普鲁士蓝@酵母菌催化剂的合成及其Fenton性能

自组装合成普鲁士蓝@酵母菌(PB@yeast)非均相Fenton催化剂,场发射扫描电镜(FE-SEM)、能量色谱(EDS)、X射线衍射(XRD)、傅里叶红外光谱(FT-IR)等表征结果表明PB纳米颗粒成功负载于酵母菌表面,形成稳定且高度分散的核壳结构复合微球;荧光增白剂CXT降解实验结果证明该复合微球兼备吸附与Fenton催化性能,酵母菌载体的吸附作用加快了废水中荧光增白剂CXT向催化剂活性位点的转移,促进FeⅢ-FeⅡ电子传递,显著提高了Fenton反应催化活性,酵母载体增强了PB纳米粒子的分散度与稳定性,有效解决PB纳米催化剂易团聚、易溶解的问题.PB@yeast催化剂经循环使用4次后对荧光增白剂CXT的去除效率无明显下降,表现出较好的催化效果和稳定性能.     

磁性载体MBBR系统对纳米ZnO颗粒的胁迫响应

为探究磁性载体移动床生物膜反应器(MBBR)系统对不同浓度纳米ZnO胁迫的响应,构建2组MBBR开展纳米ZnO胁迫实验,通过对比普通与磁性载体MBBR中COD、NH₄⁺-N去除性能、生物膜形貌、微生物群落及功能基因,分析磁性载体对纳米ZnO胁迫下MBBR中污染物去除性能及微生物的影响.结果表明:低浓度(5,10mg/L)纳米ZnO对COD、NH₄⁺-N去除无显著影响;高浓度(30,50mg/L)纳米ZnO胁迫后,磁性载体MBBR的NH₄⁺-N去除率分别降低10.57%和12.91%,低于普通载体的14.48%和16.94%.相比于NH₄⁺-N,纳米ZnO胁迫对COD去除影响较小.此外,高浓度(30,50mg/L)纳米ZnO胁迫导致更多纳米ZnO颗粒团聚并吸附于磁性载体生物膜表面,继而改变了生物膜群落结构.在10mg/L的纳米ZnO胁迫下,磁性与普通载体生物膜中微单胞菌属(Micropruina)的相对丰度均有所提...     

颗粒物对混凝过程及超滤膜污染的影响

以nm-SiO₂和μm-SiO₂体系为研究对象,使用3种不同Al形态的混凝剂（AlCl₃、Al₁₃和Al₃₀）进行混凝-超滤实验,考察不同pH值下SiO₂去除率、出水余Al及混凝预处理对膜通量的影响,借助马尔文激光粒度仪、SEM、BET和AFM表征絮体性质及在超滤膜表面的分布和作用力.结果表明,nm-SiO₂体系中SiO₂去除率均低于μm-SiO₂体系,在纳米颗粒物体系中投加混凝剂后膜通量从0.68分别提升至0.96（AlCl₃）、0.86（Al₁₃）和0.87（Al₃₀）,微米颗粒物体系中投加3种混凝剂后膜通量从0.79提升至0.80~0.84.微米级颗粒物是颗粒间的碰撞,纳米级颗粒物主要以团聚态的形式碰撞.低聚态铝（Al_a）和颗粒物形成絮体的粒径均大于150μm,体系zeta电位为负与膜表面产生斥力;在中性条件下Al₁₃与颗粒物形成絮体的强度因子远高于AlCl₃和Al₃₀,中聚态铝（Al_b）将膜孔内部较小颗粒物堵塞形成的不可逆膜污染转移成膜孔表面的可逆膜污染;高聚态铝（Al_c）具有较强吸附架桥和网捕卷扫能力,无定形、不规则的团聚态小颗粒在这一过程中形成较大絮体缓解膜污染.     

