纳米颗粒的分散及其在水与废水处理中的应用

纳米颗粒由于其吸附活性而极易产生自身团聚，这不利于纳米颗粒在使用介质中的分散并影响其应用。本文综述了近年来有关纳米颗粒在水中的分散方法、原理及影响因素，归纳总结了分散的纳米颗粒在强化水处理中的若干应用。     

纳米零价铁的制备及其去除水中对氯硝基苯的研究

通过FeSO4与KBH4反应,利用液相还原法制备纳米零价铁颗粒(NZVI),用XRD、SEM和BET对其性能进行表征。在常温常压下利用纳米铁还原废水中的对氯硝基苯(p-CNB),探讨了反应条件对还原率的影响。结果表明,制备过程中碱性物质(NaOH)的添加可以明显减小颗粒粒径,增大比表面积,提高纳米铁还原反应的效率。NZVI对于对氯硝基苯有很好的去除效果,NZVI用量、p-CNB初始浓度和pH值均对其去除效率产生影响。在纳米铁投加量为1 g/L,pH=2的条件下,添加NaOH的纳米铁能在120 min内将质量浓度为50 mg/L的对氯硝基苯基本完全降解,降解率为98.8%。此外,还对NZVI还原对氯硝基苯的机理进行了初步探讨。     

钯掺杂纳米塑料对产甲烷颗粒污泥的影响

金属掺杂纳米塑料已被广泛应用在纳米塑料的环境行为与生物效应研究中,但其中掺杂的金属是否会对其生物效应产生影响尚不清楚。以厌氧颗粒污泥为研究对象,基于乳液聚合的方法合成钯(Pd)掺杂的纳米塑料(Pd-NPs),研究它对污泥厌氧消化系统产甲烷性能、微生物群落分布和污泥胞外聚合物的影响。结果表明,Pd-NPs中的Pd会随时间的推移溶出,并通过提高厌氧消化系统中地杆菌(Geobacter)的相对丰度促进电子传递进而促进污泥厌氧消化系统产甲烷量;傅立叶变换红外光谱和三维荧光光谱结果显示,Pd-NPs能够与厌氧颗粒污泥表面胞外聚合物中蛋白质和腐殖酸类物质发生相互作用,使污泥颗粒更易絮凝。这些结果为评估金属掺杂的纳米塑料对厌氧消化系统的影响提供了一定的数据支撑。     

Fe_3O_4/SDS磁性纳米颗粒吸附水体中的Cd~（2＋）和Zn~（2＋）

一种新型纳米固相萃取吸附剂,由阴离子表面活性剂十二烷基磺酸钠（SDS）包裹在Fe3O4磁性纳米颗粒表面形成,用于吸附水溶液中的重金属离子。研究了吸附过程的主要影响因素（如SDS浓度、溶液pH等）以及解吸过程的最佳条件,并对其机理进行了初步的探讨。研究结果表明,共沉淀法制备的Fe3O4颗粒粒径分布均匀,平均粒径约为54 nm;SDS浓度为300 mg/L时,Fe3O4/SDS磁性纳米颗粒吸附Cd2＋和Zn2＋的能力最强;在一定浓度范围内,Fe3O4/SDS体系对Cd2＋和Zn2＋的吸附平衡数据符合Langmuir吸附等温方程,饱和吸附量分别为22.42 mg/g和13.95 mg/g。最终结果表明,Fe3O4/SDS磁性纳米颗粒具有较强磁分离能力和较好的吸附效果。     

Fe3O4/SDS磁性纳米颗粒吸附水体中的Cd2+和Zn2+

一种新型纳米固相萃取吸附剂,由阴离子表面活性剂十二烷基磺酸钠(SDS)包裹在Fe3O4磁性纳米颗粒表面形成,用于吸附水溶液中的重金属离子。研究了吸附过程的主要影响因素(如SDS浓度、溶液pH等)以及解吸过程的最佳条件,并对其机理进行了初步的探讨。研究结果表明,共沉淀法制备的Fe3O4颗粒粒径分布均匀,平均粒径约为54 nm;SDS浓度为300 mg/L时,Fe3O4/SDS磁性纳米颗粒吸附Cd2+和Zn2+的能力最强;在一定浓度范围内,Fe3O4/SDS体系对Cd2+和Zn2+的吸附平衡数据符合Langmuir吸附等温方程,饱和吸附量分别为22.42 mg/g和13.95 mg/g。最终结果表明,Fe3O4/SDS磁性纳米颗粒具有较强磁分离能力和较好的吸附效果。     

