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.     

ZnO-PMMA复合材料光催化去除水中低浓度氨氮

通过水热法制备纳米ZnO,采用热粘固法成功地将其负载于聚甲基丙烯酸甲酯(PMMA)微球表面,并对ZnO-PMMA复合材料光催化去除水中低浓度氨氮的能力进行了考察.同时,探究了负载比例、初始氨氮浓度、催化剂浓度和pH对低浓度氨氮去除效率的影响.实验结果显示,PMMA改善了纳米ZnO的分散性和光催化能力,ZnO-PMMA能够有效地催化去除氨氮废水.在汞灯照射下,当pH=12、温度为30℃时,1 g·L~(-1)的催化剂(ZnO-PMMA)对50 mg·L~(-1)的氨氮废水去除率达到66%,且反应产物硝氮和亚硝氮含量较低,体现了该催化剂具有将氨氮转化为N2的良好的光催化降解能力.同时,纳米材料可以简单方便地回收,减轻了对环境的潜在影响,符合绿色化学的原则.     

常规金属离子对Fe3O4磁性纳米颗粒悬浮和沉降的影响

水体中的有机质、无机盐及酸碱度是影响纳米材料迁移转化的主要因素.考察了Na~+、Mg~(2+)、Ca~(2+)、Sr~(2+)和Ba~(2+)对Fe_3O_4磁性纳米材料(Magnetic Nanoparticles,MNPs)的沉降作用.结果表明,Fe_3O_4MNPs的沉降作用是水体pH、金属离子化合价、离子强度共同影响的结果.整体上,碱土金属离子较Na~+更能加速Fe_3O_4MNPs的沉降.当pH为5.0时,浓度低于1.0 mmol·L~(-1)的Na~+、Mg~(2+)和Ca~(2+)有助于Fe_3O_4MNPs的悬浮;当浓度大于1.0 mmol·L~(-1)时,较强的离子强度促使Fe_3O_4MNPs团聚,发生沉降.当pH为9.0时,碱土金属离子较Na~+更能促使Fe_3O_4MNPs聚沉.因此,纳米颗粒在水体中的扩散和聚沉需要综合考虑金属离子种类和浓度.     

天然水体中多壁纳米碳管对纳米氧化锌颗粒团聚与沉降行为的影响

研究了淡水湖泊水体中氧化多壁纳米碳管(Oxidized-multiwalled carbon nanotubes,o-MWCNTs)对纳米氧化锌(ZnO nanoparticles,nZnO)颗粒团聚与沉降行为的影响,探讨了天然胶体及o-MWCNTs的浓度对nZnO颗粒团聚粒径、团聚速率及沉降行为的作用.结果表明,nZnO在天然水体中会发生明显沉降,相比去除天然胶体的天然水而言,天然胶体的存在显著减少了nZnO的沉降.这主要归因于nZnO-天然胶体颗粒间的作用能垒高于nZnO-nZnO颗粒间的作用能垒,使得天然胶体的存在降低了nZnO-nZnO之间的颗粒碰撞效率,从而促进nZnO悬浮.o-MWCNTs对nZnO在天然水体中沉降行为的影响与天然胶体密切相关.相比于nZnO的单独沉降,在不过膜天然水中(含天然胶体),低浓度o-MWCNTs的存在增加了颗粒间的团聚速率,从而促进nZnO的沉降,而高浓度o-MWCNTs降低了颗粒间的团聚速率和团聚体粒径,从而降低了nZnO的沉降.而在过膜天然水中(不含天然胶体),o-MWCNTs的存在显著降低了颗粒间的团聚粒径和团聚速率,从而降低了nZnO的沉降,且o-MWCNTs的浓度越高,对nZnO悬浮稳定性的促进作用越明显.     

Fe3O4纳米磁性微粒对全氟辛烷磺酸盐的吸附

采用共沉淀法合成Fe3O4纳米磁性颗粒,用透射电子显微镜(TEM)、X射线衍射仪(XRD)以及振动样品磁强计(VSM)对Fe3O4纳米磁性颗粒的粒径、形貌和磁性进行表征并研究Fe3O4纳米磁性微粒对全氟辛磺酸盐的吸附。结果表明:在PFOS初始浓度4 mg/L,pH为3,反应时间24 h,Fe3O4纳米磁性微粒投加量1.25 g/L,对全氟辛磺酸盐去除率达到90%。Fe3O4纳米磁性微粒对PFOS的吸附符合Freundlich吸附方程。     

Ecotoxicity of nanoparticles of CuO and ZnO in natural water

The acute toxicity of CuO and ZnO nanoparticles in artificial freshwater (AFW) and in natural waters to crustaceans Daphnia magna and Thamnocephalus platyurus and protozoan Tetrahymena thermophila was compared. The L(E)C₅₀ values of nanoCuO for both crustaceans in natural water ranged from 90 to 224 mg Cu/l and were about 10-fold lower than L(E)C₅₀ values of bulk CuO. In all test media, the L(E)C₅₀ values for both bulk and nanoZnO (1.1-16 mg Zn/l) were considerably lower than those of nanoCuO. The natural waters remarkably (up to 140-fold) decreased the toxicity of nanoCuO (but not that of nanoZnO) to crustaceans depending mainly on the concentration of dissolved organic carbon (DOC). The toxicity of both nanoCuO and nanoZnO was mostly due to the solubilised ions as determined by specific metal-sensing bacteria.     