金属氧化物颗粒/水界面上NOM吸附机制的研究

以腐殖酸作为天然有机物(NOM)的代表,研究了腐殖酸分子在金属氧化物(赤铁矿)颗粒/水界面上的吸附特征,分析了pH值和离子强度对界面吸附配位反应的影响,及它们对赤铁矿颗粒表面吸附密度和团聚体粒径的影响.结果表明,吸附密度随pH值的升高而减少,随离子强度的升高而增大;颗粒团聚体粒径随pH值的升高先增大后减小,随离子强度的升高而增大.pH=4时吸附密度最大,为6.22 mg/m2,但此时团聚体粒径最小;pH=5时吸附密度较小,但团聚体粒径较大;pH=8为配位反应等电点,吸附密度和团聚体粒径均较小;pH=10吸附密度最小,为0.50 mg/m2,团聚体粒径也较小.应用SS/SF混合模型初步分析了赤铁矿颗粒/水界面上腐殖酸分子的吸附构型.当pH值较低时,构型多为链状和环状;当pH值较高时,构型多为扫尾状.离子强度越高,链状和扫尾状构型越多;离子强度越低,环状构型越多.     

腐殖质胶结团聚体对苯酚的富集特征

为探讨不同腐殖质组分团聚体对苯酚富集能力的影响,应用国际腐殖酸协会（IHSS）推荐方法提取腐殖质,以Ca2+、Al3+、Fe3+为桥键离子,制备了高岭石、蒙脱石不同腐殖质组分团聚体,采用平衡吸附法研究了不同腐殖质组分团聚体对苯酚的富集特征.结果表明:高岭石不同腐殖质组分团聚体对苯酚的饱和吸附量（Q_m）大小依次为FA（富里酸）团聚体[（254.11±5.35）mg/kg] > HA（胡敏酸）团聚体[（186.14±1.61）mg/kg] > HM（胡敏素）团聚体[（120.61±1.67）mg/kg];蒙脱石不同腐殖质组分团聚体对苯酚的饱和吸附量大小依次为FA团聚体[（418.72±19.14）mg/kg）] > HA团聚体[（290.00±13.06）mg/kg）] > HM团聚体[（160.46±4.92）mg/kg）];高岭石不同腐殖质组分团聚体对苯酚的富集系数（ER）大小依次为FA团聚体（2.03±0.07）> HA团聚体（1.91±0.04）> HM团聚体（1.85±0.04）;蒙脱石不同腐殖质组分团聚体对苯酚的富集系数大小依次为FA团聚体（2.50±0.10）> HA团聚体（2.45±0.11）> HM团聚体（1.36±0.04）.研究显示,FA团聚体对苯酚的饱和吸附量和富集系数较大,对苯酚的吸附（富集）作用较强,HM团聚体对苯酚的饱和吸附量和富集系数较小,对苯酚的吸附（富集）作用较弱.不同腐殖质组分团聚体对苯酚的富集能力大小表现为FA团聚体> HA团聚体> HM团聚体.因此,FA团聚体可作为控制受苯酚污染场地土壤的首选修复剂.      

表面活性剂-Pd修饰Ti电极的制备及电化学性能表征

通过电沉积法在Ti网表面聚合表面活性剂SDBS和吡咯复合膜,从而制备Pd/PPy (SDBS)/Ti电极.CV测试表明,Pd/PPy (SDBS)/Ti电极可以在-500 my(以Hg/Hg2SO4为参比电极)左右获得-137.5 mA的氢吸附峰.SEM表明,钯颗粒在SDBS修饰的PPy复合膜表面沉积均匀,粒径在几个微米左右,甚至有纳米级颗粒存在.在高放大倍数下,可以看到细小的颗粒表面呈层叠的片状结构,空间延伸性好.在电催化还原脱氯领域有较大的应用潜力.     

