Water chemistry controlled aggregation and photo-transformation of silver nanoparticles in environmental waters

The inevitable release of engineered silver nanoparticles (AgNPs) into aquatic environments has drawn great concerns about its environmental toxicity and safety. Although aggregation and transformation play crucial roles in the transport and toxicity of AgNPs, how the water chemistry of environmental waters influences the aggregation and transformation of engineered AgNPs is still not well understood. In this study, the aggregation of polyvinylpyrrolidone (PVP) coated AgNPs was investigated in eight typical environmental water samples (with different ionic strengths, hardness, and dissolved organic matter (DOM) concentrations) by using UV–visible spectroscopy and dynamic light scattering. Raman spectroscopy was applied to probe the interaction of DOM with the surface of AgNPs. Further, the photo-transformation and morphology changes of AgNPs in environmental waters were studied by UV–visible spectroscopy, inductively coupled plasma mass spectrometry, and transmission electron microscopy. The results suggested that both electrolytes (especially Ca^2 + and Mg^2 +) and DOM in the surface waters are key parameters for AgNP aggregation, and sunlight could accelerate the morphology change, aggregation, and further sedimentation of AgNPs. This water chemistry controlled aggregation and photo-transformation should have significant environmental impacts on the transport and toxicity of AgNPs in the aquatic environments.     

近红外长余辉纳米颗粒经小鼠眼部暴露后体内分布和代谢情况

为了研究纳米颗粒通过眼部暴露后进入体内的路径及在体内的分布和代谢情况,实验采用近红外长余辉纳米探针作为示踪剂,对小鼠进行眼部暴露,随后利用活体成像技术观察其进入小鼠体内的过程及分布情况,于暴露第4天收集代谢产物,第7天取重要脏器和血液,并检测纳米探针的存在情况.结果显示纳米探针可由眼经口腔进入胃肠道中,并且纳米颗粒暴露4天后在小鼠的粪便中检测到强荧光信号,而尿液中的荧光信号较弱,暴露7 d后在小鼠的眼睑结膜、胃及眼球中检测到强荧光信号,而其余器官的荧光信号较弱.这表明通过眼部暴露后,纳米颗粒主要分布在眼和消化系统中,最后大部分经消化系统代谢.     

磁性纳米铁对厌氧颗粒污泥特性及其微生物群落的影响

考察了磁性纳米铁(Fe3O4NPs)对厌氧颗粒污泥溶解性微生物产物(SMP)、疏松胞外聚合物(LB-EPS)、紧密胞外聚合物(TB-EPS)的影响,同时利用高通量测序技术对厌氧颗粒污泥内微生物群落结构的变化进行了分析.结果表明,在长期接触实验过程中,投加Fe3O4NPs的反应器对COD去除率为83.6%,与对照组相比降低了5.7%.对照组与实验组中厌氧颗粒污泥TB-EPS含量(以VSS计)分别为178.20 mg·g-1和138.24 mg·g-1,而SMP含量分别为34.88 mg·L-1和27.44 mg·L-1;同时投加Fe3O4NPs后,在LB-EPS三维荧光(EEM)光谱中,紫外光区类腐殖酸荧光峰消失,辅酶F420荧光峰强度有所降低.在长期接触实验后,甲烷杆菌属(Methanobacterium)所占比例从76.15%增至86.76%,而甲烷丝菌属(Methanothrix)所占比例从17.1%降至7.51%,Methanothrix对于Fe3O4NPs更为敏感;总细菌群落变化明显,其中变形菌门(Proteobacteria)所占比例从66.44%降至47.16%,放线菌门(Actinobacteria)所占比例从8.97%增至17.33%,拟杆菌门(Bacteroidetes)所占比例从8.07%增至17.74%,厚壁菌门和拟杆菌门比例的增加对有机物的厌氧水解过程发挥积极的作用.     

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.     

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。     

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.     

Immobilization of non-point phosphorus using stabilized magnetite nanoparticles with enhanced transportability and reactivity in soils

Laboratory batch and column experiments were conducted to investigate the immobilization of phosphorus (P) in soils using synthetic magnetite nanoparticles stabilized with sodium carboxymethyl cellulose (CMC-NP). Although CMC-stabilized magnetite particles were at the nanoscale, phosphorus removal by the nanoparticles was less than that of microparticles (MP) without the stabilizer due to the reduced P reactivity caused by the coating. The P reactivity of CMC-NP was effectively recovered when cellulase was added to degrade the coating. For subsurface non-point P pollution control for a water pond, it is possible to inject CMC-NP to form an enclosed protection wall in the surrounding soils. Non-stabilized “nanomagnetite” could not pass through the soil column under gravity because it quickly agglomerated into microparticles. The immobilized P was 30% in the control soil column, 33% when treated by non-stabilized MP, 45% when treated by CMC-NP, and 73% when treated by both CMC-NP and cellulase.     

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.     

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.