磺胺二甲嘧啶在水溶液中的光化学降解

研究了4种光源(高压汞灯、氙灯、紫外灯和太阳光)下磺胺二甲嘧啶(SM2)的光化学降解(简写为光解)动力学.结果表明:(1)4种光源下,SM2的光解符合一级动力学方程,光解速率常数依次为紫外灯＞高压汞灯＞氙灯＞太阳光.(2)在相同条件下,SM2的光解速率常数随着初始浓度的增加而减小.(3)SM2在不同pH的缓冲溶液下的光...     

超声波降解四环素类抗生素废水

采用超声波降解模拟废水中四环素类抗生素(TCs):土霉素(OTC)、四环素(TC)和金霉素(CTC),考查废水初始浓度、初始pH、超声波输入功率密度、曝气量和自由基清除剂(正丁醇)对降解效率的影响。结果表明,超声波可以快速高效地降解废水中的TCs,CTC最易被降解,TC和OTC次之;在OTC、TC和CTC初始浓度0.25 mg/L,初始pH=8.2,声功率密度1.2 W/mL,气水体积比30∶1的条件下,超声波辐照20 min后去除率分别达到76.8%、84.0%和94.4%。在实验研究条件下,TCs去除率均随初始浓度(0.25~2.00 mg/L)的增大而降低,但总去除浓度升高;碱性条件有利于TCs降解,去除率随初始pH(6~11)升高而升高;功率密度(0.24~1.96 W/mL)越高,TCs去除率也越高;曝气后TCs的去除率明显升高,随着气水比(10∶1~60∶1)的增大,去除率逐渐上升;正丁醇有效抑制TCs超声波降解,可推断TCs主要降解途径为自由基氧化。TCs超声波降解过程符合伪一级动力学反应特征。     

Photosonochemical degradation of trichloroacetic acid in aqueous solution

The degradation of trichloroacetic acid (TCA) was studied with ultraviolet (UV) photolysis, ultrasound (US) sonolysis and their combination. It was found that the degradation in the combined processes was more significant than in the UV photolysis or sonolysis alone. The effects of pH and dissolved gases on the rate of photosonochemical degradation of TCA were investigated and the degradation kinetics, mechanism and possible degradation products were discussed in detail.     

Radiation degradation of Congo Red in aqueous solution

Radiation-induced degradation of Congo Red (an azo dye) in aqueous solution was studied both with steady-state radiolysis and time-resolve techniques of pulse radiolysis and laser flash photolysis. Decomposition and mineralization of Congo Red by gamma-rays was investigated with the changes of absorption spectra, degradation efficiency, TOC removal and pH changes of the solutions in different irradiation systems. The main radiolytic products resulting from steady-state radiolysis of Congo Red were examined by HPLC and LC-MS. Complete degradation of Congo Red was observed at different absorbed doses under diverse irradiation condition. The TOC removal of the solutions saturated with O2 or N2O reached 76% and 86% at the absorbed dose of 11.9 kGy, respectively. Pulse radiolysis and laser flash photolysis experiments were carried out to study the reaction of Congo Red with e(aq)- and ()OH. The reaction rate constants were determined.     

电催化氧化处理三唑类杀菌剂模拟废水

以三环唑和丙环唑为特征污染物,研究了TiO2-NTs/SnO2-Sb/PbO2电极电催化氧化处理模拟废水中三唑类杀菌剂的机理。实验结果表明,电催化氧化对废水中三唑类杀菌剂的降解符合一级动力学关系,且降解速率为:丙环唑>三环唑。利用气相色谱-质谱联用仪(GC-MS)和离子色谱仪(IC)对电催化氧化降解三环唑和丙环唑溶液产生的中间产物和最终产生的有机酸和无机离子进行检测分析,推断出废水中三唑类杀菌剂电催化氧化的降解路径。通过斑马鱼实验得出电催化氧化对废水中三环唑急性毒性的削减幅度较大,对丙环唑的削减幅度较小。     