磷(P)对老冲积黄壤微团聚体表面砷(As(Ⅴ))吸附-解吸的研究

本文以名山河流域老冲积黄壤为研究对象,采用批培养法研究了原土及不同粒径微团聚体(2~0.25 mm,0.25~0.053 mm,0.053~0.002mm,0.002 mm)对As(Ⅴ)、P的吸附-解吸特性和P对As(Ⅴ)吸附-解吸特性的影响.结果表明:原土及不同粒径微团聚体对As(Ⅴ)与P的吸附-解吸特性相似,等温吸附均符合Langmuir和Freundlich方程,但Langmuir方程拟合效果最佳;动力学吸附均符合Elovich和双常数方程,而Elovich方程拟合效果最好,表明原土及各粒径微团聚体对As(Ⅴ)、P的吸附均以专性吸附为主,非专性吸附为辅.原土及不同粒径微团聚体对As(Ⅴ)的最大吸附量从大到小的排序为:(0.002 mm)原土(0.053~0.002 mm)(0.25~0.053 mm)(2~0.25 mm),对P的最大吸附量的顺序为:(0.002 mm)(0.053~0.002 mm)(0.25~0.053 mm)原土(2~0.25 mm),即粒径越小其最大吸附量越高.As、P在各粒径微团聚体上解吸量与其吸附量呈指数关系.As(Ⅴ)与P共存时,原土及不同粒径微团聚体对As(Ⅴ)的吸附量随P浓度的增加而减少,As(Ⅴ)的解吸量随P浓度的增加而增加,表明P能抑制土壤对As(Ⅴ)的吸附,而促进土壤对As(Ⅴ)的解吸,且0.002 mm粒径的土壤对As(Ⅴ)的吸附-解吸受P浓度的影响最小.     

炭管膜曝气生物膜反应器亚硝化的启动试验研究

利用包裹无纺布的多微孔炭管为膜组件的膜曝气生物膜反应器,对不含有机碳的氨氮废水进行了亚硝化启动试验的研究.结果表明,在进水NH₄⁺-N 浓度为200mg/L,温度为(34±1)℃, pH 值为7.5~8.3,HRT 为8h 的条件下,通过逐步降低炭管内腔气压进而降低供氧量的方法,反应器连续运行83d,实现了稳定的亚硝化.荧光原位杂交(FISH)分析表明,硝化细菌主要集中在靠近曝气膜/生物膜界面区域,其中亚硝酸菌占优势地位,而靠近生物膜/液体界面区域硝化细菌数量较少.     

纳米零价铜活化分子氧降解水中恩诺沙星

采用纳米零价铜(nanoscale zero-valent copper,nZVC)活化分子氧对水中恩诺沙星(enrofloxacin,ENR)的去除进行了系统研究.通过表征可以发现,纳米铜粉比表面积高于微米级铜粉,无孔隙结构,表面粗糙且容易团聚.纳米级ZVC活化分子氧的性能明显优于微米级ZVC,这主要归因于其较大的比表面积,更容易被腐蚀.通过探究活化机制可以发现,活化分子氧产生的H_2O_2和表面腐蚀产生的Cu+构成了新型类Fenton体系,持续释放的羟基自由基是造成水中ENR高效去除的主导活性物种;同时,反应过程中产生的超氧自由基能够促进Cu2+还原成Cu+,从而加速ENR的去除过程.反应条件对nZVC活化分子氧降解ENR有一定的影响,较高的nZVC投加量、较低ENR浓度、较高的反应温度以及强酸性条件均有利于ENR的去除.     

复合纳米Fe_3O_4的制备及其控磷效能的研究

采用氧化沉淀法在羧甲基纤维素(CMC)体系中制备了以纳米Fe3O4为核心,外包覆羧甲基纤维素的复合纳米Fe3O4.对比研究了复合纳米Fe3O4和微米Fe3O4对水中磷的吸附以及对土壤中磷的固化,并考察了添加纤维素酶在此过程中所起的作用.结果表明,在水中微米Fe3O4的平衡吸附量为3.2 mg/g,而复合纳米Fe3O4为2.1 mg/g.当将纤维素酶(用以降解包覆在氧化铁表面的羧甲基纤维素)添加到复合纳米Fe3O4吸附磷的溶液中,复合纳米Fe3O4的除磷效率(86%)接近于微米Fe3O4(90%),说明羧甲基纤维素的存在减弱了复合纳米Fe3O4的吸附能力.在土柱实验中,将2种Fe3O4悬浊液注入到10 cm高的土壤柱中,72%的复合纳米Fe3O4穿过土壤柱溢出,而微米Fe3O4完全滞留在土壤柱中没有溢出.原始土壤的固磷率为30%,注入复合纳米Fe3O4的土壤固磷率达到45%,而将纤维素酶和复合纳米Fe3O4一起注入土壤中固磷效率提高到74%.     

