial wastewaters, such as dyes and phenols. Removal of various antibiotics by homogeneous and heterogeneous Fenton reactions is exemplified.     

Online electro-Fenton-mass spectrometry reveals 2,4′,5-trichlorobiphenyl oxidation products and binding to organic matter

Electrochemistry–mass spectrometry is used to simulate redox reactions in many research disciplines because this technique is fast and provides information on compound metabolites. However, the analysis of the degradation of refractory organic pollutants by reactive oxygen species is difficult to achieve by the electrochemistry step. Therefore, here we use online electro-Fenton-mass spectrometry to study for the first time the oxidation of 2,4′,5-trichlorobiphenyl [polychlorinated biphenyl (PCB) 31] by reactive oxygen species and the binding reactions of PCB degradation products with model substances of natural organic matter. The degradation products were identified by coupled Q Trap mass spectrometry. We observed a binding of a degradation product with γ-l-glutamyl-l-cysteinyl-glycine. We propose a transformation pathway. We conclude that online electro-Fenton-mass spectrometry is a promising technique to study the oxidation of refractory organic pollutants and further binding of degradation products with natural organic matter.     

分子电性距离矢量用于多氯代二苯并呋喃光解半衰期的QSPR研究（Molecular Electronegativity Distance Vector（MEDV）Applied to Quantitative Structure-Property Relationship Study on Photolysis Half-Lives of PCDFs）

多氯代二苯并呋喃(PCDFs)是一种典型的持久性有机污染物(POPs),光解是其在环境中转化的主要途径.以分子电性距离矢量(Molecular Electronegativity Distance Vector,MEDV)为参数,应用多元线性回归(Multiple Linear Regression,MLR)和偏最小二乘回归(PLSR)对48种PCDFs在云杉针叶和飞灰表面的光解半衰期(t1/2)进行模拟分析,均获得由2个变量所建的定量结构-性质相关(QSPR)模型.多元线性回归结果:建模相关系数(R)分别为0.860和0.836,标准偏差(SD)分别为0.052和0.053,交互检验复相关系数(Rcv)分别为0.839和0.807,外部检验相关系数(Qex)t分别为0.939和0.853;偏最小二乘回归结果:建模相关系数(R)分别为0.857和0.829,交互检验复相关系数(Rcv)分别为0.849和0.807.结果表明,MEDV能较好地表征该类分子的结构信息,所建QSPR模型具有良好的稳定性和预测能力.     

1961-2007年期间南宁紫外线辐射的变化趋势及其与皮肤癌发病相关分析

采用2002年9月至2005年10月逐日太阳总辐射、云量、太阳天顶角、臭氧、水汽压、空气污染物和紫外线辐射资料,建立了基于气象要素推算紫外线曝辐量的模型;采用该模型重建1961-2007逐日紫外线曝辐量资料,从年、春、夏、秋、冬不同尺度分析重建序列的特征;采用1991-2003年皮肤癌发病人数资料,分析紫外线曝辐量与各类皮肤癌发病人数相关性;对未来紫外线变化进行展望。主要结论有:1961-2007年,南宁紫外线曝辐量年平均日值为95.83 W.h/m2;绝对变率以夏季最大,相对变率以冬季最大,秋季绝对变率和相对变率均最小;年平均和春、夏、秋季紫外线曝辐量有微弱的下降趋势,冬季下降趋势明显;突变主要发生在1970 s中后期至1980 s初期和1990 s初期;年和各季最显著的周期是准7年,夏季还有明显的11年周期;1991-2003年鳞状细胞癌发病人数与紫外线曝辐量相关显著;基底细胞癌、鳞状细胞癌、恶性黑色瘤3种皮肤癌均好发于高紫外线辐射时间;展望2050年以前紫外线变化情况,认为:偏高年份可能在2017、2031、2045年附近,偏低年份可能在2010、2024、2038年附近。     

大气污染化学研究概况

本文综述了大气污染化学研究在国内外的发展概况,对大气污染物的表征研究和大气污染的化学过程与模式的研究,作了详细的阐述,特别对大气颗粒物的表征与来源的识别、大气光化学反应、自由基反应及其它活性物种的反应在近年的发展作了全面的总结,介绍了当今全球性大气污染的一些重大环境问题,如酸雨、臭氧层破坏、温室效应等有关大气化学研究的情况,回顾了大气污染化学对中国经济与科学发展中的重要作用。     

溴氟菊酯的光解、水解与土壤降解

在实验室测定了溴氟菊酯的光解、不同ｐＨ条件下的水解以及在太湖水稻土、江西红壤与东北黑土等３种不同土壤中的降解。试验结果表明：在３００Ｗ低压汞灯下，溴氟菊酯的水相溶液与其石油醚相济液中的光解均呈二级反应动力学方程，光解半衰期分别为１３．７与９．４ｍｉｎ；在ｐＨ为５，７，９的缓冲溶液中其水解半衰期分别为１５．６，８．３与４．２ｄ；在３种不同土壤中的降解半衰期为４．８～８．８ｄ。     

