天然水中过氧化氢生成及其光化学反应的研究进展

在综合近４０年来国外对天然水（地表水、大气水滴及降水）中过氧化氢研究成果的基础上，重点从天然水中过氧化氢的含量和分布、生成机理以及光化学反应三方面，对这一领域的研究进展作了综述。     

固相微萃取法的应用及其进展

固相微萃取（ＳＰＭＥ） 是在固相萃取（ＳＰＥ） 的基础上结合顶空分析（Ｈｅａｄｓｐａｃｅ） 建立起来的一种新的样品预处理方法,它于１９９０ 年Ｊ．Ｐａｗｌｉｓｚｙｎ 首先提出,因其携带方便、操作简便、测定快速、高效的特点,且是一种无溶剂的样品预处理方法,故在短短几年时间,广泛应用于各个研究领域,如环境（ 包括水样、土壤、空气） 以及食品、药物、毒理学等的分析研究。本文根据所查阅到的文献,对目前国际上固相微萃取法的应用发展及其研究情况作一概述,并就该方法今后的可能发展方向进行初步的探讨（６０ ,１４６ ,１５３） ！     

环境介质中手性药物对映体分离分析及环境行为研究进展

综述了国内外环境介质中手性药物的分离分析方法以及环境行为研究进展,对比了几种主要的对映体分离方法,对手性固定相的种类及特性、分离原理、影响因素和发展趋势作了简要介绍,探讨了药物对映体在污水处理工艺和天然水环境中的降解或转化规律等环境行为,介绍了药物对映体特性在污染物源解析中的应用。     

改性膨润土对水中苯胺光化学降解的催化作用研究

研究了改性膨润土对水中苯胺光化学降解的催化作用.试验了水中苯胺的光化学降解的适宜条件.结果表明,改性膨润土能有效地催化苯胺的光化学降解.     

改性膨润土对水中萃胺光化学降解的催化作用研究

研究了改性膨润土对水中苯胺光化学降解的催化作用，试验了水中苯胺的光化学降解的适宜条件，结果表明，改性膨润土能有效地催化苯胺的光化学降解。     

基于荧光猝灭的地表水光化学BOD微生物传感器的研究

选择大肠埃希氏菌、热带假丝酵母、枯草芽胞杆菌以及3种菌株间的混合菌等淡水微生物菌株,利用有机改性溶胶-凝胶包埋法在载玻片上分别固定不同淡水微生物菌株和氧猝灭荧光探针,制备出不同光化学BOD微生物传感膜,与光纤BOD测定仪耦合成光化学BOD微生物传感器.比较了单株菌、混合菌不同光化学BOD微生物传感器的荧光响应行为、重金...     

聚丙烯基改性纤维固相萃取水中的苯酚

通过高能电子束辐照的方法,在聚丙烯（PP）纤维基体上分别接枝长链丙烯酸十八酯（SA）和亲水性丙烯酸-β-羟乙酯（HEA）2种单体,并将该纤维作为固相萃取填料,用于固相萃取（SPE）水中的痕量苯酚。研究了SPE过程中上样速度、洗脱溶剂、洗脱体积以及洗脱速度等因素对纤维萃取效果的影响。结果表明,改性纤维对痕量苯酚的富集倍数达95~145倍,回收率达到90%~98%,甲醇对纤维有良好的再生效果,纤维重复使用6次以内时,吸附性能无明显变化。     

第十六届全国太阳能光化学与光催化学术会议顺利召开

正2018年10月10日-13日,由中国可再生能源学会光化学专业委员会主办,上海师范大学、上海电力学院和上海市化学化工学会联合承办的第十六届全国太阳能光化学与光催化学术会议在上海隆重举行。大会开幕式由上海师范大学资源化学教育部重点实验室执行主任卞振锋教授主持,上海师范大学副校长陈恒教授,光化学专业委员会主任南京大学邹志刚院士分别致辞。光化学专业委员会常务副主任、秘书长、中国科学院化学研究所林原研究     

光化学氧化技术去除水中有机污染物的试验研究

以自来水为试验对象，对紫外－臭氧和紫外－二氧化钛两种光化学氧化技术对水中微量有机污染物的去除进行了试验研究，结果表明两种工艺的UVA（紫外吸光度）去除率均达到80％以上，对氯仿的去除也均能达到国家饮用水标准。在此基础上，自制了一种催化剂膜，并取得了预期的处理效果，有望在新型净水技术及设备的研制和开发上得到应用。     

