石墨烯修饰的二氧化钛纳米管电极光电催化去除铜氰络合物研究

首先采用阳极氧化法制备了二氧化钛纳米管电极,进一步通过电化学循环伏安法制备了石墨烯(GO)修饰的二氧化钛纳米管电极.同时,采用SEM对电极的形貌进行了表征分析.光电化学测试分析结果表明,石墨烯修饰二氧化钛纳米管电极的电极光电响应性能得到了提高.最后,采用制备的电极为光阳极,通过光电催化氧化方法对铜氰络合物进行了去除研究.结果表明:在电压为2.0 V的条件下,采用二氧化钛纳米管电极,反应120 min后,剩余总氰的含量及铜的回收率分别为4.0%和96.3%;采用石墨烯修饰的二氧化钛纳米管,反应60 min后,剩余总氰的含量及Cu的回收率分别为0.3%和99%.可以看出,经石墨烯修饰的二氧化钛纳米管显示出了较好的光电催化去除铜氰络合物的效果.     

金属掺杂对纳米管TiO_2光催化去除水中罗丹明B的影响

采用水热合成法,将Fe(NO3)3·9H2O、ZnCl2和AgNO3对纳米管TiO2进行掺杂,使用TEM、XRD、XPS、比表面积分析仪及UV-visDRS对掺杂后的纳米管TiO2进行表征并考察其光催化氧化去除罗丹明B的效果,从而优选最佳掺杂金属。结果表明,煅烧温度可影响纳米管TiO2锐钛矿相相对含量、比表面积及禁带宽度,进而影响其光催化活性。此外,掺杂金属离子的种类不同,纳米管TiO2的光催化活性也受到影响。500℃煅烧非掺杂纳米管TiO2的存在下,光催化氧化罗丹明B的去除率为98.72%。向纳米管TiO2中掺杂Fe3+、Zn2+及Ag+时,光催化氧化罗丹明B的效果得到提高。对以上三种掺杂金属离子而言,掺杂量为1.0%(原子百分含量)的催化剂的最佳煅烧温度为550℃。其中,Fe3+掺杂纳米管TiO2光催化活性最高,50min内光催化氧化罗丹明B的去除率可达99.0%。     

强化电化学阳极去除二氯甲烷行为的探究

采用N117型杜邦质子交换膜为隔离材料制作双室电化学反应器以强化阳极氧化反应,利用Ti基电极在阳极反应室内对二氯甲烷进行电化学氧化处理。研究表明:Ti电极对DCM有优于TiO2电极和IrO2-RuO2/Ti电极的氧化活性;双室反应器中电化学氧化去除二氯甲烷反应符合一级反应动力学方程;基于节能高效原则,选取最优参数为:槽电压30 V、25 mmol/L K2SO4、反应温度为25℃、初始pH为7,在240 min时DCM(10 mg/L)去除率为93.8%,TOC的去除率为55.1%。     

适于工业应用的TiO2纳米管的阳极氧化法制备

通过阳极氧化法制备了适于工业应用的大尺寸二氧化钛纳米管阵列.考察了电极形状和面积、氧化电压、氧化时间、预处理等因素对阳极氧化法制备二氧化钛纳米管阵列形貌的影响.结果显示,电极形状对纳米管的制备没有影响;阳极氧化前打磨与否对纳米管也没有影响;氧化电压、氧化时间和电极面积对纳米管的影响较大,只有在合适的电压和时间下才能制成纳米管阵列.电极面积影响电流密度,从而影响纳米管的形貌,试验中电极最大面积为360cm2.通过试验得出工业化制备二氧化钛纳米管阵列的最佳条件是电压20V,电解时间30min,反应前不用进行打磨.实验结果显示制成的纳米管阵列对强酸强碱的耐受力强,完全可以适应工业化废水的pH变化.     