Water chemistry influences on long-term dissolution kinetics of CdSe/ZnS quantum dots

Widespread usage of engineered metallic quantum dots(QDs) within consumer products has evoked a need to assess their fate within environmental systems.QDs are mixed-metal nanocrystals that often include Cd~(2+)which poses a health risk as a nanocrystal or when leached into water.The goal of this work is to study the long-term metal cation leaching behavior and the factors affecting the dissolution processes of mercaptopropionic acid(MPA) capped CdSe/ZnS QDs in aphotic conditions.QD suspensions were prepared in different water conditions,and release of Zn2+and Cd~(2+) cations were monitored over time by size exclusion chromatography-inductively coupled plasm a-mass spectrometry.In most conditions with dissolved 02 present,the ZnS shell degraded fairly rapidly over～1 week,while some of the CdSe core remained up to 80 days.Additional MPA,Zn~(2+),and Cd2+temporarily delayed dissolution,indicating a moderate role for capping agent detachment and mineral solubility.The presence of H_2 O_2 and the ligand ethylenediaminetetraacetate accelerated dissolution,while NOM had no kinetic effect.No dissolution of CdSe core was observed when 02 was absent or when QDs formed aggregates at higher concentrations with 02 present.The shrinking particle model with product layer diffusion control best describes Zn2+and Cd~(2+) dissolution kinetics.The longevity of QDs in their nanocrystal form appears to be partly controlled by environmental conditions,with anoxic,aphotic environments preserving the core mineral phase,and oxidants or complexing ligands promoting shell and core mineral dissolution.     

CdSe/ZnS量子点对稀有鮈鲫胚胎发育的影响及其氧化应激作用

本研究以稀有鮈鲫(Gobiocypris rarus)为对象,研究了不同浓度CdSe/ZnS量子点(QDs)暴露下,稀有鮈鲫胚胎发育过程中自主运动频率、内心率和体长的变化,以及利用体内超氧化物歧化酶(SOD)和丙二醛(MDA)作为毒性指标,反映CdSe/ZnS QDs暴露对稀有鮈鲫胚胎发育的氧化应激作用.结果显示:CdSe/ZnS QDs对稀有鮈鲫胚胎72 hpf(hours post fertilization)的半致死浓度(LC50)为319.629 nmol·L-1,96 hpf的半致畸浓度(EC50)为203.312 nmol·L-1.CdSe/ZnS QDs暴露不仅影响稀有鮈鲫胚胎死亡率、畸形率、自主运动频率、孵化时间和孵化率,而且使其内心率减缓、体长缩短,导致胚胎卵凝结,心包囊肿,出现脊椎弯曲等多种毒性现象.同时发现,CdSe/ZnS QDs暴露导致稀有鮈鲫体内MDA含量增加以及SOD活力的降低.这表明CdSe/ZnS QDs对稀有鮈鲫胚胎发育具有致畸、致死作用,而氧化应激可能是引起其胚胎致畸、致死的重要机制之一.     

CdSe/ZnS量子点对斑马鱼胚胎发育的毒性效应

本研究以模式生物斑马鱼(Danio rerio)为对象,观察在不同浓度Cd Se/Zn S量子点(Cd Se/Zn S QDs)暴露下,斑马鱼胚胎形态发育、氧化应激以及金属硫蛋白MT基因和应激蛋白Hsp70基因表达变化情况.结果表明,Cd Se/Zn S QDs对斑马鱼胚胎72 hpf(hours post fertilization)的半致畸效应浓度(EC50)为316.994 nmol·L-1.QDs暴露影响了斑马鱼胚胎的死亡率、畸形率、孵化率、自主运动频率和体长,以及引起胚胎卵凝集,心包囊肿,脊椎弯曲等多种毒性效应;同时导致斑马鱼体内超氧化物歧化酶(SOD)活性变化以及丙二醛(MDA)含量增加.QDs还诱导斑马鱼MT基因和Hsp70基因表达上调,斑马鱼机体产生一系列自我保护反应来减轻QDs所造成的伤害.这表明:Cd Se/Zn S QDs对斑马鱼胚胎产生了毒性效应,其毒性可能与其核心Cd2+的释放、粒径大小以及氧化应激有关.     

