Fenton法和类Fenton法降解土壤中的二苯砷酸

本文对Fenton法与类Fenton法降解土壤中的二苯砷酸(diphenylarsinic acid,DPAA)进行了研究.考察了H2O2投加量和催化剂种类(Fe2+/Fe3+)对红壤及黑土中DPAA降解效果的影响,并采用高效液相色谱-质谱联用法(HPLC-MS/MS)对降解中间产物进行了初步鉴定.结果显示,针对红壤与黑土分别采用类Fenton法与Fenton法,在H2O2投加浓度为1 mol·L-1,含铁催化剂浓度为0.25 mol·L-1,土水比为1∶3,反应时间为1h的条件下,红壤及黑土中DPAA的降解率均可达到65%以上.HPLC-MS/MS的分析结果表明,DPAA可脱苯环形成降解产物苯砷酸(phenylarsinic acid,PAA),而PAA进一步氧化生成无机砷,这可能是Fenton/类Fenton法降解DPAA的途径之一.     

接种降解菌对土壤中邻苯二甲酸二异辛酯降解的影响

邻苯二甲酸二异辛酯〔Di-(2-Ethylhexyl)phthalate,DEHP〕是农田土壤中常被检出的有毒有机污染物,在土壤中有较长的持留性,微生物降解是其从土壤中消失的主要途径.本文采用温室盆栽试验研究了接种两株从污水处理厂活性污泥中分离得到的高效DEHP降解菌及其混合菌悬液降解土壤中DEHP污染的效果,以及土壤中添加葡萄糖和种植作物对其降解效率的影响.结果表明,在土壤初始DEHP浓度为100mg kg-1的条件下,接种两种降解菌及其混合菌悬液都可显著提高土壤中DEHP消失的速率,其残留半衰期比不接种对照缩短了32~48d,但在相同条件下接种不同降解菌的处理之间没有显著差异.土壤中添加0.6%的葡萄糖虽然可以强烈地促进土壤微生物的整体活性,但并没有提高修复效率,反而在短期内延缓了降解菌对DEHP的降解,延长了DEHP在土壤中持留的半衰期;植物生长可显著提高降解菌的降解效率,降低土壤中DEHP的残留浓度.研究结果同时也表明,只添加葡萄糖或只种植植物对土壤中DEHP的降解并没有显著的影响.图3表4参14     

邻苯二甲酸二(2-乙基己基)酯酶促降解研究

研究了本室从污水处理厂的活性污泥和塑料厂排污口土壤中分离到的两株邻苯二甲酸二(2-乙基己基)酯(DEHP)降解菌CQ0110Y和CQ0110G粗酶液的相关性状及其对DEHP的酶促降解，结果表明，菌株CQ0110Y和XQ0110G降解酶都属于胞内酶．CQ0110Y粗酶液在pH6．0～8．0之间较为稳定，CQ0110G粗酶液在pH6．0～7．5之间较为稳定，CQ0110Y和CQ0110G粗酶液在10℃较为稳定．DEHP的降解产物中含有邻苯二甲酸单(2-基己基)酯、邻苯二甲酸、苯甲酸、对羟基苯甲酸、苯酚以及一些小分子酸类和醇类物质．图4表1参9     

新型纳米CeO2催化类Fenton降解盐酸四环素

本研究分别以NaOH和NH_3·H_2O为矿化剂,Ce(NO_3)_3·6H_2O为铈源,采用水热法成功制备两种新型纳米二氧化铈材料(CeO_2-Na与CeO_2-N).XRD、FESEM、Raman和EPR等表征手段以及非均相类Fenton降解盐酸四环素(TCH)性能分析结果表明,与CeO_2-N相比,纳米CeO_2-Na催化剂具有更大的比表面积和更高的表面氧空位浓度,其对TCH的催化性能也优于CeO_2-N.在TCH初始浓度为100 mg·L~(-1),催化剂投加量为0.7 g·L~(-1)和H_2O_2投加量为10 mmol·L~(-1)的条件下,CeO_2-Na/H_2O_2/TCH体系对TCH的去除率达86%,通过简单的热处理可以恢复催化剂的催化活性.TCH的降解机理研究表明,该非均相催化体系中起主要作用的是O~-_2·自由基.本研究为纳米氧化铈催化剂的制备及其非均相类Fenton的应用提供一定的技术和理论参考.     

Fenton氧化4-氯酚降解机制研究

为了深入探讨4-氯酚（4-CP）在Fenton氧化体系中的降解机制,利用高效液相色谱（HPLC）等多种手段系统分析了反应过程中Fe2＋、Cl-、氧化中间产物对苯二酚、1,4-苯醌、4-氯邻苯二酚和4-氯间苯二酚的浓度以及氧化还原电位（ORP）的变化规律.研究结果表明,Fe2＋浓度经历了短暂的下降之后迅速上升到接近初始的...     