水中盐酸环丙沙星的超声降解

为研究超声波降解水中盐酸环丙沙星的机理,在不同超声波功率、不同盐酸环丙沙星初始浓度以及不同添加剂条件下,对盐酸环丙沙星进行超声降解研究.在实验条件下,当功率从180 W增至1 000 W时,10 mg/L盐酸环丙沙星降解率从55.2%提高到75.3%; 当功率为360 W,超声2 h时,未加添加剂时其降解率为62.5%,而加入FeSO4、NaCl、H2O2、CCl4、CuSO4、KI和N2后其降解率分别为85.3%、65.7%、70.1%、98.8%、43.6%、8.1%和51.2%.研究结果表明,FeSO4、NaCl、H2O2及CCl4的添加能促进盐酸环丙沙星的超声降解,而CuSO4、KI和N2却显著压抑其降解.盐酸环丙沙星的超声降解主要归因于·OH等活性自由基的氧化作用.     

γ-射线辐照降解水中阿莫西林

研究了60Coγ-射线辐照条件下水中阿莫西林(AMX)的辐照降解,考察了AMX初始浓度、辐照剂量、p H、H2O2、自由基消除剂(碳酸氢钠和正丁醇)以及溶解氧等因素对AMX辐照降解的影响。结果表明,γ辐照可有效降解水中AMX,当AMX初始浓度为10.0 mg/L,辐照剂量为15 k Gy时,降解率达100%,随着AMX浓度增大,其降解率降低。碱性条件有利于AMX的降解,当p H为11,且辐照剂量大于10 k Gy时,AMX的降解率在90%以上。同时,加入H2O2可以促进AMX的降解;·OH自由基消除剂的存在和缺氧条件会明显抑制γ-射线对AMX的辐照降解,分析表明,AMX的降解主要是基于·OH自由基的氧化。     

Photolytic degradation of fluoroquinolone carboxylic acids in aqueous solution

Subsequent to irradiation with a xenon lamp simulating sunlight, fluoroquinolone carboxylic acids in aqueous solution form polar pyridone dicarboxylic and tricarboxylic acids. After liquid/liquid partition with chloroform/water these substances can be isolated by ion exchange chromatography of the aqueous phase. They can be regarded as intermediate compounds on the route to a complete photomineralization. The structural elucidation is performed by such mass spectroscopic methods as MS, GC/MS and HPLC/MS, whereby HPLC/MS shows the highest reliability. Additionally¹H- and¹³C-NMR measurements confirm the structure of the main polar degradation product.     

Semiconductor-assisted photocatalytic degradation of reactive dyes in aqueous solution

This work reports the semiconductor-assisted photochemical degradation of reactive dyes. In an oxygenated-UV-ZnO system almost total decolorization of Remazol Brilliant Blue R, Remazol Black B, Reactive Blue 221 and Reactive Blue 222 was observed in reaction times of about 60 min. Extending the photochemical treatment up to 120 min, mineralization higher than 80% for all the dyes was observed. During the same period, the residual acute toxicity was significantly reduced only for Remazol Black B. A systematic optimization study carried out by factorial design showed that for the reactive dyes tested, the ZnO semiconductor exhibits a better efficiency than that observed with anatase TiO2. A synergistic effect in the coupled TiO2-ZnO system was not observed.     

Fenarimol solar degradation pathways and photoproducts in aqueous solution

The degradation photoproducts of the fungicide fenarimol obtained from irradiation of aqueous solutions with sunlight were characterised. The photoproducts resulting from samples with different exposure times were extracted and separated using chromatographic techniques. Seven main photoproducts were detected using high performance liquid chromatography with a photodiode array detector, gas chromatography with mass spectrometry detector and Fourier transform infrared spectroscopy. Structures are suggested for possible photoproducts based on the characterisation results, minimum energy geometry of the parent compound, and the mass spectral behaviour of fenarimol. These correspond to the compounds with m/z 328 (three structural isomers (a), (b) and (c)), m/z 294 (two structural isomers (a) and (b)), m/z 292, 278 and 190. Of the various major products detected, the isomer 328(a) is seen to be particularly unstable under the action of sunlight. The most stable photoproducts are found to be those with m/z 294(a), 278 and 190. However, upon prolonged solar irradiation all of these break down to produce polar, low molecular weight compounds. Comparison with our own and other results on fenarimol photolysis indicate significant solvent effects on the process. The combination of these structural characterisation results and previous data from spectroscopic and photodegradation kinetics studies allows us to suggest some possible mechanisms for the photodegradation of fenarimol under sunlight.     

