二氧化氯对颤蚓成虫灭活效果及灭活作用机制

采用对苯二甲酸（terephthalic acid,TA）作为羟基自由基（hydroxyl radical,·OH）捕捉剂,利用荧光分光光度法测定了二氧化氯（CIO2）接触后颤蚓体内-OH浓度变化,结合颤蚓灭活率、过氧化氢酶（catalase,CAT）和丙二醛（malondi．alderhyde,MDA）等指标的测试结果,研究了CIO2对颤蚓成虫的灭活效果及灭活机理。结果表明,ClO2对颤蚓成虫灭活效果显著。当C1O2投加浓度超过0．4mg／L,可对颤蚓体内·OH产生明显的诱导效应,并且·OH诱导效应与颤蚓灭活率直接相关。接触条件下CAT变化情况表明,颤蚓受到了明显的氧化胁迫,且对颤蚓体内抗氧化系统有破坏作用,MAD变化结果则表明ClO2对颤蚓的脂质过氧化作用不明显,可以对颤蚓表皮层有效渗透。上述结果证实了CIO2对颤蚓成虫的灭活作用机制之一是诱导其体内生成·OH,产生氧化胁迫,而CIO2对颤蚓抗氧化系统的破坏作用和对颤蚓表皮层的有效渗透进一步增强灭活效果。     

催化湿式过氧化（CWPO）偶氮染料反应机理及降解历程研究

采用浸渍法制备出具有较高催化活性的催化剂CuO/γ-Al2O3,通过XRD、电镜等手段对催化剂进行了表征。降解了几种不同结构的偶氮染料,并通过改变CWPO的反应条件推断了其催化反应机理。采用紫外/可见分光光度计（UV-Vis）和傅里叶红外光谱仪（IR）等手段对染料降解过程进行跟踪和分析,对比染料处理前后紫外可见光谱与红...     

微波催化剂CuO/AC微波催化氧化降解废水中的苯酚

通过浸渍法制备了CuO/AC作为微波催化剂,并采用XRD、FT-IR进行表征分析。考察了CuO担载量,微波催化剂用量、微波功率、辐照时间、pH值等因素对苯酚废水去除率的影响。结果表明,在微波功率600 W条件下,使用3 g CuO担载量0.5%的CuO/AC催化剂处理100 mL初始浓度为500 mg/L的苯酚模拟废水,反应18 min,去除率可达99.42%,相应TOC去除率为90.4%。通过添加不同氧化基团清除剂的实验发现,反应过程中产生了羟基自由基(·OH)。而添加大量H2O2或持续鼓入O2并不能有效提高苯酚的去除率。同时,还对微波催化氧化降解苯酚废水进行了动力学分析,发现其符合一级动力学方程模型,并得出表观速度常数随微波功率密度增加而增大的关系。     

Fenton试剂生成·OH的动力学研究

通过试验研究确定了Fenton试剂中羟基自由基·OH生成的动力学规律 ,系统考察了Fenton体系中三个主要因素 :H2 O2 浓度、FeSO4 浓度、pH值对羟基自由基·OH生成规律的影响情况 ,结果表明 ,这三个因素对羟基自由基的生成均有较大的影响 ,在实际生产过程中需加以严格控制 ,以保证最佳的处理效果     

电生成Fenton试剂及其对十二烷基苯磺酸钠降解的研究

以电化学方法制备·OH ,并探讨了体系内的反应机理 ;电生成·OH对十二烷基苯磺酸钠 (dodecylben zenesul phonicacid (6 ) sodiumsalt ,DBS)水溶液有明显的降解效果 ,CODCr降解率 >85 % ;比较了处理前后DBS的红外光谱、UV、I V循环伏安曲线的变化。·OH可以将DBS中的烷基碳链断裂 ,并最终将其降解为H2 O和CO2 等无机小分子。     

强化UV/Fenton法降解水中苯酚的研究

研究了UV/Fenton法处理含苯酚废水时H2 O2 和FeSO4 加入量及苯酚初始浓度对酚去除效果的影响及C2 O2 -4 对UV/Fenton法的增强效果。 [H2 O2 ]=2 0mmol/L ,[FeSO4 ]=5mmol/L ,反应 2 0min ,苯酚初始浓度为 5 0mg/L时 ,酚去除率达 99%。UV/Fenton体系中引入C2 O2 -4 后可有效提高对紫外和可见光的利用率 ,进而提高了对高浓度苯酚废水去除效果     