一种基于电化学氧化法预处理制药废水的工艺

探究活性炭-电化学氧化联用工艺对制药废水进行预处理,以石墨-PTFE复合电极为阴极、Fe电极为阳极,通过在阴极表面通入空气的方式产生H2O2,进而与Fe2+发生Fenton反应。考察了单一电化学法与活性炭-电化学氧化联用工艺对废水降解过程的影响,分析出水中COD、氨氮、盐分的变化情况。结果表明,电化学法可有效降低水中有机污染物,同时将活性炭与电化学氧化联用显示出更高的处理效果,尤其在处理高浓废水时,COD、氨氮降解率可达82%和64%,对废水预处理领域有一定的指导意义。     

均相Fenton法处理石化废水反渗透浓水

采用均相Fenton法处理石化废水反渗透浓水,考察了H2O2浓度、Fe2+浓度、初始p H以及反应温度等因素对处理效果的影响,并分析了反渗透浓水的可生化性及污染物变化特征。结果表明,在H2O2浓度为75.0 mmolL,Fe2+浓度为7.5 mmolL,初始p H为3.0,反应温度为25℃的条件下,反应2.0 h后反渗透浓水TOC浓度由198.4 mgL降到111.6 mgL,有机物矿化去除率达43.7%,BOD5CODCr由0.11提高至0.28,反渗透浓水污染物浓度大幅降低,可生化性也得到明显改善。反渗透浓水处理前后的三维荧光光谱(EEM)分析结果表明,均相Fenton法对反渗透浓水中荧光有机物总去除率可达78.7%,改善了反渗透浓水的可生化性。     

L-组氨酸-赤藓红复合膜修饰电极同时检测对苯二酚、邻苯二酚

利用循环伏安法制备了L-组氨酸-赤藓红复合膜修饰玻碳电极(L-His-Erythrosine/GCE).采用扫描电镜(SEM)观察修饰电极的表面形貌结构,并用电化学阻抗谱(EIS)、循环伏安法(CV)表征修饰电极的电化学性能.在此基础上用差分脉冲伏安法(DPV)研究了对苯二酚(HQ)和邻苯二酚(CC)混合物在该电极上的电催化氧化,结果表明,L-His-Erythrosine/GCE对HQ及CC的电化学氧化具有显著的催化作用,两种异构体在该修饰电极上的氧化过电位明显降低,峰电流显著增大,二者氧化峰电位间隔达108m V,表明制备的修饰电极可用于HQ和CC的同时检测.在最佳实验条件下,HQ与CC浓度在1.2×10-6~1.1×10-4mol·L-1范围内与氧化峰电流呈良好线性关系,检出限分别为0.19μmol·L-1(HQ)和0.16μmol·L-1(CC)(S/N=3).另外,此修饰电极具有较好的重现性和较强的抗干扰能力,将修饰电极用于实际水样品中HQ和CC的测定,其加标回收率分别为99.9%~100.6%(HQ)、99.2%~100.2%(CC).     

β-PbO2和BDD电极处理印染反渗透浓水性能

系统比较了β-PbO₂/Ti-Ti和BDD/Si-Ti两种电极体系处理实际印染行业反渗透浓水(ROC)的性能,考察了同步去除化学需氧量(COD)和总氮(TN)的动力学,以及对废水可生化性的改善情况.结果表明,BDD/Si-Ti电极体系的析氧电位(2.45V)和析氯电位(1.90V),以及阳极氧化电位和阴极还原电位的绝对值均高于β-PbO₂/Ti-Ti电极体系;两种电极体系对COD以及TN的去除符合拟一级动力学,其中BDD/Si-Ti电极体系对COD去除的表观速率常数和能量利用效率均优于β-PbO₂/Ti-Ti电极体系;而β-PbO₂/Ti-Ti电极体系对TN去除的表观速率常数和能量利用效率更优.β-PbO₂/Ti-Ti电极体系在5mA/cm²的电流密度下电解15min,可使反渗透浓水BOD/COD从0.18升至0.42(提高1.33倍),而BDD/Si-Ti电极体系仅提升0.78倍.两者相比,BDD/Si-Ti电极体系适用于矿化污染物,β-PbO₂/Ti-Ti电极体系适用于改善废水可生化性.     