Fenton法氧化处理水中土霉素的研究

为了评价Fenton法预处理抗生素生产废水中残留的高浓度土霉素的可行性,对Fenton试剂(Fe2 -H2O2)法催化氧化降解水溶液中的土霉素进行了研究.探讨了H2O2与Fe2 投加比例、投加量以及起始pH值对降解效果的影响,同时考察了土霉素废水中大量共存的草酸根离子对氧化过程的影响.结果表明,当H2O2与Fe2 按照5:1的比例投加时降解效率最高,最佳初始pH值在3.0-4.0之间.在最佳投加比例下,H2O2投加量为0.9 mmol/L,100 mg/L的土霉素可在10 min内得到完全降解.最佳反应条件下经过处理后土霉素水溶液TOC的去除率达40%左右,可生化性(BOD5/COD)也得到明显的改善.水中共存的草酸根离子对氧化效率具有明显的影响,但通过增加亚铁离子的量可以消除草酸的影响.     

Reductive degradation of nitrobenzene in aqueous solution by zero-valent iron

The reductive degradation of nitrobenzene (NB) by zero-valent iron was investigated. Experimental results showed that the degradation of NB was influenced by pH and NB concentration. The optimum pH value was found to be 3.0 for the reductive degradation of NB in the tested pH ranges of 3.0-12.0. The formation rate of aniline, a major reductive product of NB, followed zero-order kinetics at various pH levels. Furthermore, GC/MS analysis showed that aniline, azobenzene and azoxybenzene were the reductive products of NB by zero-valent iron. With the analysis of the products with GC/MS and FTIR, possible reductive pathways of NB by zero-valent iron were suggested.     

Abiotic transformation of DDT in aqueous solutions

Significant concentrations of chlorinated pesticides such as 1,1,1-trichloro-2,2-bis(4-chlorophenyl)ethane (DDT) and its two main transformation products, 1,1-dichloro-2,2-bis(4-chlorophenyl)ethane (DDD) and 1,1-dichloro-2,2-bis(4-chlorophenyl)ethylene (DDE) are still present in soil and sediment systems more than 30 years after DDT use was banned in the United States. DDT enters waterways via the runoff from industrial point sources, agricultural lands and atmospheric deposition. We evaluated zero-valent iron (Fe(0)), ferrous sulfide (FeS), as well as combining them with hydrogen peroxide (H(2)O(2)) as viable treatment technologies for degrading DDT in an aqueous solution. Treatment of DDT with Fe(0) and FeS resulted in approximately 88% and 56% transformation of DDT within 150h, respectively. DDE production was insignificant in all systems. The DDT removal was slower with FeS than with Fe(0), but the amounts of DDD and DDE produced did not exceed baseline. Treatment with a 1:1 mixture of Fe(0)-FeS removed about 95% of the added mass of DDT within 4days and generated significant amounts of DDD and minor amounts of DDMU. When small amounts of H(2)O(2) were introduced halfway through the Fe(0) and FeS treatment times, the mass of DDT decreased by 87% and 96%, respectively, within 2days. Our results demonstrate that mixtures of Fe(0)-FeS in combination with H(2)O(2) can be used for rapid and efficient removal of DDT from aqueous solutions.     

Titanium dioxide mediated photocatalytic degradation of 17beta-estradiol in aqueous solution

Photocatalytic degradation of 17beta-estradiol (E2) in aqueous medium mediated with titanium dioxide (TiO(2)) was studied. Moreover, effect of TiO(2) dosage on the degradation efficiency was investigated. Particular attention was paid to the identification of intermediates and analysis of photocatalytic degradation mechanism of E2 under neutral and alkaline conditions. The degradation efficiency of E2 increased with increasing concentration of TiO(2) but decreased due to light scattering as TiO(2) concentration was greater than 0.5mgml(-1). Several intermediates were formed during photocatalytic degradation of E2. However, only a few of the compounds could be identified and confirmed by LC-MS and LC-MS/MS. Six intermediates were observed by photocatalytic oxidation under alkaline conditions, namely 2-hydroxyestradiol, 10epsilon-17beta-dihydroxy-1,4-estradien-3-one (DEO), 10epsilon-hydroperoxide-17beta-hydroxy-1,4-estradien-3-one and three kinds of dicarboxylic acids formed by the opening of aromatic ring. In addition to the six intermediates mentioned above, 17beta-hydroxy-1,4-estradien-3-one (EO) was observed under neutral conditions and in the presence of methanol. Based on these intermediates, which were hardly degraded even after E2 was fully degraded, the mechanism of E2 degradation by TiO(2) photocatalysis was elucidated.     