新型正渗透汲取液的试制及其处理浓盐水的应用

选取柠檬酸盐改良磁性纳米颗粒汲取液作为正渗透汲取液,研究其在浓盐水处理中的应用效果,采用热合成方法控制温度为30、60和90℃时制成了柠檬酸盐改良磁性纳米颗粒(MNP0、MNP1和MNP2)。对3种磁性纳米颗粒进行表征的结果显示,随反应温度的升高,分散性提高,同时温度升高,更有利于柠檬酸盐包覆到磁性纳米颗粒的表面。不同温度条件下合成的3种柠檬酸盐磁性纳米颗粒处理浓盐水测定水通量和反向盐通量研究表明,MNP2的水通量较MNP0和MNP1高,为23 L·(m~2·h)-1,且水通量下降较稳定,反向盐通量较小。不同粒径的MNP2处理浓盐水研究结果表明,水通量随粒径的减小呈现增加趋势,粒径为3.5 nm时的渗透压和水通量最高且减压渗透(pressure relief osmosis,PRO)模式下水通量较正渗透(forward osmosis,FO)模式高。     

纳米复合可见光催化剂Ag_3PO_4/凹凸棒石的制备及其性能研究

采用化学沉淀法将高分散纳米Ag_3PO_4颗粒负载到纯化的凹凸棒石(ATP)表面,得到了具有可见光响应、高活性的纳米复合可见光催化剂Ag_3PO_4/ATP。采用X射线衍射、扫描电子显微镜、紫外—可见漫反射光谱、红外吸收光谱、热重和比表面积分析等技术对催化剂的相结构和微观形貌等进行了表征。结果表明,ATP因其具有较大的负载表面使得负载的Ag_3PO_4纳米颗粒变小、分散程度增强且光吸收边红移,增加了Ag_3PO_4/ATP的活性位点。可见光条件下,当Ag_3PO_4负载量为45%(质量分数)时,Ag_3PO_4/ATP对亚甲基蓝的准一级动力学表观速率常数是Ag_3PO_4的2.39倍。     

好氧颗粒污泥的性质及其在脱氮除磷中的应用

阐述了好氧颗粒污泥的污泥特性、培养条件和影响因素 ,比较了三种SBR反应器中颗粒污泥特性的差异 ,介绍了好氧颗粒污泥的形成机理及其在脱氮除磷过程中的应用情况     

磁性Fe_3O_4纳米颗粒的制备及在水处理中的应用

众所周知,纳米颗粒在去除水中污染物的过程中易团聚,还会造成水体的二次污染。磁性Fe_3O_4纳米颗粒因其能迅速从水中分离的特性而被广泛关注。改性之后的磁性Fe_3O_4纳米颗粒在水中污染物的去除方面有很好的应用。对磁性Fe_3O_4纳米颗粒及其载体或复合物的制备方法进行了概述,重点对水中污染物的去除从3个方面进行了阐述:磁性Fe_3O_4纳米材料对水中重金属的吸附、有机物的吸附及水中细菌和医疗废物的处理。     

人工纳米材料在水-生物膜体系中的环境行为与毒性效应研究进展

随着纳米技术的飞速发展,人工纳米材料随人类活动以及纳米产品进入水-生物膜体系的环境行为以及毒性效应受到越来越多的关注。概述了纳米材料释放到水体后可能发生的环境行为及机理,阐述了纳米颗粒对生物膜中细菌活性的毒性作用,并揭示了生物膜抵抗纳米毒性的机制,为深入研究纳米颗粒在水体中的环境行为及生态效应提供重要的理论依据。     

Water-soluble ions in nano/ultrafine/fine/coarse particles collected near a busy road and at a rural site

This study investigated water-soluble ions in the sized particles (particularly nano (PM(0.01-0.056))/ultrafine (PM(0.01-0.1))) collected using MOUDI and Nano-MOUDI samplers near a busy road site and at a rural site. The analytical results demonstrate that nano and coarse particles exhibited the highest (16.3%) and lowest (8.37%) nitrate mass ratios, respectively. The mass ratio of NO(3)(-) was higher than that of SO(4)(2-) in all the sized particles at the traffic site. The secondary aerosols all displayed trimodal distributions. The aerosols in ultrafine particles collected at the roadside site exhibited Aitken mode distributions indicating they were of local origin. This finding was not observed for those ultrafine particles collected at the rural site. The mass median diameters (MMDs) of the nano, ultrafine, and fine particles were smaller at the traffic site than at the rural site, possibly related to the contribution of mobile engine emissions.     

