Nitrate-induced photodegradation of atenolol in aqueous solution: kinetics, toxicity and degradation pathways

The extensive utilization of β-blockers worldwide led to frequent detection in natural water. In this study the photolysis behavior of atenolol (ATL) and toxicity of its photodegradation products were investigated in the presence of nitrate ions. The results showed that ATL photodegradation followed pseudo-first-order kinetics upon simulated solar irradiation. The photodegradation was found to be dependent on nitrate concentration and increasing the nitrate from 0.5 mM L⁻¹ to 10 mM L⁻¹ led to the enhancement of rate constant from 0.00101 min⁻¹ to 0.00716 min⁻¹. Hydroxyl radical was determined to play a key role in the photolysis process by using isopropanol as molecular probe. Increasing the solution pH from 4.8 to 10.4, the photodegradation rate slightly decreased from 0.00246 min⁻¹ to 0.00195 min⁻¹, probably due to pH-dependent effect of nitrate-induced OH formation. Bicarbonate decreased the photodegradation of ATL in the presence of nitrate ions mainly through pH effect, while humic substance inhibited the photodegradation via both attenuating light and competing radicals. Upon irradiation for 240 min, only 10% reduction of total organic carbon (TOC) can be achieved in spite of 72% transformation rate of ATL, implying a majority of ATL transformed into intermediate products rather than complete mineralization. The main photoproducts of ATL were identified by using solid phase extraction-liquid chromatography-mass spectrometry (SPE-LC-MS) techniques and possible nitrate-induced photodegradation pathways were proposed. The toxicity of the phototransformation products was evaluated using aquatic species Daphnia magna, and the results revealed that photodegradation was an effective mechanism for ATL toxicity reduction in natural waters.     

Degradation of diuron in aqueous solution by ozonation

Degradation of diuron [3-(3,4-dichlorophenyl)-1,1-dimethylurea] in aqueous solution and the proposed degradation mechanism of diuron by ozonation were investigated. The factors that affect the degradation efficiency of diuron were examined. The generated inorganic ions and organic acids during the ozonation process were detected. Total organic carbon removal rate and the amount of the released Cl(-) increased with increasing ozonation time, but only 80.0% of the maximum theoretical concentration of Cl(-) at total mineralization was detected when initial diuron concentration was 13.8 mg L(-1). For N species, the final concentrations of NO3(-) and NH4+ after 60 min of reaction time were 0.28 and 0.19 mg L(-1), respectively. The generated acetic acid, formic acid and oxalic acid were detected during the reaction process. The main degradation pathway of diuron by ozonation involved a series of dechlorination-hydroxylation, dealkylation and oxidative opening of the aromatic ring processes, leading to small organic species and inorganic species. The degradation efficiency of diuron increased with decreasing initial diuron concentration. Higher pH value, more ozone dosage, additive Na2CO3, additive NaHCO3 and additive H2O2 were all advantageous to improve the degradation efficiency of diuron.     

Degradation of diuron in aqueous solution by ozonation

Degradation of diuron [3-(3,4-dichlorophenyl)-1,1-dimethylurea] in aqueous solution and the proposed degradation mechanism of diuron by ozonation were investigated. The factors that affect the degradation efficiency of diuron were examined. The generated inorganic ions and organic acids during the ozonation process were detected. Total organic carbon removal rate and the amount of the released Cl^? increased with increasing ozonation time, but only 80.0% of the maximum theoretical concentration of Cl^? at total mineralization was detected when initial diuron concentration was 13.8 mg L^?1. For N species, the final concentrations of NO₃ ^? and NH₄ ⁺ after 60 min of reaction time were 0.28 and 0.19 mg L^?1, respectively. The generated acetic acid, formic acid and oxalic acid were detected during the reaction process. The main degradation pathway of diuron by ozonation involved a series of dechlorination-hydroxylation, dealkylation and oxidative opening of the aromatic ring processes, leading to small organic species and inorganic species. The degradation efficiency of diuron increased with decreasing initial diuron concentration. Higher pH value, more ozone dosage, additive Na₂CO₃, additive NaHCO₃ and additive H₂O₂ were all advantageous to improve the degradation efficiency of diuron.     

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.     

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.     

活性碳纤维电极法去除水中敌草隆的研究

实验研究了活性炭纤维电极对敌草隆的去除作用。考察了电流强度以及敌草隆浓度对敌草隆去除的影响,对活性炭纤维用于吸附和用作电极去除敌草隆的效应进行了比较分析。结果表明,在0.01～0.05 A内,敌草隆的去除随着电流强度的增加而增加,其去除率为58%～91%。敌草隆浓度在5～40 mg/L时,其去除率随着浓度的增加而减小,但至1.5 h 时,去除率均可达95%以上。对于20 mg/L的敌草隆,活性炭纤维对其吸附去除率为90%左右,重复使用导致去除效率下降;活性炭纤维电极电化学氧化对其去除率达95%,并且重复使用其效果未见下降。活性炭纤维电极电化学氧化导致敌草隆分子结构破坏、苯环开环发生分解而最终得以去除。活性炭纤维电极可用于水中敌草隆的去除。     