磁性纳米吸附剂Fe3O4·ZrO(OH)2的合成及对水中氟和砷的吸附性能

用共沉淀法将ZrOCl2·8H2O包裹在磁性纳米Fe3O4表面,合成了一种针对高浓度含砷含氟废水的高效新型磁性纳米吸附剂Fe3O4·ZrO(OH)2.研究考察了吸附剂对氟和砷的吸附容量、反应平衡时间以及pH对吸附效果的影响.实验表明,磁性纳米Fe3O4·ZrO(OH)2吸附剂对水中F-和As(Ⅲ/Ⅴ)等温吸附模型符合Langmuir和Freundlich模型.对溶液中总氟和总砷的吸附容量分别可达70.42 mg/g和133.33 mg/g.通过拟二级动力学方程可得知吸附过程在20 min左右即可达到平衡.随着pH的不断增加,吸附剂对氟的吸附容量逐渐降低,而对砷的吸附量则是先增加后减少.     

掺硼金刚石三电极系统处理垃圾渗滤液实验研究

实验以掺硼金刚石电极为阳极构建三电极系统处理稳定的垃圾渗滤液.考察了稀释比、初始pH值、电流密度和极板间距4个因素对垃圾渗滤液污染物去除率的影响.实验结果表明,电流密度、稀释比是影响电化学氧化垃圾渗滤液的主要因素,极板间距、初始pH值对电化学氧化垃圾渗滤液的影响较小.在稀释比为1:2、电流密度为75 mA/cm2、pH值未调节、极板间距为10 mm最优工况时,经过5 h电化学氧化后NH4+-N、COD均能完全去除;NH4+-N、COD去除率分别满足线性方程y =21.759t、y =20.717t,对应的线性相关系数为0.9923和0.9925.最优工况条件下,BDD电极电化学氧化垃圾渗滤液的能耗为260 kWh/m3.     

Fenton氧化水中间氯硝基苯的动力学与机制研究

结合Fenton氧化反应动力学模型研究了Fenton氧化水中间氯硝基苯(m-ClNB)的影响因素和降解机制.结果表明:(1)反应初始pH、H2O2浓度、Fe2+浓度、污染物初始浓度和反应温度对m-ClNB的降解均有明显影响.在反应初始pH为3.5、m-ClNB初始摩尔浓度为0.444mmol/L、H2O2摩尔浓度为21.55mmol/L、Fe2+摩尔浓度为0.054mmol/L、反应温度为(25土1)℃的条件下,m-ClNB的去除效果较好.(2)建立了Fenton氧化m-ClNB的准一级反应动力学模型,且m-ClNB的降解与该模型拟合良好.基于不同反应温度时的准一级反应速率常数(kap),得到了m-ClNB降解的阿累尼乌斯公式,且活化能为36.51kJ/mol.(3)气相色谱(GC)/质谱(MS)和高效液相色谱(HPLC)/MS分析表明,Fenton氧化m-ClNB的主要产物有4-氯-2-硝基苯酚及其同分异构体、羟基乙酸、草酸、丁二酸、丙二酸、6-氯己酸、乙醛酸、2,2-二羟基丙二酸和2-乙基丙二酸等.     

He-Ne激光诱变选育高效石油烃降解菌的研究

采用He-Ne激光器对绿针假单胞菌(Pseudomonas chlororaphis)进行激光诱变育种。在激光照射功率10 mW,时间10 min条件下,筛选到一株遗传性状稳定的高效石油烃降解菌PS 2。摇瓶实验发现当培养液中初始柴油含量为0.2%～0.5%(V/V)、温度为30℃左右、pH值为7～8的条件下,突变菌PS 2对石油烃的降解效果最好。在最适生长条件下,突变菌PS 2在120 h内将培养液中的石油烃完全降解且不存在延滞期,比出发菌株少用24 h。结果表明,He-Ne激光诱变育种技术是获得高效石油烃降解菌的有效途径之一。     

An investigation into reservoir NOM reduction by UV photolysis and advanced oxidation processes

A comparison of four treatment technologies for reduction of natural organic matter (NOM) in a reservoir water was made. The work presented here is a laboratory based evaluation of NOM treatment by UV-C photolysis, UV/H(2)O(2), Fenton's reagent (FR) and photo-Fenton's reagent (PFR). The work investigated ways of reducing the organic load on water treatment works (WTWs) with a view to treating 'in-reservoir' or 'in-pipe' before the water reaches the WTW. The efficiency of each process in terms of NOM removal was determined by measuring UV absorbance at 254 nm (UV(254)) and dissolved organic carbon (DOC). In terms of DOC reduction PFR was the most effective (88% removal after 1 min) however there were interferences when measuring UV(254) which was reduced to a lesser extent (31% after 1 min). In the literature, pH 3 is reported to be the optimal pH for oxidation with FR but here the reduction of UV(254) and DOC was found to be insensitive to pH in the range 3-7. The treatment that was identified as the most effective in terms of NOM reduction and cost effectiveness was PFR.     