表层土壤中有机污染物的光化学行为

本文首先简要介绍了光化学反应的基本原理。然后 ,重点介绍了研究表层土壤中有机污染物光化学行为的实验方法 ,影响光化学行为的因素及影响机理 ,光化学反应与吸附、迁移等的互相作用。最后阐述了这方面存在的问题 ,并且提出了一些建议     

Photochemistry of hydrolytic iron (III) species and photoinduced degradation of organic compounds. A minireview

On the basis of the research literature of the last fifty years, we have reviewed the photochemical properties of different hydrolytic Fe(III) species and the photodegradation of organic compounds in aqueous solutions initiated by them (mainly including low-molecular-weight Fe(III)-OH complexes, Fe(III) oxides (Fe2O3) and Fe(III) hydroxides (FeOOH)). Furthermore, the feasibility and prospects of the novel photochemical methods of using Fe(III) salts and oxides in wastewater treatments are being discussed in this paper.     

高价铬及双酚A在铁-乳酸体系中的同时光处理

研究了Fe(Ⅲ)-乳酸配合物体系同时对Cr(Ⅵ)的光还原及双酚A(BPA)的光氧化处理,考察了光源、初始pH值、Fe(Ⅲ)、乳酸盐、Cr(Ⅵ)及BPA初始浓度等因素对Cr(Ⅵ)及BPA光处理效率的影响。结果表明:光照条件下,铁-乳酸配合物能有效实现对六价铬及BPA的同时光处理。同一体系中,Cr(Ⅵ)的光还原快于BPA的光氧化,Fe(Ⅲ)初始浓度的增加可同时提高Cr(Ⅵ)的光还原效率和BPA的光氧化效率;Fe(Ⅲ)-乳酸盐配合物光解产生的Fe(Ⅱ)是Cr(Ⅵ)的主要还原剂,其次级光反应中产生的.OH是BPA的氧化剂。     

Photodegradation of hexabromocyclododecane (HBCD) by Fe(III) complexes/H2O2 under simulated sunlight

Hexabromocyclododecane (HBCD) is a globally produced brominated flame retardant used primarily as an additive flame retardant in polystyrene and textile products. Photodegradation of HBCD in the presence of Fe(III)-carboxylate complexes/H₂O₂ was investigated under simulated sunlight. The degradation of HBCD decreased with increasing pH in the Fe(III)-oxalate solutions. In contrast, the optimum pH was 5.0 for the Fe(III)-citrate-catalyzed photodegradation within the range of 3.0 to 7.0. For both Fe(III)-oxalate and Fe(III)-citrate complexes, the increase of carboxylate concentrations facilitated the photodegradation. The photochemical removal of HBCD was related to the photoreactivity and speciation distribution of Fe(III) complexes. The addition of H₂O₂ markedly accelerated the degradation of HBCD in the presence of Fe(III)-citrate complexes. The quenching experiments showed that ·OH was responsible for the photodegradation of HBCD in the Fe(III)-carboxylate complexes/H₂O₂ solutions. The results suggest that Fe(III) complexes/H₂O₂ catalysis is a potential method for the removal of HBCD in the aqueous solutions.     

The role of organic ligands in ferrous-induced photochemical degradation of 2,4-dichlorophenoxyacetic acid

Recent studies have shown that hydrogen peroxide is generated in a ferrioxalate-induced photoreductive reaction, but information about the effect of organic ligands on the photochemical behaviour of ferrous species is limited. The degradation of the herbicide 2,4-dichlorophenoxyacetic acid (2,4-D) by a ferrous-catalyzed oxidation in the presence of various ligands such as formate, citrate, malelate, oxalate, and ethylenediaminetetra-acetic acid (EDTA) was studied. The experiments were conducted under either dark or irradiated (350n m) conditions. Forty-two percent and 34% of 2,4-D were removed by the Fe(2+)/oxalate/UV and Fe(2+)/citrate/UV processes, respectively, after 30 min of reaction and oxidative intermediates were obtained in both cases. The presence of hydroxylated intermediates suggests that 2,4-D may be attacked by hydroxyl radicals, which are the products of the photo-Fenton-like reaction. As such, hydrogen peroxide was produced by the photolysis of ferrous oxalate or ferrous citrate, referred to hereafter as photogenerated H(2)O(2). As expected, the total removal percentage of 2,4-D jumped to 97% when 1mM of hydrogen peroxide (so-called spiked H(2)O(2)) was externally added to the reaction vessel to initiate the Fe(2+)/oxalate/UV process. Therefore, the treatment of 2,4-D by the Fe(2+)/oxalate/H(2)O(2)/UV system can be operated in two steps: the photolysis of ferrous oxalate first, followed by adding the spiked H(2)O(2) sometime after the commencement of the reaction. A two-phase model has been developed to describe this tandem ferrous-catalyzed photooxidation, which would help to achieve the mineralization of 2,4-D.     