壳聚糖/纳米CdS复合颗粒可见光光催化降解猩红B动力学研究

采用仿生矿化法制备了壳聚糖/纳米CdS复合颗粒光催化剂,并用于可见光光催化降解猩红B染料模拟废水,研究了猩红B初始浓度、pH、催化剂投加量和催化剂重复使用次数等因素对猩红B光催化降解的影响.X射线衍射(XRD)分析表明,壳聚糖能有效负载CdS纳米微晶.采用Langmuir-Hinshelwood模型描述壳聚糖/纳米CdS复合颗粒可见光光催化降解猩红B反应动力学行为,在猩红B初始质量浓度较低(≤20 mg/L)时,光催化降解过程符合假一级动力学方程.降低猩红B初始浓度和溶液pH都可显著增大光催化降解速率常数;催化剂投加量小于0.7 g/L时,光催化降解速率随其增加而增大,但催化剂投加量过大会使光催化降解速率减小;催化剂重复使用第5次时,猩红B光催化降解速率常数仍为第1次使用时的63.4%.     

Toxicity,uptake, and accumulation of nano and bulk cerium oxide particles in <Emphasis Type="Italic">Artemia salina</Emphasis>

Although the toxicological impact of metal oxide nanoparticles has been studied for the last few decades on aquatic organisms, the exact mechanism of action is still unclear. The fate, behavior, and biological activity of nanoparticles are dependent on physicochemical factors like size, shape, surface area, and stability in the medium. This study deals with the effect of nano and bulk CeO₂ particles on marine microcrustacean, Artemia salina. The primary size was found to be 15 ± 3.5 and 582 ± 50 nm for nano and bulk CeO₂ (TEM), respectively. The colloidal stability and sedimentation assays showed rapid aggregation of bulk particles in seawater. Both the sizes of CeO₂ particles inhibited the hatching rate of brine shrimp cyst. Nano CeO₂ was found to be more toxic to A. salina (48 h LC₅₀ 38.0 mg/L) when compared to bulk CeO₂ (48 h LC₅₀ 92.2 mg/L). Nano CeO₂-treated A. salina showed higher oxidative stress (ROS) than those treated with the bulk form. The reduction in the antioxidant activity indicated an increase in oxidative stress in the cells. Higher acetylcholinesterase activity (AChE) was observed upon exposure to nano and bulk CeO₂ particles. The uptake and accumulation of CeO₂ particles were increased with respect to the concentration and particle size. Thus, the above results revealed that nano CeO₂ was more lethal to A. salina as compared to bulk particles.     

Water-based condensation particle counters for environmental monitoring of ultrafine particles

TSI Inc. (Shoreview, MN) has introduced three new water-based condensation particle counters (WCPCS) that were designed to detect airborne particles larger than 2.5 nm (model 3786), 5 nm (model 3785), and either 10 or 20 nm (model 3782). These WCPCs are well suited for real-time, environmental monitoring of number concentration of airborne ultrafine particles. Their unique design incorporates the use of water as the working fluid instead of alcohol. Water is odor free, readily available, and eliminates the problem of water condensation and absorption into alcohol working fluids during operation in humid environments. In this study, the performance of three TSI WCPCs was characterized for several aerosol compositions, including sucrose, salt (NaCl), dioctyl sebacate (DOS), dioctyl phthalate (DOP), emery oil (poly-alpha-olefin), silver, impurity residue particles, and ambient aerosol particles. All particles were size selected using a nano differential mobility analyzer (nano-DMA; model 3085, TSI Inc.) to create monodisperse challenge aerosols. The challenge aerosol was mixed uniformly with clean makeup flow and split into a WCPC and a reference instrument to determine the counting efficiency of the WCPC. For the model 3785 WCPC, the D50 (i.e., the particle diameter with 50% counting efficiency) was determined to be 3.1 nm for salt particles, 4.7 nm for sucrose and ambient particles, 5.6 nm for silver particles, and >50 nm for ultrapure oil particles. The sensitivity to oil droplets increased dramatically (D50 < 10 nm) when the oil was slightly contaminated. The D50 of model 3786 ultrafine water-based CPC (UWCPC) was 2.4 nm for impurity residue particles. The D50 of the model 3782 WCPC was 10.8 (with a nominal setting of 10 nm) or 19.8 nm (with a nominal setting of 20 nm) for sucrose particles. All three WCPCs have response times of less than 2 or 3 sec and are therefore able to detect fast-changing events.     