铁锰矿类Fenton异相光催化降解有毒有机染料

选取6种天然铁锰矿石为光催化剂,以可见光(λ420nm)照射下活化H2O2降解有机染料罗丹明B(RhodamineB,RhB)为探针反应,筛选出活性较高的天然矿石(磁赤铁矿)催化降解RhB及2,4-二氯苯酚(2,4-Dichlorophenol,DCP).实验表明,可见光下磁赤铁矿在pH=7.0的介质体系,H2O2浓度为3×10-3mol·l-1条件下可有效降解RhB.通过反射紫外光谱、原子吸收分光光度法、XRD初步表征了磁赤铁矿组成结构;采用紫外-可见吸收光谱(UV-vis)、红外光谱(IR)、总有机碳(TOC)测定等方法,研究了其可见光照射下对RhB光催化降解特性.结果表明,在实验条件下RhB矿化率达60%,DCP矿化率达到63.93%.利用电子自旋捕捉技术(ESR)跟踪测定RhB降解过程中氧化物种,表明催化降解过程涉及羟基自由基(·OH)氧化过程.拟定异相矿石类Fenton体系与传统均相Fenton体系相比,具有反应介质pH范围宽(3.0—7.0)、可见光激发及催化剂易得廉价等优势。     

超声波/Fenton试剂联用降解水中的吡啶

采用超声波/Fenton联用技术降解水中的吡啶,探讨了吡啶初始浓度、反应温度、pH值、H2O2浓度、超声波声能密度和超声波频率对降解效果的影响及规律,实验发现,在所研究的吡啶初始浓度范围内,随着吡啶初始浓度的增大,其降解率减小;同时,随着反应温度、pH值、H2O2浓度和超声波声能密度的增大,吡啶的降解率增大;对于24.55kHz和30.19kHz两种频率而言,超声波频率愈高吡啶的去除率愈大,而对于30.19kHz和34.19kHz两种频率而言,吡啶去除率随频率的变化关系不明显,超声波和Fenton联用对吡啶进行降解比二者单独降解吡啶有更好的处理效果,另外,对于不同初始浓度的吡啶溶液来说,在所研究的浓度范围内,超声波/Fenton试剂联用降解吡啶的反应属于一级动力学反应,     

不同活性物种对光催化降解水中邻苯二甲酸二甲酯动力学的贡献研究

采用光催化氧化技术对邻苯二甲酸二甲酯（DMP）进行降解研究,并在基础上考察了催化剂量,溶液pH和溶液初始浓度对降解速率的影响。且采用Langmuir-Hinshelwood动力学模型来描述DMP的光催化降解,研究表明DMP的光催化降解符合假一级动力学。系统研究了光催化降解DMP过程中不同活性物种对光催化反应速率的贡献,实验结果表明：在TiO2光催化降解DMP的过程中,？OH为主要的活性物种,其对DMP的降解速率贡献高于94%,而其它活性物种（ecb-,hvb＋,O2？-和H2O2）对光催化贡献较小。     

Fenton法与光Fenton法降解2,4-D的研究

对Fenton法与光Fenton法降解农药2,4-D进行了研究.探索了反应条件对降解效果的影响;确定了反应动力学和处理效率;同时考察了主要阴离子对反应效率的影响;以及不同条件下体系中羟自由基(·OH)的产生规律.结果表明,过氧化氢或亚铁离子的浓度过低或过高都对2,4-D的降解有不利影响,氧化剂与催化剂之间的最佳比例为5:1,最佳初始pH值在3.0-3.5之间.在最佳条件下,氧化剂与2,4-D比例为1:1时,可在10min内降解85%的农药,TOC去除率也达80%以上.引入紫外线,可在降低氧化剂剂量下达到同样效果.碳酸根和磷酸根分别在不同程度上影响2,4-D的降解效率.各种条件对体系中·OH产生效率的影响与2,4-D降解效果的变化规律一致,说明·OH是导致2,4-D降解的活性基团.     

A modified steam distillation method for volatile acids determination in anaerobic digestors

A modified steam distillation method for the accurate determination of low levels of volatile acids found primarily in low rate anaerobic digestors has been developed. The interference of bicarbonate alkalinity is minimal with complete removal of carbon dioxide from the sample prior to distillation. This removal can be achieved by boiling the acidified sample for 30 min in an erlenmeyer flask with ground‐glass neck attached to a reflux condenser.     