Quantitation of Hydroxyl Radicals from Photolysis of Fe(III)-Citrate Complexes in Aerobic Water (5 pp)

Background For their high photoreactivity, Fe(III)-carboxylate complexes are important sources of H2O2 for some atmospheric and surface waters. Citrate is one kind of carboxylate, which can form complexes with Fe(III). In our previous study, we have applied Fe(III)-citrate complexes to degrade and decolorize dyes in aqueous solutions both under UV light and sunlight. Results have shown that carboxylic acids can promote the photodegradation efficiency. It is indicated that the photolysis of Fe(III)-citrate complexes may cause the formation of some reactive species (e. g. H2O2 and ·OH). This work is attempted to quantify hydroxyl radicals generated in the aqueous solution containing Fe(III)-citrate complexes and to interpret the photoreactivity of Fe(III)-citrate complexes for degrading organic compounds. Methods By using benzene as the scavenger to produce phenol, the photogeneration of ·OH in the aqueous solution containing Fe (III)-citrate complexes was determined by HPLC. Results and Discussion In the aqueous solution containing 60.0/30.0 mM Fe(III)/citrate and 7.0 mM benzene at pH 3.0, 96.66 mM ·OH was produced after irradiation by a 250W metal halide light (l ≥ 313 nm) for 160 minutes. Effects of initial pH value and concentrations of Fe(III) and citrate on ·OH radical generation were all examined. The results show that the greatest photoproduction of ·OH in the aqueous solution (pH ranged from 3.0 to 7.0) was at pH 3.0. The photoproduction of ·OH increased with increasing Fe(III) or citrate concentrations. Conclusion In the aqueous solutions containing Fe(III)-citrate complexes, ·OH radicals were produced after irradiation by a 250W metal halide light. It can be concluded that Fe(III)-citrate complexes are important sources of ·OH radicals for some atmospheric and surface waters. Recommendations and Outlook It is believed that the photolysis of Fe(III)-citrate complexes in the presence of oxygen play an important role in producing ·OH both in atmospheric waters and surface water where high concentrations of ferric ions and citrate ions exist. The photoproduction of ·OH has a high oxidizing potential for the degradation of a wide variety of natural and anthropogenic organic and inorganic substances. We can use this method for toxic organic pollutants such as organic dyes and pesticides.     

Photochemical decomposition of environmentally persistent short-chain perfluorocarboxylic acids in water mediated by iron(II)/(III) redox reactions

The photochemical decomposition of short-chain (C(3)-C(5)) perfluorocarboxylic acids (PFCAs) was investigated. Direct photolysis in water proceeded slowly with the 220- to 460-nm light emission from a xenon-mercury lamp to form F(-), CO(2), and shorter-chain PFCAs. Addition of a small amount of Fe(3+) to the aqueous solutions of the PFCAs dramatically enhanced their photochemical decomposition under an oxygen atmosphere: when the (initial PFCA)/(initial Fe(3+)) molar ratio was 13.5 (initial PFCA concentration=67.3mM), the pseudo-first-order rate constants for the PFCA decomposition were 3.6-5.3 times those with photolysis alone, and the turnover number for the catalytic PFCA decomposition [i.e., (moles of decomposed PFCA)/(moles of initial Fe(3+))] reached 6.71-8.68 after 24h of irradiation. The catalysis can be explained by photoredox reactions between PFCA, Fe(3+)/Fe(2+) and oxygen via photo-induced complexation of Fe(3+) with the PFCAs.     

Atmospheric production of oxalic acid/oxalate and nitric acid/nitrate in the Tampa Bay airshed: Parallel pathways

Oxalic acid is the dominant dicarboxylic acid (DCA), and it constitutes up to 50% of total atmospheric DCAs, especially in non-urban and marine atmospheres. A significant amount of particulate H₂Ox/oxalate (Ox) occurred in the coarse particle fraction of a dichotomous sampler, the ratio of oxalate concentrations in the PM₁₀ to PM_2.5 fractions ranged from 1 to 2, with mean±sd being 1.4±0.2. These results suggest that oxalate does not solely originate in the gas phase and condense into particles. Gaseous H₂Ox concentrations are much lower than particulate Ox concentrations and are well correlated with HNO₃, HCHO, and O₃, supporting a photochemical origin. Of special relevance to the Bay Region Atmospheric Chemistry Experiment (BRACE) is the extent of nitrogen deposition in the Tampa Bay estuary. Hydroxyl radical is primarily responsible for the conversion of NO₂ to HNO₃, the latter being much more easily deposited. Hydroxyl radical is also responsible for the aqueous phase formation of oxalic acid from alkenes. Hence, we propose that an estimate of OH can be obtained from H₂Ox/Ox production rate and we accordingly show that the product of total oxalate concentration and NO₂ concentration approximately predicts the total nitrate concentration during the same period.     