Toxicity of nanosized and bulk ZnO, CuO and TiO2 to bacteria Vibrio fischeri and crustaceans Daphnia magna and Thamnocephalus platyurus

As the production of nanoparticles of ZnO, TiO2 and CuO is increasing, their (eco)toxicity to bacteria Vibrio fischeri and crustaceans Daphnia magna and Thamnocephalus platyurus was studied with a special emphasis on product formulations (nano or bulk oxides) and solubilization of particles. Our innovative approach based on the combination of traditional ecotoxicology methods and metal-specific recombinant biosensors allowed to clearly differentiate the toxic effects of metal oxides per se and solubilized metal ions. Suspensions of nano and bulk TiO2 were not toxic even at 20 g l(-1). All Zn formulations were very toxic: L(E)C50 (mg l(-1)) for bulk ZnO, nanoZnO and ZnSO4.7H2O: 1.8, 1.9, 1.1 (V. fischeri); 8.8, 3.2, 6.1 (D. magna) and 0.24, 0.18, 0.98 (T. platyurus), respectively. The toxicity was due to solubilized Zn ions as proved with recombinant Zn-sensor bacteria. Differently from Zn compounds, Cu compounds had different toxicities: L(E)C50 (mg l(-1)) for bulk CuO, nano CuO and CuSO4: 3811, 79, 1.6 (V. fischeri), 165, 3.2, 0,17 (D. magna) and 95, 2.1, 0.11 (T. platyurus), respectively. Cu-sensor bacteria showed that toxicity to V. fischeri and T. platyurus was largely explained by soluble Cu ions. However, for Daphnia magna, nano and bulk CuO proved less bioavailable than for bacterial Cu-sensor. This is the first evaluation of ZnO, CuO and TiO2 toxicity to V. fischeri and T. platyurus. For nano ZnO and nano CuO this is also a first study for D. magna.     

Phytotoxicity of nanoparticles—problems with bioassay choosing and sample preparation

For a full estimation of the risk related with the presence of engineered nanoparticles (ENPs) in the environment, the use of the current ecotoxicological methods may prove insufficient. In the study presented herein, various methods of assessment of ecotoxicity were applied to compare the phytotoxicity of three ENPs: nano-ZnO, nano-TiO₂ and nano-Ni. The toxicity was assayed both for aqueous solutions of the ENPs (the germination/elongation test and Phytotestkit F^TM) and for ENPs added to soil (Phytotoxkit F^TM and modified Phytotoxkit F^TM). Lepidium sativum was used as a test plant. The scope of the study also included the assessment of the effect of the method of ENP application to the soil (as powder and aqueous suspension) on their phytotoxicity. In the course of the study, no effect of the studied ENPs and their bulk counterparts on the germination of seeds was observed. The root growth inhibition of L. sativum depended on the kind of test applied. The trend between concentration of ENPs and effect depended on the method used and kind of ENPs. For most nanoparticles (despite of the method used), the differences in phytotoxicity between nano and bulk particles were observed. Depending on the kind of ENPs, their phytotoxicity differs between water and soil. ZnO (nano and bulk) and nano-Ni were more toxic in soil than in water. For TiO₂ and bulk-Ni, reverse trend was observed. A different method of ENP application to soil differently affects the phytotoxicity.     

Synergistic adsorption and advanced oxidation activated by persulfate for degradation of tetracycline hydrochloride using iron-modified spent bleaching earth carbon

