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.     

Decomposition of phorate in aqueous solution by ozonation

Phorate (O,O-diethyl S-ethylthiomethyl phosphorodithioate) dissolved in aqueous solution was almost completely decomposed by ozonation to form various species within 10 minutes of reaction time for the experimental conditions examined in this research. The generation rate of sulfate was found to be fairly independent of solution pH value. However, the formation of phosphate and carbonate was more favorable for alkaline solutions where hydroxyl free radical is the primary oxidative species. The reaction rates increased with initial gaseous ozone concentrations, indicating the reaction was mass transfer-controlled within the experimental range of this research. Combining the analytical results by various instruments, including gas chromatograph equipped with an electron ionization detector (GC-EID), high performance liquid chromatography (HPLC), ion chromatography (IC), and total organic carbon (TOC), the temporal sequence of phorate ozonation was proposed in this study. The oxidation of sulfur atoms on the phosphorus-sulfur double bond or carbon-sulfur-carbon bond by ozonation was found to occur at first to form sulfate and various intermediates.     

Degradation of anthraquinone dye C.I. Reactive Blue 19 in aqueous solution by ozonation

This study investigated the degradation of anthraquinone reactive dye C.I. Reactive Blue 19 (RB-19) with initial concentration of 100 mg L⁻¹ in aqueous solution by ozone oxidation. The results of UV/VIS and FTIR spectra showed that the anthraquinone structures, nitrogen linkages and amino groups of RB-19 were destroyed under direct ozone reaction. The identification by LC–MS and GC–MS analyses indicated that some organic acids (e.g., phthalic acids) and 1,3-indanone could be the primary degradation products, respectively. The Microtox toxicity of the ozonated RB-19 solution initially increased but subsequently decreased when ozonation time increased. This detoxification accompanied biodegradability enhancement revealed by BOD/COD ratio increasing from 0.15 to 0.33 after 10 min of ozonation.     

Decomposition of 2-mercaptothiazoline in aqueous solution by ozonation

This study investigates the ozonation of 2-mercaptothiazoline (2-MT). The 2-MT is one of the important organic additives for the electroplating solution of the printed wiring board industry and has been widely used as a corrosion inhibitor in many industrial processes. It is of concern for the aquatic pollution control especially in the wastewaters. Semibatch ozonation experiments in the completely stirred tank reactor are performed under various concentrations of input ozone. The concentrations of 2-MT, sulfate, and ammonium are analyzed at specified time intervals to elucidate the decomposition of 2-MT during the ozonation. In addition, the time variation of the dissolved ozone concentration (C(ALb)) is continuously monitored in the course of experiments. Total organic carbon (TOC) is chosen and measured as a mineralization index of the ozonation of 2-MT. The results indicate that the decomposition of 2-MT is efficient, while the mineralization of TOC is limited via the ozonation only. Simultaneously, the yield of sulfate with the maximum value of about 47% is characterized by the increases of TOC removal and ozone consumption. These results can provide some useful information for assessing the feasibility of the treatment of 2-MT in the aqueous solution by the ozonation.     

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。     

Photo-Fenton-assisted ozonation of p-Coumaric acid in aqueous solution

The degradation of p-Coumaric acid present in olive oil mill wastewater was investigated as a pretreatment stage to obtain more easily biodegradable molecules, with lower toxicity that facilitates subsequent anaerobic digestion. Thus, photo-Fenton-assisted ozonation has been studied and compared with ozonation at alkaline pH and conventional single ultraviolet (UV) and acid ozonation treatments. In the combined process, the overall kinetic rate constant was split into various components: direct oxidation by UV light, direct oxidation by ozone and oxidation by hydroxyl radicals. Molecular and/or radical ozone reaction was studied by conducting the reaction in the presence and absence of tert-butylalcohol at pHs 2, 7 and 9. Ozone oxidation rate increases with pH or by the addition of Fenton reagent and/or UV radiation due to generation of hydroxyl radicals, *OH. Hydrogen peroxide and ferrous ion play a double role during oxidation since at low concentrations they act as initiators of hydroxyl radicals but at high concentrations they act as radical scavengers. Finally, the additional levels of degradation by formation of hydroxyl radicals have been quantified in comparison to the conventional single processes and an equation is proposed for the reaction rate as a function of studied operating variables.     