Heterogeneous photocatalytic degradation of methyl orange in schwertmannite/oxalate suspension under UV irradiation

Introduction

Schwertmannite was synthesized through an oxidation of FeSO₄ by Acidithiobacillus ferrooxidans LX5 cell suspension at an initial pH?2.5 and 28°C for 3?days and characterized using X-ray diffraction spectroscopy and scanning electron microscope. The schwertmannite photocatalytic degradation of methyl orange (MO) by oxalate was investigated at different initial pH values, concentrations of schwertmannite, oxalate, and MO.

Results

The results demonstrated that photodegradation of MO in the presence of schwertmannite or oxalate alone was very weak. However, the removal of MO was significantly enhanced when schwertmannite and oxalate coexisted in the reaction system. Low pH (4 or less) was beneficial to the degradation of MO. The optimal doses of schwertmannite and oxalate were 0.2?g?L^?1 and 2?mM, respectively. Hydroxyl radicals (·OH) and Fe(II), the intermediate products, were also examined during the reaction to explore their correlation with the degradation of MO.

Conclusion

A possible mechanism for the photocatalytic decomposition of MO in the study was proposed. The formation of Fe(III)-oxalate complexes on the surface of schwertmannite was a precursor of H₂O₂ and Fe(II) production, further leading to the yield of ·OH responsible for the decomposition of MO.     

Photochemical formation of hydroxyl radicals catalyzed by montmorillonite

In this work, the photooxidation of benzene and the formation of phenol in aqueous suspensions of the iron-rich montmorillonite under irradiation of a 250W metal halide lamp (lambda> or = 365nm) were investigated. We confirmed that hydroxyl radicals (()OH) were produced by illuminating montmorillonite and was responsible for the photooxidation of benzene in aqueous suspensions of montmorillonite. Low pH value facilitated the formation of hydroxyl radicals in the pH range of 2.0-10.0. The ()OH concentration increased with increasing the concentration of montmorillonite in aqueous solutions in the range of 0-20.0gl(-1). Higher concentration like 25.0gl(-1) montmorillonite inhibited the ()OH production. Iron, predominantly free iron in the clays, is believed to be one of the most important factors determining ()OH formation. Structural irons in montmorillonite have contributions to ()OH formation, especially in the presence of carboxylate ions. The formation of ()OH from montmorillonite under irradiation of near UV and visible light indicates that clays might play important role not only in transfer through adsorption but also in transformation through oxidation of organic compounds on the surface of clay particles in air, water, soil or even top sediments.     

Variation in CO2 assimilation rate induced by simulated dew waters with different sources of hydroxyl radical (*OH) on the needle surfaces of Japanese red pine (Pinus densifora Sieb. et Zucc.)

The hydroxyl radical (*OH) is generated in polluted dew on the needle surfaces of Japanese red pine (Pinus densiflora Sieb. et Zucc.). This free radical, which is a potent oxidant, is assumed to be a cause of ecophysiological disorders of declining trees on the urban-facing side of Mt. Gokurakuji, western Japan. Mists of *OH-generating N(III) (HNO2 and NO2-) and HOOH + Fe + oxalate solutions (50 and 100 microM, pH 5.1-5.4) simulating the dew water were applied to the foliage of pine seedlings grown in open-top chambers in the early morning. Needles treated with 100 microM N(III) tended to have a greater maximum CO2 assimilation rate (Amax), a greater stomatal conductance (g(s)) and a greater needle nitrogen content (Nneedle), suggesting that N(III) mist acts as a fertilizer rather than as a phytotoxin. On the other hand, needles treated with 100 microM HOOH + Fe + oxalate solution showed the smallest Amax, g(s), and Nneedle, suggesting that the combination of HOOH + Fe + oxalate caused a decrease in needle productivity. The effects of HOOH + Fe + oxalate mist on pine needles were very similar to the symptoms of declining trees at Mt. Gokurakuji.