低频超声辐照降解间苯二酚水溶液的研究

利用低频超声波对模拟间苯二酚废水进行研究，主要讨论间苯二酚本身性质以及超声操作声强对降解的影响，并通过自由基清除剂实验判定该反应的反应类型。结果表明，间苯二酚本身性质以及超声声强对间苯二酚的超声降解影响都比较大，并且该超声降解反应过程以自由基氧化反应为主，同时该反应遵循表观一级动力学反应特征。初始浓度为200mg／L的间苯二酚反应液经强度0．4W／cm^２的超声波辐照4h后，降解率为48．6％。     

低频超声辐照降解间苯二酚水溶液的研究

利用低频超声波对模拟间苯二酚废水进行研究,主要讨论间苯二酚本身性质以及超声操作声强对降解的影响,并通过自由基清除剂实验判定该反应的反应类型.结果表明,间苯二酚本身性质以及超声声强对间苯二酚的超声降解影响都比较大,并且该超声降解反应过程以自由基氧化反应为主,同时该反应遵循表观一级动力学反应特征.初始浓度为200mg/L的间苯二酚反应液经强度0.4 W/cm2的超声波辐照4 h后,降解率为48.6%.     

Reducing degradation of azo dye by zero-valent iron in aqueous solution

The reducing degradation kinetics of five azo dyes, Acid orange II, Acid orange IV, Acid orange GG, Acid red 3B and Orange I, by zero-valent iron powder in aqueous solution were studied. It showed that the degradation is a two-step reaction, with the first step being reversible. Solution acidity and iron surface area are the factors greatly influencing the degradation rates, and with increasing of acidity and iron surface area, the degradation rates increase.     

超声波-光催化联合降解苯酚废水研究

超声降解和光催化降解均为自由基历程的高级氧化技术,同时,超声空化能够改善传质效果,因此,二者耦合能否产生协同效果是值得研究的。本文考察了苯酚溶液的超声降解、光降解、光催化降解、超声-光催化降解以及温度对光降解和光催化降解的影响。结果表明,40kHz,0.4w/cm2的超声波对苯酚没有明显的降解作用,而对光催化降解只有轻微的促进作用。光降解和光催化降解的过程曲线显著不同,但温度对二者均有显著的促进作用。     

超声辐照对水中化学污染物的降解

超声辐照处理水中化学污染物取得了良好的效果，受到人们的关注。论述了超声辐照降解化学污染物的反应机理、降解速度、影响因素及超声辐照对微生物的影响；同时也指出了超声技术的发展方向和实际应用中面临的问题。     

Photocatalytic degradation kinetics and mechanism of phenobarbital in TiO2 aqueous solution

5-Ethyl-5-phenylpyrimidine-2,4,6(1H, 3H, 5H)-trione is an anti-convulsant used to treat disorders of movement, e.g. tremors. This work deals with the transformation of phenobarbital by UV/TiO₂ heterogeneous photocatalysis, to assess the decomposition of the pharmaceutical compound, to identify intermediates, as well as to elucidate some mechanistic details of the degradation. The photocatalytic removal efficiency of 100 μm phenobarbital is about 80% within 60 min, while the degradation efficiency of phenobarbital was better in alkaline solution. The study on contribution of reactive oxidative species (ROSs) has shown that OH is responsible for the major degradation of phenobarbital, while the photohole, photoelectrons and the other ROSs have the minor contribution to the degradation. Finally, based on the identification of degradation intermediates, two main photocatalytic degradation pathways have been tentatively proposed, including the hydroxylation and cleavage of pyrimidine ring in the phenobarbital molecule respectively. Certainly, the phenobarbital can be mineralized when the photocatalytic reaction time prolongs.