Fenton 法降解抗生素磺胺间甲氧嘧啶钠

应用Fenton高级氧化技术降解水溶液中抗生素磺胺间甲氧嘧啶钠(SMMS),系统探讨了起始pH、CSMMS、CFe2+、CH2O2和温度等因素对SMMS降解效果的影响。结果表明:CSMMS=4.53 mg/L,pH=4.0,CH2O2=0.49 mmol/L,CFe2+=19.51μmol/L,T=25℃为最佳反应条件。在最佳条件下,87.4%的SMMS可以在120 min内降解。反应动力学研究表明Fenton氧化降解SMMS分为两个阶段,快速反应阶段和慢速反应阶段,并建立了两阶段动力学模型,模型拟合结果较好。研究结果为含有SMMS的污废水处理提供了基础数据和科学参考。     

臭氧光催化降解水中甲醛的研究

研究比较了3种光化学方法对水中低浓度甲醛的降解效果,考察了初始pH值、甲醛浓度和臭氧投加速率等因素对臭氧光催化(TiO_2/UV/O_3)降解甲醛的影响。结果表明,紫外臭氧(UV/O_3)、光催化(TiO_2/UV)和TiO_2/UV/O_3对甲醛的降解均符合表观一级反应动力学,TiO_2/UV/O_3降解甲醛的一级表观速率常数大于TiO_2/UV与UV/O_3之和,说明臭氧、光催化有明显的协同作用。pH值对臭氧光催化降解甲醛的速率几乎没有影响;甲醛初始浓度增加,表观反应速率常数下降,但甲醛的绝对去除量仍随初始浓度的增加而显著增加;臭氧投加速率增加,降解速率增加。甲醛降解的主要中间产物为甲酸,但甲酸在臭氧光催化反应过程中也快速降解而被矿化,说明臭氧光催化是一种能安全有效去除甲醛的方法。     

Photo-induced degradation of diuron in aqueous solution by nitrites and nitrates: kinetics and pathways

The photo-induced degradation of diuron (3-(3,4-dichlorophenyl)-1,1-dimethylurea) in aqueous solution under simulated solar irradiation has been investigated in the presence of NO3-/NO2- ions. The degradation rates were compared by varying environmental parameters including substrate and inducer concentrations, oxygen content and pH. The photoproducts were identified by extensive LC-ESI-MS and LC-ESI-MS-MS studies after SPE preconcentration on prepacked cartridges. In both NO3- and NO2- conditions, oxidation of the N-(CH3)2 terminus group is the main process leading to the N-monodemethylated (NHCH3), N-formyl (N(CH3)CHO) and the uncommon and unstable carbinolamine (N(CH3)CH2OH) by-products. Cl/OH substituted and nitrated phenylureas are formed minorily. Degradation pathways involving OH* and NO2* (or dimer) radicals as reactive species are proposed.     

水溶液中活性艳红KE-3B的臭氧超声联合脱除

采用臭氧/超声联合技术去除模拟废水中的活性艳红KE-3B。臭氧/超声处理前后KE-3B的紫外可见吸收谱没有明显的变化。臭氧/超声联合作用、单独臭氧化和单独超声处理脱除活性艳红KE-3B模拟废水5 min后的去除率分别为97%、73%和5%,表明臭氧/超声联合降解活性染料具有更高的氧化速率。实验研究了pH值、臭氧投加量、超声能量密度、反应温度对超声/臭氧降解活性艳红KE-3B反应速率的影响,在实验研究范围内,随着溶液初始pH的增大,KE-3B的去除率先增大后减小,超声能量密度的改变对KE-3B的去除影响不大,温度升高有利于氧化反应的进行。在溶液初始pH值为9.0,臭氧投加量3.2 g/h,超声能量密度176 W/L,反应温度20℃时,浓度为100 mg/L的活性艳红KE-3B溶液的去除率最高。     

Mineralization of C.I. Reactive Yellow 84 in aqueous solution by sonolytic ozonation

The operational parameters and mechanism of mineralization of C.I. Reactive Yellow 84 (RY84), one of the azo dyes, in aqueous solution were investigated using sonolytic ozonation (US/O(3) oxidation). Of the pseudo-first-order degradation rate constants of TOC reduction, 9.0 x 10(-4), 7.3 x 10(-3) and 1.8 x 10(-2)min(-1) were observed with US, O3, and a combination of US and O3, respectively. These results illustrate that ozonation combined with sonolysis for removal of TOC is more efficient than ozonation alone or ultrasonic irradiation alone without considering the operating costs. With the initial pH value at 10.0, the ozone dose at 4.5 g h(-1), the energy density of ultrasound at 176 W l(-1), and the initial concentration of RY84 at 100 mg l(-1), the extent of mineralization measured as TOC loss was maximized. The variation of the concentrations of related ions (oxalate, formate, acetate, NO3(-), NO2(-), NH4(+), Cl(-), and SO4(2-)) during the reaction process was monitored. Other organic intermediates detected by GC/MS were N-methyleneaniline, phthalic acid, 4-hydroxyphthalic acid, isocyanatobenzene, aniline, 4-iminocyclohexa-2,5-dien-1-one, butene diacid and urea. Based on these findings, a tentative degradation pathway was proposed.     