In vitro cytotoxicity of CdSe/ZnS quantum dots with different surface coatings to human keratinocytes HaCaT cells

Quantum dots (QD) nanoparticles have been widely used in biomedical and electronics fields, because of their novel optical properties. Consequently it confers enormous potential for human exposure and environmental release. To increase the biocompatibility of QDs, a variety of surface coatings or functional groups are added to increase their bioactivity and water solubility. Human adult low calcium high temperature (HaCaT) cells are the epithelial cells derived from adult human skin that exhibits normal differentiation capacity and a DNA fingerprint pattern that is unaffected by long-term cultivation, transformation, or the presence of multiple chromosomal alternations. Human keratinocytes, HaCaT cells were used to systematically evaluate the cytotoxicity of biocompatible QD made of CdSe metal core and ZnS shell with three different coatings and at three different wavelengths (530, 580 and 620 nm). In terms of half- maximal inhibitory concentration, QSA-QDs with amine-polyethyleneglycol coating and QSH-QDs with amphiphilic polymer coating were not cytotoxic, while QEI-QDs with polyethylenimine coating were highly toxic to the HaCaT cells in comparison to a reference CuInS2/ZnS. QEI-QDs led to significant increase in reactive oxygen species, decrease in mitochondrial membrane potential and DNA damage in HaCaT cells. The mechanisms of toxicity of QEI-530 and QEI-580 can be attributed to the combination of intracellular reactive oxygen species production and loss of MMP. The QDs toxicity can be attributed to the polyethylemimine surface coating which was highly toxic to cells in comparison with amine-polyethyleneglycol, but not due to the release of cadmium ions.     

Role of quantum dots nanoparticles in the chemical treatment of colored wastewater: Catalysts or additional pollutants

The objective of the study was to investigate the presence and the activity of quantum dots nanoparticles in colored wastewaters. The special interest is devoted to the investigation of their role in the typical treatment of water or wastewater, studying their influence on the effectiveness of applied treatments methods. The standard chemical processes for water treatment and disinfection (direct UV photolysis and direct ozonation) were applied for the degradation of colored organic pollutant, reactive azo dye, in the presence/absence of CdSe/ZnS core-shells quantum dots. The obtained results indicated that investigated nanoparticles inhibit the overall efficiency of applied processes, especially in the case of direct UV photolysis, although catalytic effect might be expected in part due to the semiconductor nature of quantum dots. Such results lead to a conclusion that CdSe/ZnS nanoparticles behave as additional pollutants in the system. They should be removed from the system prior the treatment, because their presence could decrease the efficiency, i.e., prolong the time of treatment and correspondingly increase the costs of the treatment process.     

Enhanced photocatalytic activity of quantum-dot-sensitized one-dimensionally-ordered ZnO nanorod photocatalyst

An efficient photocatalyst was fabricated by assembling quantum dots （QDs） onto one-dimensionally-ordered ZnO nanorods, and the photocatalytic properties for Methyl Orange degradation were investigated by scanning electron microscopy, transmission electron microscopy, X-ray diffraction, UV-Vis-NIR absorption spectroscopy and photoluminescence. The results indicate that the catalyst with assembled QDs is more favorable for the degradation than the pristine ZnO nanorods. The QDs with core-shell structure lower the photocatalytic ability due to the higher carder transport barrier of the ZnS shell layer. Besides its degradation efficiency, the photocatalyst has several advantages given that the one-dimensionally-ordered ZnO nanorods have been grown directly on indium tin oxide substrates. The article provides a new method to design an effective and easily recyclable photocatalyst.     