Carbamazepine degradation by photolysis and titanium dioxide photocatalysis

We investigated the degradation of carbamazepine by photolysis/ultraviolet (UV)-C only and titanium dioxide photocatalysis. The degradation of carbamazepine by UV-only and titanium-dioxide-only (adsorption) reactions were inefficient, however, complete degradation of carbamazepine was observed by titanium dioxide photocatalysis within 30 min. The rate of degradation increased as initial carbamazepine concentration decreased, and the removal kinetics fit well with the Langmuir-Hinshelwood model. The addition of methanol, a radical scavenger, decreased carbamazepine removal, suggesting that the hydroxide radical played an important role during carbamazepine degradation. The addition of oxygen during titanium dioxide photocatalysis accelerated hydroxide radical production, thus improving mineralization activity. The photocatalytic degradation was more efficient at a higher pH, whereas the removal of carbamazepine and acridine (a major intermediate) were more efficient under aerobic conditions. The mineralization of carbamazepine during photocatalysis produced various ionic by-products such as ammonium and nitrate by way of nitrogen dioxide.     

Hydrogen peroxide mediated photodegradation of phenol as studied by a flash photolysis/HPLC technique

The technique of flash photolysis followed by high-performance liquid chromatography has been applied to the study of the photodegradation of phenol (I) in the presence of hydrogen peroxide. Progress of the reaction of I (0.1 mM) in undegassed aqueous solution ([H2O2]/[I] = 200/l) was observed by using multiple flashes (16 J). Analysis after a single flash indicated that catechol and hydroquinone were the primary products of the reaction. The reaction was found to be independent of pH in the range 7.0-9.0, but the yield of degradation decreased at pH > 9.0 and at pH < 7.0. The effects of the hydrogen peroxide concentration and flash energy on the chemical yield of the pollutant degradation, and product formation, were investigated as well. The mechanism of the reaction is discussed. A possibility of the application of flashlamps as powerful sources of the UV irradiation in industrial reactors for wastewater treatment is suggested.     

Oxidative degradation of chlorophenol derivatives promoted by microwaves or power ultrasound: a mechanism investigation

Background, aim, and scope

Phenols are the most common pollutants in industrial wastewaters (particularly from oil refineries, resin manufacture, and coal processing). In the last two decades, it has become common knowledge that they can be effectively destroyed by nonconventional techniques such as power ultrasound (US) and/or microwave (MW) irradiation. Both techniques may strongly promote advanced oxidation processes (AOPs). The present study aimed to shed light on the effect and mechanism of US- and MW-promoted oxidative degradation of chlorophenols; 2,4-dichlorophenoxyacetic acid (2,4-D), a pesticide widespread in the environment, was chosen as the model compound.

Materials and methods

2,4-D degradation by AOPs was carried out either under US (20 and 300 kHz) in aqueous solutions (with and without the addition of Fenton reagent) or solvent-free under MW with sodium percarbonate (SPC). All these reactions were monitored by gas chromatography–mass spectrometry (GC–MS) analysis and compared with the classical Fenton reaction in water under magnetic stirring. The same set of treatments was also applied to 2,4-dichlorophenol (2,4-DCP) and phenol, the first two products that occur a step down in the degradation sequence. Fenton and Fenton-like reagents were employed at the lowest active concentration.

Results

The effects of US and MW irradiation were investigated and compared with those of conventional treatments. Detailed mechanisms of Fenton-type reactions were suggested for 2,4-D, 2,4-DCP, and phenol, underlining the principal degradation products identified. MW-promoted degradation under solvent-free conditions with solid Fenton-like reagents (viz. SPC) is extremely efficient and mainly follows pyrolytic pathways. Power US strongly accelerates the degradation of 2,4-D in water through a rapid generation of highly reactive radicals; it does not lead to the formation of more toxic dimers.

Discussion

We show that US and MW enhance the oxidative degradation of 2,4-D and that a considerable saving of oxidants and cutting down of reaction times is thereby achieved. The results support the interpretation of previously published data and improve the understanding of the factors of direct degradation along different pathways.

Conclusions

Oxidative pathways for 2,4-D, 2,4-DCP, and phenol were proposed by a careful monitoring of the reactions and detection of intermediates by GC–MS.

Recommendations and perspectives

The understanding of the factors that affect chlorophenols degradation along different pathways may facilitate the optimization of the treatment. Type of energy source (US or MW), power, and frequency to be applied could be designed in function of the operative scenario (amount of pollutant in soil, water, or oils).     