Ionic dye adsorption by zinc oxide nanoparticles

The adsorption behaviour of Basic Red 12, Acid Orange 7 and Acid Blue 1 on zinc oxide nanoparticles (ZNP) has been investigated to understand the physicochemical process involved and to explore the possible use of nanoparticles in the treatment and management of textile waste matter. The dye removal capacity of ZNP towards Basic Red 12, Acid Orange 7 and Acid Blue 1 was found to be 15.64, 6.78 and 6.38 mg g^?1, respectively. The adsorption process was pH dependent and optimum pH values of 9.0, 2.0 and 4.0 were obtained for Basic Red 12, Acid Orange 7 and Acid Blue 1, respectively. Equilibrium was established after 1.0 h for all dyes. Langmuir, Freundlich and Temkin isotherm models were applied to the system. The adsorbent ZNP was characterised using scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), Brunauer–Emmett–Teller (BET) and Fourier transform infrared (FTIR) techniques. SEM analysis revealed the noticeable nanoporous morphology of the material. The results of FTIR spectroscopy showed that the process is driven by an electrostatic complexation mechanism. XRD studies revealed the nanocrystalline structure of ZNP. BET surface area measurement suggested a high pore volume and large surface area for the adsorbent. The kinetic measurements suggested pseudo-second-order kinetic processes with high regression coefficients and smaller standard error of estimate values and lower residual sum of squares. The thermodynamic measurements suggested that all processes were exothermic and accompanied by negative values for Δ G⁰, Δ S⁰ and Δ H⁰.     

Distribution and bioavailability of ceria nanoparticles in an aquatic ecosystem model

Along with the increasing utilization of engineered nanoparticles, there is a growing concern for the potential environmental and health effects of exposure to these newly designed materials. Understanding the behavior of nanoparticles in the environment is a basic need. The present study aims to investigate the distribution and fate of ceria nanoparticles in an aquatic system model which consists of sediments, water, hornworts, fish and snails, using a radiotracer technique. Concentrations of ceria in the samples at regular time intervals were measured. Ceria nanoparticles were readily removed from the water column and partitioned between different organisms. Both snail and fish have fast absorption and clearance abilities. Hornwort has the highest bioaccumulation factors. At the end of the experiment, sediments accumulated most of the nanoparticles with a recovery of 75.7 ± 27.3% of total ceria nanoparticles, suggesting that sediments are major sinks of ceria nanoparticles.     

Impact of nano-CuO stress on rice (Oryza sativa L.) seedlings

Indiscriminate release of metal oxide nanoparticles (NPs) into the environment due to anthropogenic activities has become a serious threat to the ecological system including plants. The present study assesses the toxicity of nano-CuO on rice (Oryza sativa cv. Swarna) seedlings. Three different levels of stress (0.5 mM, 1.0 mM and 1.5 mM suspensions of copper II oxide, <50 nm particle size) were imposed and seedling growth performance was studied along control at 7 and 14 d of experiment. Modulation of ascorbate–glutathione cycle, membrane damage, in vivo ROS detection, foliar H₂O₂ and proline accumulation under nano-CuO stress were investigated in detail to get an overview of nano-stress response of rice. Seed germination percentage was significantly reduced under stress. Higher uptake of Evans blue by nano-CuO stressed roots over control indicates loss of root cells viability. Presence of dark blue and deep brown spots on leaves evident after histochemical staining with NBT and DAB respectively indicate severe oxidative burst under nano-copper stress. APX activity was found to be significantly increased in 1.0 and 1.5 mM CuO treatments. Nevertheless, elevated APX activity might be insufficient to scavenge all H₂O₂ produced in excess under nano-CuO stress. That may be the reason why stressed leaves accumulated significantly higher H₂O₂ instead of having enhanced APX activity. In addition, increased GR activity coupled with isolated increase in GSH/GSSG ratio does not seem to prevent cells from oxidative damages, as evident from higher MDA level in leaves of nano-CuO stressed seedlings over control. Enhanced proline accumulation also does not give much protection against nano-CuO stress. Decline in carotenoids level might be another determining factor of meager performance of rice seedlings in combating nano-CuO stress induced oxidative damages.     

名山河流域黄壤无机纳米微粒对钙的吸附解吸特征

以名山河流域老冲积黄壤无机纳米微粒为对象,从纳米尺度分析钙的吸附解吸机制对土壤养分状况的影响,并采用等温吸附法和静态解吸法,比较不同土地利用方式下钙的吸附解吸特征差异.结果表明:1)不同土地利用方式土壤无机纳米微粒对钙的吸附解吸量均随钙质量浓度增加而增加,在低质量浓度范围内吸附量增加较快,在高质量浓度范围内增加趋缓,不同土地利用方式下钙的吸附能力从高到低为水田(2 580.69 mg/kg)、茶园(2 452.30 mg/kg)、旱地(1 935.10mg/ks)、林地(1 867.36mg/kg)、果园(1 520.65 mg/kg),土壤无机纳米微粒对钙的解吸率从大到小为果园、林地、旱地、茶园、水田,且解吸率随外加钙质量浓度增加而增大;2)去除土壤组分(有机质、游离氧化铁)后,无机纳米微粒对钙的吸附量及解吸量均有所增加,5种土地利用方式吸附增加量从大到小为水田、旱地、茶园、林地、果园;3)去除土壤组分前后,无机纳米微粒对钙的等温吸附均以Freundlich方程拟合效果最佳,相关系数在0.954 5～0.989 0,达到极显著水平,Langmuir方程与Temkin方程拟合效果不佳.研究表明,钙离子以非专性吸附为主,专性吸附为辅,有机质和游离氧化铁的存在会阻碍土壤对钙的吸附及解吸.