Sonocatalytic degradation of tetracycline antibiotic in aqueous solution by sonocatalysis

Tetracycline (TC), one of the most common antibiotics, is often poorly bio-degraded in conventional wastewater treatment plants. In this study, the sonocatalytic degradation of TC was investigated using TiO₂ nano-particles as catalyst. The effect of pH, initial TC concentrations, reaction times, and H₂O₂ concentrations were evaluated. The efficacy of ultrasonic irradiation alone in the removal of this pollutant was negligible but removal efficiency increased upon addition of TiO₂ up to 250 mg L^?1; increase of pH and initial TC concentration attenuated TC degradation. Addition of H₂O₂ raised the removal efficiency so that complete removal of TC was achieved within 75 min.     

Hydrogen peroxide (H2O2) requirement for the oxidation of crude oil in contaminated soils by a modified Fenton's reagent

The oxidation of soil organic matter (SOM) and total petroleum hydrocarbon were investigated in two soils at eight different hydrogen peroxide (H₂O₂) concentrations to determine the optimal H₂O₂ dosage for the efficient remediation of soils contaminated by crude oil with minimal SOM removal. In our study, H₂O₂ concentrations up to 1100 mM increased the SOM destruction up to 10%–15% in the two soils while no improvement of the crude oil removal efficiencies was observed. The results indicate that the destruction of SOM significantly limits the oxidation of crude oil because SOM might consume H₂O₂ more effectively than crude oil at H₂O₂ concentrations above 1100 mM. In addition, H₂O₂ concentrations higher than 1100 mM were not expected for both soils because of the extremely rapid H₂O₂ decomposition, and low H₂O₂ utilization, of both soils.     

Effect of silica additive on the thermal stability of catalysts for NOx abatement

The aim of the plesent investigation was to study the effect of SiO₂ addition on the thermal deactivation of V₂O₅/WO₃/TiO₂ catalysts used for NOx pollution abatement. The results suggest that the degradation of the catalytic properties is strongly correlated to the structural ageing which is, in turn, mainly related to the anatase–rutile phase transformation and to the WO₃ phase segregation. The addition of SiO₂ strongly influences the temperature at which these phenomena occur. In fact, it was found that the introduction of this oxide stabilizes the material, retarding the collapse of surface area, and increases the temperature of the anatase to rutile phase transition.     

过氧化氢和一氧化氮在小球藻抗阿特拉津胁迫中的作用

过氧化氢(H_2O_2)和一氧化氮(NO)作为信号分子,可调节植物生长、发育以及应对外源性胁迫。利用过氧化氢酶(CAT)以及NO清除剂(PTIO),研究了除草剂阿特拉津(atrazine,100μg·L~(-1))影响小球藻生长的机理,并分析内源性H_2O_2和NO在小球藻抗除草剂胁迫中的作用。研究结果表明,阿特拉津在诱发小球藻细胞死亡的过程中,不同程度促发了H_2O_2和NO生成;外源CAT可通过清除H_2O_2和诱导NO来缓解阿特拉津对小球藻的生长抑制;PTIO与阿特拉津的联合实验进一步证实,小球藻体内的NO诱导与H_2O_2的爆发无关,它们之间的合成没有相关性。因此,除草剂阿特拉津主要通过诱导小球藻体内的H_2O_2爆发来破坏藻细胞,抑制其生长,与NO的信号传递无关。     

Decolorisation of Acid Blue 74 by ultraviolet/H<Subscript>2</Subscript>O<Subscript>2</Subscript>

The photodegradation of Acid blue 74 in aqueous solution employing a H₂O₂/ultraviolet system in a photochemical reactor was investigated. The kinetics of decolorization were studied by application of a kinetic model. The results show that the reaction of decolorization followed pseudo-first order kinetics. We demonstrate that there is an optimum H₂O₂ concentration, at which the rate of the decolorization reaction is maximum. Irradiation at 253.7 nm of the dye solution in the presence of H₂O₂ results in complete discoloration after ten minutes of treatment.     

Photocatalytic formation of hydrogen peroxide over highly porous illuminated ZnO and TiO2thin film

The photocatalytic formation of hydrogen peroxide over ZnO and TiO₂thin films has been investigated in aqueous phase in the presence of molecular oxygen as an electron acceptor. These films are highly porous and showed enhanced catalytic activity in the photochemical formation of hydrogen peroxide. The amount of H₂O₂formed during 2 hour light illumination is 4–6 μM and the rates of formation of hydrogen peroxide of both the films are almost comparable. The yield of hydrogen peroxide increases with the increase in irradiation time and a trend of steady state concentration of H₂O₂is observed in the case of TiO₂thin film. Photodissolution of ZnO particles is observed in some extent during the process of prolonged UV light illumination.     

