长期暴露下纳米二氧化钛对典型淡水藻体砷累积与生物转化的影响

以铜绿微囊藻(Microcystis aeruginosa)和斜生栅藻(Scenedesmus obliquus)为研究对象,通过室内培养实验,研究了长期暴露下纳米二氧化钛(nano-TiO_2)对五价砷[As(Ⅴ)]在典型淡水藻体中累积与生物转化的影响.结果表明不同藻类对无机砷的吸收和转化能力差异很大.长期暴露下斜生栅藻累积的砷(As,以DW计,下同)高达(819.66±11.25)μg·g-1,比铜绿微囊藻累积的As[(355.95±8.31)μg·g-1]高2倍多.Nano-TiO_2可增加藻体对As的吸收累积,降低了培养基中As的含量.同时,nano-TiO_2可增加藻体对As(Ⅴ)的生化转化;其中,铜绿微囊藻中有机砷以二甲基砷(DMA)为主,而斜生栅藻中有机砷以一甲基砷(MMA)为主.另外,长期暴露下nano-TiO_2处理的铜绿微囊藻和斜生栅藻向培养基释放的甲基砷小于对照组,表明长期暴露中的nano-TiO_2不能促进藻体内甲基砷的释放.研究结果可促进nano-TiO_2与As相互作用时生态风险的理解.     

Photocatalytic activity of TiO2 containing anatase nanoparticles and rutile nanoflower structure consisting of nanorods

A series of TiO2 with different crystal phases and morphologies was synthesized via a facile hydrothermal process using titanium nbutoxide and concentrated hydrochloric acid as raw materials. The photocatalytic activity of the samples was evaluated by degradation of Methyl Orange in aqueous solution under UV-Visible light irradiation. On the basis of detailed analysis of the characterizing results of high-resolution transmission electron microscopy, X-ray powder diffraction measurements, X-ray photoelectron spectroscopy and Brunauer-Emmett-Teller measurement, it was concluded that the photo-activity of the catalyst is related directly to the 3D morphology and the crystal phase composition. An excellent catalyst should have both a futile 3D flower-like structure and anatase granulous particles. The 3D flower-like structure could enhance light harvesting, as well as the transfer of reactant molecules from bulk solution to the reactive sites on TiO2. In addition, the optimum anatase/rutile phase ratio was found to be 80：20, which is beneficial to the effective separation of the photogenerated electron-hole pairs.     

Application of Cellulose Microfibrils in Polymer Nanocomposites

Cellulose microfibrils obtained by the acid hydrolysis of cellulose fibers were added at low concentrations (2–10% w/w) to polymer gels and films as reinforcing agents. Significant changes in mechanical properties, especially maximum load and tensile strength, were obtained for fibrils derived from several cellulosic sources, including cotton, softwood, and bacterial cellulose. For extruded starch plastics, the addition of cotton-derived microfibrils at 10.3% (w/w) concentration increased Young’s modulus by 5-fold relative to a control sample with no cellulose reinforcement. Preliminary data suggests that shear alignment significantly improves tensile strength. Addition of microfibrils does not always change mechanical properties in a predictable direction. Whereas tensile strength and modulus were shown to increase during addition of microfibrils to an extruded starch thermoplastic and a cast latex film, these parameters decreased when microfibrils were added to a starch–pectin blend, implying that complex interactions are involved in the application of these reinforcing agents.     

纳米二氧化硅对秀丽线虫的毒性作用研究

为探讨二氧化硅纳米颗粒(SiNP)的毒性作用.以微米SiO2和空白做对照,将尺寸为20和60 nm的SiNP分别以0.2,1.0和5.0 g·L-13个浓度对模式生物秀丽隐杆线虫进行染毒.通过第一代和第二代线虫体长、身体弯曲频率、头部摆动频率以及第一代线虫后代数目、世代时间等发育、运动和生殖的相关评价指标,对SiNP毒...     