溴代甲烷在253.7nm条件下的光氧化机理及其对臭氧光解损耗影响的动力学

本文研究了在２５３．７ｎｍ的紫外光照条件下，ＣＨ３Ｂｒ，ＣＨ２Ｂｒ２以及ＣＨ３Ｂｒ＋Ｏ２／Ｏ３物ＣＨ２Ｂｒ３＋Ｏ２／Ｏ３等体系的光化学反应过程，通过ＦＴＩＲ以及ＵＶ－Ｖｉｓ对产物进行了分析。并提出反应机理予以解释。     

环境污染物导致氧化应激的关键信号通路及其检测方法

环境污染物能够以多种途径进入生物体内,在体内产生含氧自由基等活性氧物质,并通过多种信号通路及酶反应引起氧化应激,造成生物体内的脂质过氧化、蛋白质损伤、DNA表达改变、酶失活等,从而引发心血管疾病、风湿类疾病、感染及癌症等的发生。本文对环境污染物致氧化应激产生的原因、涉及的信号通路及酶反应、造成的危害,以及常见的基于细胞模型的氧化应激检测方法进行了综述,期望为评价环境污染物和检测氧化损伤提供参考。     

Study on degradation process of famotidine hydrochloride in aqueous samples

The kinetics of famotidine (FAM) transformation under the influence of various factors, important from the environmental point of view, was investigated in aqueous solutions. The degradation processes using UV, H₂O₂, UV/H₂O₂, H₂O₂/Fe²⁺, and UV/H₂O₂/Fe²⁺ were studied. Direct photolysis and H₂O₂-assisted photolysis showed a pseudo-first-order kinetics, while the Fenton and the photo-Fenton processes fit second-order kinetics. The provided experiments proved a high resistance of FAM to direct photolysis. Its stability depends highly on the pH of the reaction solutions. The rate of FAM direct photolysis in acidic solutions was almost negligible. The reaction rate of FAM photolysis at pH 8–9 was 3.7 × 10^?3 min^?1 with DT₅₀ about 3 h 7 min. It was found that the presence of H₂O₂ in the reaction environment enhances the rate of photolysis of FAM. The observed rates of reaction were 5.1 × 10^?3 min^?1 and 3.7 × 10^?3 min^?1 in acidic and basic solutions, respectively. The used Fenton systems appeared to be the most efficient in FAM removal. The rate of reaction depends on concentration of Fe²⁺ and H₂O₂. It was observed that the presence of UV-light enhances the reaction rate by two to six times in comparison to the classical Fenton system. Additionally, FAM behavior in natural water under solar irradiation was examined. The irradiation experiments were carried out in batch experiments with simulated sunlight.     

环境污染物导致氧化应激的关键信号通路及其检测方法

环境污染物能够以多种途径进入生物体内,在体内产生含氧自由基等活性氧物质,并通过多种信号通路及酶反应引起氧化应激,造成生物体内的脂质过氧化、蛋白质损伤、DNA表达改变、酶失活等,从而引发心血管疾病、风湿类疾病、感染及癌症等的发生。本文对环境污染物致氧化应激产生的原因、涉及的信号通路及酶反应、造成的危害,以及常见的基于细胞模型的氧化应激检测方法进行了综述,期望为评价环境污染物和检测氧化损伤提供参考。     

Is atmospheric oxidation capacity better in indicating tropospheric O3 formation?

● This study summarizes and evaluates different approaches that indicate O₃ formation. ● Isopleth and sensitivity methods are useful but have many prerequisites. ● AOC is a better indicator of photochemical reactions leading to O₃ formation. Tropospheric ozone (O₃) concentration is increasing in China along with dramatic changes in precursor emissions and meteorological conditions, adversely affecting human health and ecosystems. O₃ is formed from the complex nonlinear photochemical reactions from nitrogen oxides (NO_x = NO + NO₂) and volatile organic compounds (VOCs). Although the mechanism of O₃ formation is rather clear, describing and analyzing its changes and formation potential at fine spatial and temporal resolution is still a challenge today. In this study, we briefly summarized and evaluated different approaches that indicate O₃ formation regimes. We identify that atmospheric oxidation capacity (AOC) is a better indicator of photochemical reactions leading to the formation of O₃ and other secondary pollutants. Results show that AOC has a prominent positive relationship to O₃ in the major city clusters in China, with a goodness of fit (R²) up to 0.6. This outcome provides a novel perspective in characterizing O₃ formation and has significant implications for formulating control strategies of secondary pollutants.     

Photodegradation of pesticides .1. Photolysis rates and half‐life of acylanilides and their major metabolites in water

The photolysis in water solution of three fungicides (Metalaxyl, Benalaxyl, and Furalaxyl) was studied under artificial light. At λ = 254 Benalaxyl and Furalaxyl underwent fast degradation with rearrangement reactions less complex than those of Metalaxyl. Under A = 254–290 the photolysis was very fast and Benalaxyl and Furalaxyl show a common behaviour. This was found to be a kinetic consecutive process leading, at first, to N‐2,6‐xylyl‐D,L‐alaninate (II), which was degraded to 2,6‐dimethylaniline (IV). This amine gives unknown products. Metalaxyl underwent a parallel/consecutive photodegradtion to give (II) and N‐(methoxyacetyl)‐2,6‐dimethylaniline (VI). While (II) was easily converted to (IV) as earlier, (VI) was more stable to photolysis. Under λ > 290 all the fungicides shown very slow degradation with pseudo first order rate constants. The photoproducts were degraded faster than the parent compounds by factors from 13 to 1800. The presence of photosensitizer in water (humic acids or acetone) resulted in total decomposition of fungicides and of their photoproducts.     