超滤-反渗透双膜技术深度处理乙烯生产废水

采用超滤-反渗透双膜技术对乙烯化工厂二级生化处理出水进行深度处理,考察了超滤膜对乙烯生产废水的预处理性能,研究了超滤-反渗透双膜技术各单元对废水中污染物的去除效果,并探索了不同清洗方式下膜通量的恢复情况。试验结果表明:超滤能有效地去除废水浊度、胶体物质和细菌,为反渗透提供良好的进水水质;超滤-反渗透膜系统产水水质稳定,平均脱盐率达到98%以上。采用0.2%HCl和反渗透产水配制的清洗液(pH>2)对系统进行循环清洗,能够有效去除膜污染,恢复膜通量。     

超滤-反渗透集成膜技术深度处理酒精废水

采用超滤-反渗透集成膜技术对酒精废水二级生化处理出水进行深度处理,考察了不同超滤膜对废水的预处理性能,研究了超滤-反渗透集成膜技术对废水污染物的去除效果,并探索了不同清洗方式对反渗透膜通量恢复的影响。试验结果表明:超滤能有效地去除废水浊度和大分子有机物,为反渗透提供良好的进水水质;超滤-反渗透膜系统产水浊度、硬度、总铁均小于0.1 NTU、0.03 mmol/L和0.03 mg/L,电导率处于60~120μS/cm之间,可回用作锅炉补充水;酸洗+碱洗组合清洗方式能有效恢复反渗透膜通量,其废水膜通量可恢复为新膜废水通量的93.75%。     

Effects of two sludge application on fractionation and phytotoxicity of zinc and copper in the soil

The potential harm of heavy metals is a primary concern in application of sludge to the agricultural land. A pot experiment was conducted to evaluate the effect of two sludges on fractionation of Zn and Cu in soil and their phytotoxicity to pakchoi. The loamy soil was mixed with 0%, 20%, 40%, 60% and 80% (by weight) of digested sewage sludge (SS) and composted sludge (SC). The additions of both sludges caused a significant raise in all fractions, resulting in that exchangeable (EXCH) and organic bound (OM) became predominance of Zn and organic bound Cu occupied the largest portion. There was more available amount of Zn and Cu in SS treatments than SC treatments. During the pot experiment, the concentration of Zn in EXCH, carbonate (CAR) and OM and Cu in EXCH and OM fractions decreased in all treatments, so their bioavailability reduced. Germination rate and plant biomass decreased when the addition rate was high and the best yield appeared in 20% mixtures at the harvest of pakchoi. The two sludges increased tissue contents of Zn and Cu especially in the SS treatments. Zn in pakchoi was not only in relationship to ΔEXCH and ΔCAR forms but also in ΔOM forms in the sludge-soil mixtures. Tissue content of Cu in pakchoi grown on SC-soils could not be predicted by ΔEXCH. These correlation rates between Zn and Cu accumulation in pakchoi and variation of different fractions increased with time, which might indicate that sludges represented stronger impacts on the plant in long-term land application.     

Intraspecific differences in effects of co-contamination of cadmium and

A hydroponic experiment was carried out to study intraspecific differences in the effects of different concentrations of cadmium (Cd)(0-10 mg/L) and arsenate (As(V)) (0-8 mg/L) on the growth parameters and accumulation of Cd and As in six wheat varieties Jing-9428, Duokang-1, Jingdong-11, Jing-411, Jingdong-8 and Zhongmai-8. The endpoints of wheat seedlings, including seed germination,biomass, root length and shoot height, decreased with increasing the Cd and As concentrations. Significant differences in seed germination, biomass, root length, shoot height and the accumulation of Cd and As were observed between the treatments and among the varieties (p ＜ 0.05). The lethal dosage 50% were about 20, 80, 60, 60, 80 and 20 mg As/L for Jing-9428, Duokang-1, Jingdong-11,Jing-411, Jingdong-8 and Zhongmai-8, respectively, and the corresponding values for Cd were about 30, 80, 20, 40, 60 and 10 mg Cd/L, respectively. Among the six varieties, Duokang-1 was found to be the most resistant to Cd and As toxicity, and Zhongmai-8 was the most sensitive to Cd and As co-contamination. The resistance of the six varieties was found dependant on the seedling uptake of Cd and As. Duokang-1 was the most suitable for cultivation in Cd and As co-contaminated soils.     