太湖典型草、藻型湖区有色可溶性有机物的吸收及荧光特性

2004年4月对太湖典型草、藻型湖区东太湖和梅梁湾有色可溶性有机物(CDOM)的吸收和荧光特性进行了研究.通过实验测定方法得到东太湖和梅梁湾CDOM的光谱吸收系数及其荧光值.结果表明,溶解性有机碳(DOC)的浓度在6.3～17.2 mg/L间变化,其均值为9.08±2.66 mg/L;CDOM在280 nm和355 nm的吸收系数分别为11.2～32.6 m^-1(平均值17.46m-1±5.75 m^-1)和2.4m～8.3 m^-1(平均值4.17 m^-1±1.47 m^-1);355 nm波长处CDOM的比吸收系数为0.31～0.64 L·(mg·m)^-1,平均值0.46L·(mg·m)^-1±0.08 L·(mg·m)^-1.355 nm的激发波长、450 nm的发射波长处的荧光值的变化范围0.50～3.91 nm^-1(平均值1.32nm-1±0.84 nm^-1).2类草、藻型湖区的DOC浓度、CDOM吸收系数、355 nm处荧光值均存在显著性差异,但CDOM比吸收系数和指数函数斜率则没有显著性差异,由此则反映了CDOM来源的一致性.CDOM的吸收系数与DOC浓度的相关性随波长的降低而增加,在短波部分存在明显的正相关.355 nm处的荧光值、DOC浓度与CDOM吸收系数存在如下显著性的正相关关系:F_n(355)=0.544(±0.035)a(355)-0.946(±0.152),DOC=1.537(±0.196)a(355)+2.683(±0.862).280～500 nm、280～360 nm、360～440 nm指数函数斜率分别为14.37μm^-1±0.73μm^-1、19.17μm-1±0.84μm^-1、13.38μm-1±0.82μm^-1.     

One-pot molten salt method for constructing CdS/C3N4 nanojunctions with highly enhanced photocatalytic performance for hydrogen evolution reaction

The construction of heterojunction photocatalysts for efficiently utilizing solar energy has attracted considerable attention to solve the energy crisis and reduce environmental pollution. In this study, we use the energy released from an easily-occurred exothermic chemical reaction to serve as the drive force to trigger the formation of Cd S and C₃N₄ nanocomposites which are successfully fabricated with cadmium nitrate and thiourea without addition of any solvents and prot...     

上升流速对CANON工艺稳定性及微生物群落的影响

采用膨胀颗粒污泥床（EGSB）反应器作为全程自养脱氮（CANON）工艺启动运行的装置,考察了不同上升流速对CANON工艺脱氮性能的影响,并对固定生物膜-活性污泥（IFAS）系统内颗粒污泥粒径的变化和生物膜上的生物量进行定量分析,同时对颗粒污泥和生物膜上的微生物进行高通量分析,探究在不同聚集体上微生物群落结构的特点.结果表明,在连续运行过程中,上升流速由2m/h增加至6m/h的过程中,总氮去除负荷由0.20kg/（m³·d）逐渐增加至0.66kg/（m³·d）,而ΔNO₃^--N/ΔNH₄⁺-N的比值稳定在0.11,成功实现了CANON的高效稳定运行.当上升流速增加至8m/h时,CANON工艺脱氮性能失稳,总氮去除负荷（NRR）降低至0.42kg/（m³·d）,污泥平均粒径由1.3mm减小到0.9mm.上升流速恢复至6m/h后,CANON脱氮工艺脱氮性能逐渐恢复,最终NRR稳定在0.60kg/（m³·d）以上,污泥平均粒径恢复至1.2mm,生物膜生物量的比生长速率为0.0024d^-1.高通量测序显示,颗粒污泥中主要以氨氧化细菌（AerAOB）功能菌Nitrosomonas（2.45%）,和厌氧氨氧化细菌（AnAOB）功能菌Candidatus Kuenenia（2.38%）为主要菌属;而生物膜中主要是AnAOB功能菌Candidatus Kuenenia（9.78%）、Candidatus Brocadia（4.23%）,同时还检测出少量AerAOB功能菌Nitrosomonas（0.40%）.结果表明两种微生物在不同聚集体上存在一定的差异性.