臭氧催化氧化降解苯胺的机理

对臭氧单独氧化和臭氧催化氧化下的苯胺降解效率进行了比较,并通过液质联机分析了氧化过程中产物变化情况。实验结果表明,催化剂MnO2-CuO-CeO2/沸石的添加能有效地提高臭氧氧化苯胺的降解率,当苯胺初始浓度为200mg/L,反应20 min后,苯胺的去除率由原来的75%提高到89%;通过LC-MS分析,臭氧催化氧化苯胺降解过程中代谢产物依次为对亚胺醌、对苯醌、马来酸和草酸,并由此推断出了臭氧催化氧化降解苯胺的途径。     

UV/Fenton氧化降解水溶液中甲基叔丁基醚的试验研究

采用UV／Fenton技术对污染水体中的甲基叔丁基醚（MTBE）进行了氧化降解试验。结果表明，在室温条件下，当H2O2为10mmol／L，FC＋为2mmol／L，pH为2．4时，起始摩尔浓度为1mmol／L的MTBE在30min内可去除99％；结果还显示了MTBE的降解分两个阶段，第一阶段是在UV／Fe^2＋／H2O2下的快速降解，第二阶段由于Fe^2＋的大量消耗而降解相对较慢。     

超声联合过硫酸钠去除水中三氯生

采用超声（US）联合过硫酸钠（SPS）对水中三氯生（TCS）的去除进行了研究,GC/MS鉴定识别了联用工艺降解产物,考察了US功率、SPS的投加量、pH值、碳酸盐和溴离子等对TCS去除的影响。结果表明2,4-二氯苯酚（2,4-DCP）为其主要降解产物,US/SPS工艺强化了单独US去除效果,SPS浓度为4 mmol·L-1,US功率为600 W时,初始浓度为 410 μg·L-1的TCS 120 min后去除率可达100%。TCS的降解符合拟一级反应动力学方程,其动力学常数K=0.028 min-1。TCS的去除率随SPS浓度的增加先增大后减小,实验范围内（0~600 W）TCS去除率随US功率增加而增大,强酸强碱环境不利于TCS的去除,TCS去除率随碳酸氢钠浓度的增加先减小后增大,碳酸钠的加入对TCS去除影响不大,溴离子对TCS的去除具有抑制作用。     

Ozonation of metoprolol in aqueous solution: ozonation by-products and mechanisms of degradation

This study investigated the degradation pathway of metoprolol, a widely used β-blocker, in the ozonation via the identification of generated ozonation by-products (OPs). Structure elucidation of OPs was performed using HPLC coupled with quadrupole time-of-flight high-resolution mass spectrometry. Seven OPs were identified, and four of these have not been reported elsewhere. Identified OPs of metoprolol included aromatic ring breakdown by-products; aliphatic chain degraded by-products and aromatic ring mono-, di-, and tetrahydroxylated derivatives. Based on the detected OPs, metoprolol could be degraded through aromatic ring opening reaction via reaction with ozone (O₃) and degradation of aliphatic chain and aromatic ring via reaction with hydroxyl radical (?OH).     

Fenton试剂氧化降解水中的盐酸四环素

利用Fenton试剂对水中盐酸四环素（TC）氧化降解,考察H2O2/Fe2+（摩尔比）、Fenton试剂投加量、溶液pH值对盐酸四环素去除的影响,研究了盐酸四环素降解过程及动力学特征。研究结果表明：对于初始浓度为0.10 mmol·L-1的盐酸四环素,最优反应条件为pH值3.0,H2O2/Fe2+=10：1（物质的量之比）,H2O2施加量1.58 mmol·L-1。在该条件下反应60 min,盐酸四环素降解率达88.47%,对应TOC去除率为18.48%;紫外可见光谱扫描结果表明氧化过程中盐酸四环素的共轭结构被首先破坏;分别采用一级和二级动力学方程拟合降解过程,结果表明反应过程遵循二级动力学模型。     