Toxic effects of acetochlor, methamidophos and their combination on nifH gene in soil

Toxic effects of two agrochemicals on nifH gene in agricultural black soil were investigated using denaturing gradient gel electrophoresis （DGGE） and sequencing approaches in a microcosm experiment. Changes of soil nifH gene diversity and composition were examined following the application of acetochlor, methamidophos and their combination. Acetochlor reduced the nifH gene diversity （both in gene richness and diversity index values） and caused changes in the nifH gene composition. The effects of acetochlor on nifH gene were strengthened as the concentration of acetochlor increased. Cluster analysis of DGGE banding patterns showed that nifH gene composition which had been affected by low concentration of acetochlor （50 mg/kg） recovered firstly. Methamidophos reduced nifH gene richness that except at 4 weeks. The medium concentration of methamidophos （150 mg/kg） caused the most apparent changes in nifH gene diversity at the first week while the high concentration of methamidophos （250 mg/kg） produced prominent effects on nifH gene diversity in the following weeks. Cluster analysis showed that minimal changes of nifH gene composition were found at 1 week and maximal changes at 4 weeks. Toxic effects of acetochlor and methamidophos combination on nifH gene were also apparent. Different nifH genes （bands） responded differently to the impact of agrochemicals： four individual bands were eliminated by the application of the agrochemicals, five bands became predominant by the stimulation of the agrochemicals, and four bands showed strong resistance to the influence of the agrochemicals. Fifteen prominent bands were partially sequenced, yielding 15 different nifH sequences, which were used for phylogenetic reconstructions. All sequences were affiliated with the alpha- and beta-proteobacteria, showing higher similarity to eight different diazotrophic genera.     

Arsenic uptake by arbuscular mycorrhizal maize （Zea mays L.） grown in an arsenic-contaminated soil with added phosphorus

The effects of arbuscular mycorrhizal (AM) fungus (Glomus mosseae) and phosphorus (P) addition (100 mg/kg soil) on arsenic (As) uptake by maize plants (Zea mays L.) from an As-contaminated soil were examined in a glasshouse experiment.Non-mycorrhizal and zero-P addition controls were included.Plant biomass and concentrations and uptake of As,P,and other nutrients,AM colonization,root lengths,and hyphal length densities were determined.The results indicated that addition of P significantly inhibited root colonization and development of extraradical mycelium.Root length and dry weight both increased markedly with mycorrhizal colonization under the zero-P treatments,but shoot and root biomass of AM plants was depressed by P application.AM fungal inoculation decreased shoot As concentrations when no P was added,and shoot and root As concentrations of AM plants increased 2.6 and 1.4 times with P addition,respectively.Shoot and root uptake of P,Mn,Cu,and Zn increased,but shoot Fe uptake decreased by 44.6%,with inoculation, when P was added.P addition reduced shoot P,Fe,Mn,Cu,and Zn uptake of AM plants,but increased root Fe and Mn uptake of the nonmycorrhizal ones.AM colonization therefore appeared to enhance plant tolerance to As in low P soil,and have some potential for the phytostabilization of As-contaminated soil,however,P application may introduce additional environmental risk by increasing soil As mobility.     

Distribution and ecological effect of mercury in Laogang landfill, Shanghai, China

Laogang landfill near Shanghai is the largest landfill in China, and receives about 10000 t of daily garbage per day, Samples of topsoil and plants were analyzed to evaluate mercury pollution from the landfill. For topsoil samples, there were significant correlations among total mercury （HgT）, combinative mercury （Hgc） and gaseous mercury （HgG）, and content of total organic carbon （TOC）, but, no significantly relationship was found between Hg content and filling time. Hg content changes in vertical profiles with time showed that the average Hgv of profiles 1992, 1996, and 2000 was similar, but their average HgG was quite different. HgT was significantly correlated with Hgc in profile 1992 and 2000, and Hgv was significantly correlated with Hg6 in profile 1996. HgG/Hgv ratio in profile samples decreased in the order of （HgG,/HgT）1992〉（HgG/HgT）1996〉〉（HgG/HgT）2000. A simple outline of Hg release in landfill could be drawn： with increasing of filling time, degradation undergoes different biodegradation, accordingly, gaseous mercury goes through small, more, and small proportion to total mercury. Distribution of Hg in plants was inhomogeneous, following the order of leaf〉root〉stem. The highest value of leaf may be associated with higher atmospheric Hg from landfill. Ligneous plants （e.g. Phyllostachys glanca, Prunus salicina and Ligustrum lucidum） are capable of enriching more Hg than herbaceous plants.     