有序介孔碳载金/L-赖氨酸/纳米金修饰电极的制备及其对邻苯二酚、对苯二酚的检测响应研究

通过化学还原的方法合成有序介孔碳负载纳米金粒子,并构筑有序介孔碳载金/L-赖氨酸/纳米金复合膜修饰玻碳电极;利用扫描电镜观察介孔碳和介孔碳复合膜的微观结构,并用循环伏安法、电化学阻抗谱表征自组装电极的过程.在此基础上用差分脉冲伏安法研究对苯二酚和邻苯二酚混合物在该电极上的电催化氧化,研制了一种基于有序介孔碳载金/L-赖氨酸/纳米金复合膜修饰电极分别检测对苯二酚和邻苯二酚的传感器.在最优的实验条件下,该传感器在对苯二酚和邻苯二酚浓度为1×10-6～8×10-4mol·L-1的范围内具有良好的线性关系,检出限分别为3×10-7mol·L-1、7×10-7mol·L-1.     

新型磁性聚谷氨酸吸附剂对水中Pb2+的吸附去除

德岛大学安澤幹人首次利用γ-PGA在Fe3O4磁性纳米颗粒上进行涂层,制得了γ-聚谷氨酸-Fe3O4磁性纳米颗粒（PG-M）.本实验利用透射电镜以及扫描电镜对PG-M吸附剂的形貌进行了分析,发现PG-M与未涂层的Fe3 O4具有相似的形状以及大小,均为不规则的层状结构,且晶粒直径在120～320 nm之间;实验中针对性地对水溶液中Pb2＋进行了吸附探讨.在振荡实验中,通过主要参数的变化（pH值、吸附时间、竞争离子浓度、腐殖酸浓度）,得到如下结果：吸附最佳pH值为7.0;吸附量随着吸附时间的延长而增长,吸附平衡时间为45 min;Na＋对PG-M去除Pb2＋没有很强的干扰性,而Ca2＋则显示出一定的干扰作用;腐殖酸对吸附效果的影响是复杂的,表现为先增强吸附效果,随后降低吸附效果;最佳条件时Pb2＋的最大吸附量为93.3 mg/g.PG-M对Pb2＋的吸附均能较好地符合Freundlich和Langmuir等温吸附模型,其中Langmuir方程能更好地描述PG-M的吸附特征,说明PG-M在水溶液中对金属离子的吸附为单分子层吸附.PG-M吸附符合准二级动力学模型（r2〉0.99）.不同浓度的HCl和HNO3溶液的再生实验发现,0.1 mol/L的HCl溶液作为吸附再生液,可取得较好的再生效果.表明PG-M是可再生的,具有较好的经济性和可持续性.     

Laboratory investigation of Waelz slag stabilization

Electric Arc Furnace dusts are considered hazardous waste due to their high heavy metals content (zinc, lead, etc.). The Waelz process is one of the most efficient technologies, in terms of capacity and quality, able to recover nearly the 90% of zinc contained in such EAF dusts. Unfortunately, the resulting slag still has eco-compatibility problems, although its mechanical and chemical properties are suitable for civil engineering applications. Stabilization tests, by quartz addition, were performed on EAF dusts in a laboratory furnace. Temperature, treatment time and cooling rate were varied in order to define the best conditions for regulating the formation of a stable microstructure able to hinder the release of substances. Microstructural characterization was carried-out using SEM and XRD analysis. Leaching tests were performed according to EN 12457-2 standards and water analyses were performed using ICP-OES. The best chemical stability was achieved when dust powders were mixed with 20% of silica and water-cooled.     