与环境污染物转化相关的细菌厌氧呼吸研究动态

基于细菌呼吸理论为基础的环境有毒物质降解为环境污染治理提供了新的策略和方法,是近年来研究的热点问题.细菌呼吸是自然界中一个最基本、最重要的生物代谢过程,具有很大的灵活性和多样性,且与生态环境密切相关.在厌氧条件下,细菌利用环境中多种有毒物质作为呼吸链末端电子受体进行厌氧呼吸,在有毒物质被还原甚至降解的同时实现电子在呼吸链上的传递,形成跨膜的质子浓度电势梯度,进而转化为其生长代谢所需的能量.细菌以环境有毒物质为电子受体的厌氧呼吸不断被发现,这对于深入理解细菌呼吸的本质具有重要的理论意义,同时对于有毒物质的降解及元素的生物地球化学循环具重要的环境学意义,对于提高对地球表面有毒物质污染生物修复策略的认识具有重要的现实意义.图1表1参45     

Photocatalytic degradation of phenol in water using TiO2 and ZnO

Photocatalytic degradation of chemical pollutants in water was investigated using semiconductor oxide catalysts, zinc oxide (ZnO) and titanium dioxide (TiO2) and phenol as the substrate. Influence of various parameters such as characteristics of the catalyst, irradiation time, substrate and catalyst concentrations, pH etc. has been studied and optimum conditions for the complete degradation of phenol in water have been identified. In terms of activity and durability TiO2 is far superior to ZnO. Mixing ZnO with TiO2 does not affect its activity significantly. The process is especially relevant in view of its potential for the treatment of wastewater containing pollutants, using solar radiation as the energy source.     

Toxizitätsänderungen in Photoreaktionen von Azaarenen

The azaarenes and the structurally analogous PAH accompany each other and occur ubiquitously in nature. Photochemical conversions like direct photolysis or the photoreaction with nitrate are important natural degradation reactions of azaarenes. Furthermore, photoreactions with chlorine and bromine radicals can be expected in nature. The reactions generate a large number of oxidized, nitrated and halogenated products with unknown toxicity. In this paper, a first screening of changes is reported in acute toxicity during the course of the photochemical reactions. As test system luminescent bacteria are used. For quinoline, isoquinoline and phthalazine the investigations show different changes of the toxicity of the reaction mixtures in dependence on the respective reaction type. The toxicity of the reaction mixtures of quinazoline and quinoxaline increases in all reactions investigated. Furthermore the reactions of bromine radicals with azaarenes also show an increase of the toxicity in all cases. Compared with the azaarenes in all reactions products with significantly higher toxicity are formed.     

Photochemical reactions of musk ketone

The photolysis of musk ketone in cyclohexane and methanol afforded several cyclization products while the product spectrum in cyclohexene and squalene was characterized by an amino derivative and a ring expansion product, respectively. On cellulose stearate layers the photochemical reactions of musk ketone proceeded readily both under sun simulator and in natural sunlight and several photoproducts identified in solvent experiments were detected. Photoproducts were isolated by preparative HPLC and TLC and analyzed by means of HPLC, GC/MS, MS, LC/MS, ¹H‐ and ¹³C‐NMR.     

大气污染指示植物的研究

自50年代以来.为寻找一种经济、实用和灵敏的方法来监测环境变化,开展了大量大气污染指示植物的研究.这些工作包括用植物叶片典型症状、树皮、草本植物、附生植物指示气体污染(O_3、PANs、NO_x、SO_2、HF、乙烯等)、粉尘以及重金属污染.进入80年代以后,有关研究集中到利用植物富集的污染物含量结合计算机等先进技术指示和监测大气环境变化及进行大气质量评价.本文对国内外开展的大气污染指示植物研究的历史及其主要方法作了简要介绍,并就利用植物指示和监测大气污染的若干问题进行了探讨.     

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.     

Solar photo-oxidation of recalcitrant industrial wastewater: a review

Conventional methods to clean wastewater actually lead to incomplete treatments, calling for advanced technologies to degrade recalcitrant pollutants. Herein we review solar photo-oxidation to degrade the recalcitrant contaminants in industrial wastewater, with focus on photocatalysts, reactor design and the photo-Fenton process. We discuss limitations due to low visible-light absorption, catalyst collection and reusability, and production of toxic by-products. Photodegradation of refractory organics by solar light is controlled by pH, photocatalyst composition and bandgap, pollutant properties and concentration, irradiation type and intensity, catalyst loading, and the water matrix.