Different proxies for the reactivity of aquatic sediments towards oxygen: A model assessment

Information on benthic carbon mineralization rates is often derived from the analysis of oxygen microprofiles in sediments. To enable a direct comparison of different sediment environments, it is often desirable to characterize sediments by a single proxy that expresses their “reactivity” towards oxygen. For this, there are three commonly used proxies: the oxygen penetration depth (OPD), the oxygen flux at the sediment-water interface (DOU), and the maximum volumetric oxygen consumption rate (R_max). The OPD can be directly determined from the oxygen depth profile, while the DOU is usually obtained by a linear fit to the oxygen gradient either in diffusive boundary layer. The oxygen consumption rate R_max requires the fitting of a reactive-transport model to the data profile. This article shows that the OPD alone is a suboptimal proxy, because it shows a strong dependence on the half-saturation constant K_s, and secondly, because it is sensitive to the particular re-oxidation conditions right above the oxic-anoxic interface. Similarly, the volumetric oxygen consumption rate R_max is rather strongly dependent on the kinetic model formulation employed. To show this we fitted three different (Bouldin, Blackman and Monod) kinetics to the same oxygen data profiles. When fitting these models, the R_max values obtained differed by 20% for exactly the same oxygen profile. Accordingly, if one reports R_max values, it is crucial to specify the kinetic model alongside. Overall, DOU emerges as sediment reactivity proxy which is the least model dependent.     

H_2O_2致大鼠RTE细胞系氧化应激作用及GSH保护作用的体外研究

许多具有氧化作用的空气污染物,均能使细胞产生氧化损伤,使胸腺基质淋巴生成素(thymic stromal lymphopoietin,TSLP)含量上升。而TSLP是一种启动过敏性炎症的重要因子,会导致哮喘等疾病发生率的上升。在本研究中用过氧化氢(H_2O_2)模拟具有氧化作用的空气污染物进行染毒,研究细胞氧化应激水平的变化,并讨论还原型谷胱甘肽(GSH)对细胞受氧化损伤的保护作用。将大鼠支气管上皮细胞(RTE)分组培养,每组设置6个平行实验,分别用低、中、高剂量H_2O_2染毒3 h;高剂量设置1个重复,作为保护组,在染毒前用GSH保护2 h。结果显示,高剂量组H_2O_2(3.2 mmol·L~(~(-1)))染毒的细胞,其细胞活力下降(P0.01),丙二醛(MDA)水平上升(P0.01),TSLP水平上升(P0.05),与之相比,用GSH保护后的同剂量染毒组,上述指标得到全面缓解(P0.01)。这表明高浓度的H_2O_2会损伤细胞活力,并使MDA及TSLP水平上升,而GSH对TSLP及MDA的升高有极显著的抑制作用,即对细胞有一定的保护作用。     

培养基对大型溞(Daphnia magna)生长、繁殖和子代的影响

大型溞(Daphnia magna)急性活动抑制试验和繁殖试验是研究和评价新化学物质对水生生物危害性的重要手段之一。由于经济合作与发展组织(Organization for Economic Co-operation and Development, OECD)测试导则推荐的Elendt M4培养基中含有的乙二胺四乙酸(EDTA)可能会影响金属离子的活性,不适合用于含有金属离子样品的毒理学测试。为选出合适的替代培养基,采用Elendt M4培养基、美国材料与试验协会(American Society for Testing and Materials, ASTM)推荐的ASTM培养基和国际标准化组织(International Organization for Standardization, ISO)推荐的ISO培养基进行大型溞繁殖试验,并收集繁殖试验中亲溞产下的非头胎幼溞进行重铬酸钾的急性活动抑制试验。结果表明,3种培养基对大型溞的生长、存活均无抑制作用,ASTM培养基和ISO培养基中大型溞的繁殖量分别为111±10和70±13,显著低于Elendt M4培养基的132±4 (P 0.05)。3种培养基中大型溞的繁殖量均能满足OECD 211-2012大型溞繁殖试验标准中繁殖量大于60的要求,但在ISO培养基中有死胎出现。重铬酸钾对Elendt M4培养基、ASTM培养基和ISO培养基中繁殖幼溞的24 h半数效应浓度(24 h-EC_(50))值分别为1.29、1.84和0.772 mg·L~(-1),均在OECD 202-2004大型溞急性活动抑制试验标准要求的0.6～2.1 mg·L~(-1)范围内,说明3种培养基中繁殖的大型溞均能用于大型溞急性活动抑制试验的标准测试中。综上所述,进行含有金属离子样品的毒理测试时,ASTM培养基和ISO培养基均可用于大型溞的短期驯养和急性活动抑制试验,ASTM培养基还可以用于长期驯养和繁殖试验。以上结果为大型溞毒性试验中试验培养基的选择提供理论依据。