Influence of extracellular polymeric substances from activated sludge on the aggregation kinetics of silver and silver sulfide nanoparticles

• The NPs aggregation in the electrolyte solution is consistent with the DLVO theory. • In NaNO₃ and low Ca(NO₃)₂, EPS alleviates the NPs aggregation by steric repulsion. • In high Ca(NO₃)₂, EPS accelerates the NPs aggregation by exopolysaccharide bridging. • Ag₂S NPs have stronger stability compared with Cit-Ag NPs in aqueous systems. Extracellular polymeric substances (EPS) in activated sludge from wastewater treatment plants (WWTPs) could affect interactions between nanoparticles and alter their migration behavior. The influence mechanisms of silver nanoparticles (Ag NPs) and silver sulfide nanoparticles (Ag₂S NPs) aggregated by active EPS sludge were studied in monovalent or divalent cation solutions. The aggregation behaviors of the NPs without EPS followed the Derjaguin-Landau-Verwey-Overbeek (DLVO) theory. The counterions aggravated the aggregation of both NPs, and the divalent cation had a strong neutralizing effect due to the decrease in electrostatic repulsive force. Through extended DLVO (EDLVO) model analysis, in NaNO₃ and low-concentration Ca(NO₃)₂ (<10 mmol/L) solutions, EPS could alleviate the aggregation behaviors of Cit-Ag NPs and Ag₂S NPs due to the enhancement of steric repulsive forces. At high concentrations of Ca(NO₃)₂ (10‒100 mmol/L), exopolysaccharide macromolecules could promote the aggregation of Cit-Ag NPs and Ag₂S NPs by interparticle bridging. As the final transformation form of Ag NPs in water environments, Ag₂S NPs had better stability, possibly due to their small van der Waals forces and their strong steric repulsive forces. It is essential to elucidate the surface mechanisms between EPS and NPs to understand the different fates of metal-based and metal-sulfide NPs in WWTP systems.     

Effect of two TiO2 nanoparticles on the growth of unicellular green algae using the OECD 201 test guideline: influence of the exposure system

This work aimed at assessing the influence of different exposure systems to perform the commonly used OECD 201 freshwater algal growth inhibition test in the context of nanoparticles hazard assessment. Two distinct TiO₂ nanoparticles were considered and three different exposure systems were investigated: Erlenmeyers flasks and 24-well microplates (both using an orbital shake system), and an alternative system using cylindrical vials and magnetic stirring. All three systems are in accordance with the OECD 201 test guideline recommendations. We concluded that the exposure systems applied to achieve the test can substantially affect the ecotoxicological results and the subsequent calculated ECx. The selected systems influenced both the interaction between algal cells and TiO₂ nanoparticles as well as the growth inhibition recorded. Disparities in ecotoxicity relative to the TiO₂ nanoparticles tested were also observed and are finally discussed.     

Catalytic activity of noble metal nanoparticles toward hydrodechlorination: influence of catalyst electronic structure and nature of adsorption

In this study, stabilized Pd, Pt and Au nanoparticles were successfully prepared in aqueous phase using sodium carboxymethyl cellulose (CMC) as a capping agent. These metal nanoparticles were then tested for catalytic hydrodechlorination toward two classes of organochlorinated compounds (vinyl polychlorides including trichloroethylene (TCE), tetrachloroethylene (PCE), and alkyl polychlorides including 1,1,1-trichloroethane (1,1,1-TCA), and 1,1,1,2-tetrachloroethane (1,1,1,2-TeCA)) to determine the rate-limiting steps and to explore the reaction mechanisms. The surface area normalized reaction rate constant, k_SA, showed a systematic dependence on the electronic structure (the density of states at the Fermi level) of the metals, suggesting that adsorption of organochlorinated reactants on the metal catalyst surfaces is the rate-limiting step for catalytic hydrodechlorination. Hydrodechlorination rates of 1,1,1-TCA and 1,1,1,2-TeCA agreed with the bond strength of the first (weakest) dissociated C-Cl bond, suggesting that C-Cl bond cleavage, which is the first step for dissociative adsorption of the alkyl polychlorides, controlled the catalytic hydrodechlorination rate. However, hydrodechlorination rates of TCE and PCE correlated with the adsorption energies of their molecular (non-dissociative) adsorption on the noble metals rather than with the first C-Cl bond strength, suggesting that molecular adsorption governs the reaction rate for hydrodechlorination of the vinyl polychlorides.