At present, tetracycline hydrochloride (TCH) is a widely used antibiotic, and is often detected in water, posing a serious harm to human and ecological health. In this study, spent bleaching earth (SBE) was pyrolyzed to obtain spent bleaching earth carbon (SBE@C) and the nano Fe⁰/SBE@C prepared after zero-valent iron loading was adopted to remove TCH in water for the first time. The combination of nano Fe⁰/SBE@C and PS, the strong adsorption of SBE@C coupled with the oxidation of free radicals could achieve TCH efficient removal. The effects of nano Fe⁰ load, nano Fe⁰/SBE@C dosage, solution initial pH, and PS/TCH molar ratio on TCH removal efficiency in nano Fe⁰/SBE@C?+?PS system were studied. The results indicate that the optimal reaction conditions are 5% nano Fe⁰ load, 0.2 g/L nano Fe⁰/SBE@C dosage, initial pH of 3, PS/TCH molar ratio of 100:1. Under these conditions, TCH removal efficiency could reach 91%. Meanwhile, response surface methodology (RSM) was applied to predict optimal value of reaction conditions. The removal efficiency corresponding to the predicted optimal conditions was consistent with the actual removal efficiency obtained from the experiment. Moreover, six reaction systems were tested, and TCH removal efficiency in the SBE@C?+?PS system was 22.6%. When nano Fe⁰ was loaded on SBE@C, TCH removal efficiency in Fe⁰/SBE@C?+?PS system increased to 78.2%, in which TCH was first adsorbed on the surface of nano Fe⁰/SBE@C, and then was degraded by the oxidation of SO₄^?? and ?OH. Totally, the nano Fe⁰/SBE@C?+?PS system displayed excellent TCH removal efficiency, good stability and reusability, exhibiting a promise toward TCH removal.

     

Determination of sterols, estrogens and inorganic ions in waste water and size-segregated aerosol particles emitted from waste water treatment

Concentrations of steroids and inorganic ions were measured in waste water of an aerated sand trap as well as in aerosol particles emitted from this tank at the waste water treatment plant (WWTP) of Bayreuth, Germany, in January and February 2003. The investigations comprised seven sterols, two estrogens, and several inorganic ions. Since an appropriate method for the determination of sterols in waste water was not available, a new method based on solid phase extraction was developed. The concentrations of the sterols coprostanol and cholesterol amounted to 30-180 microg l(-1) in waste water and to 400-5000 pg m(-3) in aerosol particles. All other sterols were present in markedly lower concentrations. The mean concentrations of the two estrogens estrone and 17beta-estradiol were about 165 pg m(-3) in aerosol particles. The steroid concentrations in both waste water and aerosol particles varied greatly over time, however with the exception of coprostanol, no clear correlation was detected between concentrations in waste water and aerosol particles.     

平板炭气凝胶电极电吸附除氟

采用自制的炭气凝胶平板电极进行模拟水样中氟的电吸附去除研究,通过单因子实验优化了该电吸附技术的操作参数和适用的溶液条件,并研究了反接电极法的再生效果。研究结果表明,自制的炭气凝胶平板由纳米颗粒组成三维网络结构,比表面积为670.90 m2/g,具有良好的充放电可逆性和迅速形成表面双电层的特点。静态电吸附除氟效果最佳的条件为:水样氟离子浓度6 mg/L,pH 7.0,极板间距4 cm,电压1.6 V;共存物质硝酸根、腐殖酸、碳酸根和碳酸氢根等对氟离子的电吸附具有一定的促进作用。吸附氟离子后的炭气凝胶材料的比表面、孔体积、电容值有所减小。对于吸附氟离子后的炭气凝胶平板电极,采用反接电极法取得较好再生效果的条件为:流动状态、电压1.6 V、极板间距4 cm。再生后的炭气凝胶电极与原始炭气凝胶相比,依然具有良好的充放电可逆性。     

Seasonal and spatial distribution of nonylphenol in Lanzhou Reach of Yellow River in China

Nonylphenol (NP) is known as an endocrine disruptor and consequently has drawn much environmental concern. This study focused on seasonal variation and spatial distribution of NP in various matrices including water, suspended particles, and sediment taken from Lanzhou Reach of Yellow River in China. NP was measured in July and November in 2004. Concentrations of NP in water ranged from 34.2 to 599.0 ng/l, in suspended particles from 49.6 to 2835.2 ng/g dry wt, and in sediment from 38.4 to 863.0 ng/g dry wt. In terms of most water and suspended particles samples, concentrations were higher in warmer seasons than in colder seasons. Good linear correlations (R(2)=0.90 in July, R(2)=0.97 in November) were obtained for NP concentrations between water and suspended particles. In terms of sediment samples, concentrations were higher in November than in July, probably due to greater deposition of suspended particles. Reasonable linear correlations (R(2)=0.60 in July, R(2)=0.79 in November) were obtained for NP concentrations between water and sediment.