水溶液中甲基橙的超声化学降解动力学研究

研究了水溶液中甲基橙的超声化学降解动力学。结果表明 ,水溶液中甲基橙可通过超声化学方法降解 ,降解动力学为一级反应 ,降解速率常数为 -2 .2 5× 10 - 3m in- 1。甲基橙降解速率随初始浓度的升高而降低 ,随介质温度的下降而升高 ,随介质酸度的变化而变化。 H2 O2 、F e2 +和 I- 等自由基促进剂可有效加速甲基橙的降解     

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。     

Aerobic degradation of diuron by aquatic microorganisms

Abstract

Degradation of diuron [3‐(3,4‐dichlorophenyl)‐l,1‐dimethyl‐urea] by microorganisms obtained from pond water and sediment was determined under aerobic conditions. Enrichment procedures were used to isolate cultures capable of degrading the herbicide. Several mixed fungal/bacterial and mixed bacterial cultures were isolated that could degrade diuron. The mixed cultures degraded 67–99% of the added diuron forming from six to seven products which were separated via TLC. The major degradation product detected in most culture extracts was 3,4‐dichloroaniline. Other identified products formed were 3‐(3,4‐dichlorophenyl)‐1‐methylurea and 3‐(3,4‐dichlorophenyl)urea.     

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.     

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。     

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...     

Abiotic degradation of imazethapyr in aqueous solution

The photodegradation of imazethapyr [2-(4,5-dihydro-4-méthyl-4-(1-méthylethyl)-5-oxo-1H-imidazol-2-yl)-5-ethyl-3-pyridinecarboxylic acid] in aqueous solution in the presence of titranium dioxide (TiO2) and humic acids (HA) at different ratios of herbicide/TiO2 and herbicide/humic acids was studied at pH 7.0. Irradiation was carried out with polychromatic light using Heraeus apparatus equipped with xenon lamp to simulate sunlight having a spectral energy distribution similar to solar irradiation (>290 nm). The concentration of remaining herbicide was followed using a High Pressure Liquid Chromatograph (HPLC) equipped with UV detector at 230 nm. In pure aqueous solution imazethapyr degrades slowly and the photodegradation leads to the formation of two metabolites labelled A and B. The presence of TiO2 caused enhancement of the degradation rate. The presence of HA induced an increase of the photodegradation of the pesticide with respect to pure aqueous solution.     

The degradation of chlorpyrifos and diazinon in aqueous solution by ultrasonic irradiation: effect of parameters and degradation pathway

In this paper, elimination of two types of organophosphorus pesticides (OPPs), chlorpyrifos and diazinon spiked in aqueous solution by ultrasonic irradiation was investigated. Results showed that chlorpyrifos and diazinon could be effectively and rapidly degraded by ultrasonic irradiation, and the degradation of both pesticides was strongly influenced by ultrasonic power, temperature and pH value. Furthermore, two and seven products for the degradation of chlorpyrifos and diazinon formed during ultrasonic irradiation have been identified by gas chromatography-mass spectrometry, respectively. The hydrolysis, oxidation, hydroxylation, dehydration and decarboxylation were deduced to contribute to the degradation reaction and the degradation pathway for each pesticide under ultrasonic irradiation was proposed. Finally, the toxicity evaluation indicated that the toxicity decreased for diazinon solution after ultrasonic irradiation, but it increased for chlorpyrifos solution. The detoxification of OPPs by ultrasonic irradiation was discriminative.     

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.     

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.     

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。     

Ozonation of Cationic Red X-GRL in aqueous solution: degradation and mechanism

Ozonation of the azo dye Cationic Red X-GRL was investigated in a bubble column reactor at varying operating parameters such as oxygen flow rate, temperature, initial Cationic Red X-GRL concentration, and pH. The conversion of dye increased with the increasing of pH and oxygen flow rate. As the reaction rate constant and the volumetric mass transfer coefficient increase while the ozone equilibrium concentration decreases with the temperature, there is a minimum conversion of dye at 25 degrees C. The increasing of initial dye concentration leads to a decreasing conversion of dye while the ozonation rate increases. The formation of intermediates and the variation of pH, TOC, and nitrate ion during ozonation were investigated by the use of some analytical instruments such as GC/MS, GC, and IC. The intermediates of weak organic acids lower the pH value of the solution. The probable degradation mechanism of the Cationic Red X-GRL in aqueous solution was deliberated with the aid of Molecular Orbital calculations. The N(12)-C(13) site in Cationic Red X-GRL, instead of the N(6)-N(7) site, is found to be the principal site for ozone cycloaddition in the degradation processes. During the degradation process, among the six nitrogen atoms of Cationic Red X-GRL, one is transferred into a nitrate ion, one is converted into an amine compound, and the remaining four are transformed into two molecules of nitrogen.