Different reaction mechanisms of diphenylether and 4-bromodiphenylether with nitrous acid in the 355 nm laser flash photolysis of mixed aqueous solution

The microscopic reaction mechanisms of diphenylether (DPE) and 4-bromodiphenylether (4-BrDPE) with nitrous acid (HNO(2)) in the absence of O(2) have been explored by the 355nm laser flash photolysis. It was proposed that OH radical, from the photolysis of HNO(2), added to DPE forms the C(12)H(10)O-OH adduct while added to 4-BrDPE forms the 4-BrDPE-OH and 4-BrOH-DPE adducts. The first-order decay rate constants of the C(12)H(10)O-OH adduct, 4-BrDPE-OH adduct and 4-BrOH-DPE adduct were measured to be (1.86+/-0.14)x10(5)s(-1), (2.19+/-0.04)x10(5)s(-1) and (1.56+/-0.03)x10(5)s(-1), respectively. The final photolysis products of DPE and HNO(2) identified by GC/MS analysis were phenol, o-hydroxydiphenylether, p-hydroxydiphenylether and p-nitrodiphenylether, while the final photolysis product of 4-BrDPE and HNO(2) identified by LC/MS analysis was mainly the dimer.     

A laser flash photolysis study of the decay of SO4- and Cl2- radical anions in the presence of Cl- in aqueous solutions

The rate constant for the reaction of sulphate radical (SO4-) with Cl- has been determined using laser photolysis, at 248 nm, of peroxodisulphate anions to produce the radicals and time resolved optical absorption of the transient species (at 450 or 480 nm for SO4- and 350 nm for Cl2-) for the kinetic determinations. The experiments were performed, in the absence of added sulphate, as a function of temperature and ionic strength and yielded (at an ionic strength of 0.0157 M): kIV = (9.90+/-0.16) x 10(9) exp((-7.12+/-2.0) kJ mol(-1)/RT) M(-1) s(-1), where the errors reflect the 2sigma statistical error. This reaction produces Cl2-, the formation and decay of which were also monitored allowing a determination of the rate constant of its second-order self-recombination reaction which gave k = (6.50+/-1.40) x 10(8) M(-1) s(-1) at 293 K and zero ionic strength.     

The degradation of endocrine disruptor di-n-butyl phthalate by UV irradiation: a photolysis and product study

The direct photolysis of an important endocrine disruptor compound, di-n-butyl phthalate (DBP), has been investigated under monochromatic UV irradiation at 254 nm over a wide pH range (3-11). The investigation was carried out under idealized conditions and has considered both reaction kinetics and the degradation mechanism. It was found that more than 90% of DBP can be degraded within an hour of irradiation in water. A simple model has been developed and used to predict the initial DBP photolysis rate constant at different pH values and initial DBP concentrations. The major decomposition mechanism of DBP is believed to involve the hydrolytic photolysis of the carbon in the alpha and/or beta-position of the ester chain with the production of aromatic carboxylic derivatives. Additionally, multi-degradation pathways are proposed for acid-catalyzed hydrolytic photolysis (pH 3-5), which was found to be useful in explaining the photo-degradation of DBP under acidic conditions. The use of 254 nm UV to photo-degrade DBP was found to be a relatively fast and clean process, especially in neutral to basic conditions.     

Studies on degradation of glyphosate by several oxidative chemical processes: Ozonation,photolysis and heterogeneous photocatalysis

Several different Advanced Oxidation Processes (AOPs) including ozonation at pH 6.5 and 10, photolysis and heterogeneous photocatalysis using TiO₂ as semiconductor and dissolved oxygen as electron acceptor were applied to study the degradation of glyphosate (N-phosphonomethyl glycine) in water. The degree of glyphosate degradation, the reactions kinetic and the formation of the major metabolite, aminomethyl phosphonic acid (AMPA), were evaluated. Ozonation at pH 10 resulted in the maximum mineralization of glyphosate. It was observed that under the experimental conditions used in this study the degradation of glyphosate followed the first-order kinetics. The half-life obtained for glyphosate degradation in the O₃/pH 10 process was 1.8 minutes.     

无过氧化氢添加Fenton氧化法降解有机物的可行性研究

Fenton反应可以氧化分解有机物,在反应中的关键氧化剂羟基自由基(HO·)是通过亚铁离子与过氧化氢作用生成的,因此,传统的Fenton氧化必须由外部添加过氧化氢.研究了一种新的方法,即采用Nafion膜固定化亚铁离子,并通过光催化反应提供Fenton氧化所需的过氧化氢,使得Fenton反应在不添加过氧化氢的条件下也能够连续进行.结果表明,以甲酸为代表有机物,该方法可以在不添加过氧化氢的条件下起到分解甲酸的作用.而且,通过对负载亚铁离子Nafion膜的再生,可以使该方法的降解能力保持在稳定的范围.