Degradation of bisphenol A in aqueous solution by persulfate activated with ferrous ion

Degradation of bisphenol A (BPA) in aqueous solution was studied with high-efficiency sulfate radical (SO₄ ^?·), which was generated by the activation of persulfate (S₂O₈ ^2?) with ferrous ion (Fe²⁺). S₂O₈ ^2? was activated by Fe²⁺ to produce SO₄ ^?·, and iron powder (Fe⁰) was used as a slow-releasing source of dissolved Fe²⁺. The major oxidation products of BPA were determined by liquid chromatography-mass spectrometer. The mineralization efficiency of BPA was monitored by total organic carbon (TOC) analyzer. BPA removal efficiency was improved by the increase of initial S₂O₈ ^2? or Fe²⁺ concentrations and then decreased with excess Fe²⁺ concentration. The adding mode of Fe²⁺ had significant impact on BPA degradation and mineralization. BPA removal rates increased from 49 to 97 % with sequential addition of Fe²⁺, while complete degradation was observed with continuous diffusion of Fe²⁺, and the latter achieved higher TOC removal rate. When Fe⁰ was employed as a slow-releasing source of dissolved Fe²⁺, 100 % of BPA degradation efficiency was achieved, and the highest removal rate of TOC (85 %) was obtained within 2 h. In the Fe⁰–S₂O₈ ^2? system, Fe⁰ as the activator of S₂O₈ ^2? could offer sustainable oxidation for BPA, and higher TOC removal rate was achieved. It was proved that Fe⁰–S₂O₈ ^2? system has perspective for future works.     

Fe(Ⅱ)活化过硫酸钠去除水中三氯生

采用Fe2+活化过硫酸钠（SPS）对水中三氯生（TCS）的去除进行了研究,考察了Fe2+、SPS的投加量、TCS初始浓度、pH值和腐殖酸（HA）等对TCS去除的影响,GC-MS鉴定识别了降解产物。结果表明Fe2+活化SPS工艺能有效去除TCS,2,4-二氯苯酚（2,4-DCP）为其主要降解产物,SPS浓度为1.0 mmol·L-1,Fe2+的投加量为0.4 mmol·L-1时,初始浓度为460 μg·L-1的TCS 2 min后去除率可达93.87％,TCS慢速反应阶段的降解符合一级反应动力学方程,其动力学常数K=0.140 min-1。TCS的去除随Fe2+浓度的增加先增大后减小,高浓度的Fe2+不利于2,4-DCP的降解,适量提高SPS浓度有利于TCS的去除和2,4-DCP的降解,TCS去除随初始浓度增大而降低,酸性环境有利于TCS的去除,腐殖酸对TCS的去除具有抑制作用,低浓度腐殖酸不利于2,4-DCP的降解。     

Degradation of dyes from aqueous solution by Fenton processes: a review

Several industries are using dyes as coloring agents. The effluents from these industries are increasingly becoming an environmental problem. The removal of dyes from aqueous solution has a great potential in the field of environmental engineering. This paper reviews the classification, characteristics, and problems of dyes in detail. Advantages and disadvantages of different methods used for dye removal are also analyzed. Among these methods, Fenton process-based advanced oxidation processes are an emerging prospect in the field of dye removal. Fenton processes have been classified and represented as “Fenton circle”. This paper analyzes the recent studies on Fenton processes. The studies include analyzing different configurations of reactors used for dye removal, its efficiency, and the effects of various operating parameters such as pH, catalyst concentration, H₂O₂ concentration, initial dye concentration, and temperature of Fenton processes. From the present study, it can be conclude that Fenton processes are very effective and environmentally friendly methods for dye removal.     

臭氧氧化法处理反渗透浓缩垃圾渗滤液

采用臭氧氧化法处理经反渗透膜处理后的浓缩垃圾渗滤液,考察了反应时间、臭氧投量、pH和温度对COD,色度以及浓缩液中腐殖酸的去除影响,通过BOD₅/COD变化分析了臭氧氧化对浓缩液生化性的提高作用。结果表明：在pH 8.0,温度30℃,臭氧投量5 g/h,反应时间90 min的条件下,浓缩液的COD、色度以及浓缩液中腐殖酸的去除率分别达到67.6%、98.0%和86.1%, BOD₅/COD从0.008提升到0.26,生化性有很大提高。