EDTA-enhanced phytoremediation of lead contaminated soil by Bidens maximowicziana

Phytoremediation is a potential cleanup technology for the removal of heavy metals from contaminated soils.Bidens maximowicziana is a new Pb hyperaccumulator,which not only has remarkable tolerance to Pb but also extraordinary accumulation capacity for Pb.The maximum Pb concentration was 1509.3 mg/kg in roots and 2164.7 mg/kg in overground tissues.The Pb distribution order in the B. maximowicziana was:leaf>stem>root.The effect of amendments on phytoremediation was also studied.The mobility of soil Pb and the Pb concentrations in plants were both increased by EDTA application.Compared with CK(control check),EDTA application promoted translocation of Pb to overground parts of the plant.The Pb concentrations in overground parts of plants was increased from 24.23-680.56 mg/kg to 29.07-1905.57 mg/kg.This research demonstrated that B.maximowicziana appeared to be suitable for phytoremediation of Pb contaminated soil,especially,combination with EDTA.     

Potential of plant polyphenol oxidases in the decolorization and removal of textile and non-textile dyes

In this study an effort has been made to use plant polyphenol oxidases; potato （Solanum tuberosum） and brinjal （Solanum melongena）, for the treatment of various important dyes used in textile and other industries. The ammonium sulphate fractionated enzyme preparations were used to treat a number of dyes under various experimental conditions. Majority of the treated dyes were maximally decolorized at pH 3.0. Some of the dyes were quickly decolorized whereas others were marginally decolorized. The initial first hour was sufficient for the maximum decolorization of dyes. The rate of decolorization was quite slow on long treatment of dyes. Enhancement in the dye decolorization was noticed on increasing the concentration of enzymes. The complex mixtures of dyes were treated with both preparations of polyphenol oxidases in the buffers of varying pH values. Potato polyphenol oxidase was significantly more effective in decolorizing the dyes to higher extent as compared to the enzyme obtained from brinjal polyphenol oxidase. Decolorization of dyes and their mixtures, followed by the formation of an insoluble precipitate, which could be easily removed simply by centrifugation.     

Decomposition of alachlor by ozonation and its mechanism

Decomposition and corresponding mechanism of alachlor, an endocrine disruptor in water by ozonation were investigated. Results showed that alachlor could not be completely mineralized by ozone alone. Many intermediates and final products were formed during the process, including aromatic compounds, aliphatic carboxylic acids, and inorganic ions. In evoluting these products, some of them with weak polarity were qualitatively identified by GC-MS. The information of inorganic ions suggested that the dechlorination was the first and the fastest step in the ozonation of alachlor.     

Enzymatic oxidation of aqueous pentachlorophenol

The influence of the nonionic surfactant Tween 80 on pentachlorophenol （PCP） oxidation catalyzed by horseradish peroxidase was studied. The surfactant was tested at concentrations below and above its critical micelle concentration （CMC）. Enhancement of PCP removal was observed at sub-CMCs. The presence of Tween 80 in the reaction mixture reduced enzyme inactivation which occurred through a combination of free radical attack and sorption by precipitated products. A simple first-order model was able to simulate time profiles for enzyme inactivation in the presence or absence of Tween 80. At supra-CMCs, the surfactant caused noticeable reductions in PCP removal, presumably through micelle partitioning of PCP which precluded the hydrophobic PCP molecule from interacting with the enzyme.     

Effect of sorbed and desorbed Zn(Ⅱ) on the growth of a green alga (Chlorella pyrenoidosa)

Toxic effect of Zn(Ⅱ) on a green alga (Chlorella pyrenoidasa) in the presence of sepiolite and kaolinite was investigated.The Zn-free clays were found to have a negative impact on the growth of C.pyrenoidosa in comparison with control samples (without adding any clay or Zn(Ⅱ)).When Zn(Ⅱ) was added,the algae in the presence of clays could be better survived than the control samples,which was actually caused by a decrease in Zn(Ⅱ) concentration in the solution owing to the adsorption of Zn(Ⅱ) on the clays.When the solution system was diluted,the growth of algae could be further inhibited as compared to that in a system which had the same initial Zn(Ⅱ) concentration as in the diluted system.This in fact resulted from desorption of Zn(Ⅱ) from the zinc-contaminated clays,although the effect varied according to the different desorption capabilities of sepiolite and kaolinite.Therefore the adsorption and desorption processes of Zn(Ⅱ) played an important part in its toxicity,and adsorption and desorption of pollutants on soils/sediments should be well considered in natural eco-environmental systems before their risk of toxicity to aquatic organisms was assessed objectively.