Zero-valent iron nanoparticles in treatment of acid mine water from in situ uranium leaching

Acid mine water from in situ chemical leaching of uranium (Straz pod Ralskem, Czech Republic) was treated in laboratory scale experiments by zero-valent iron nanoparticles (nZVI). For the first time, nZVI were applied for the treatment of the real acid water system containing the miscellaneous mixture of pollutants, where the various removal mechanisms occur simultaneously. Toxicity of the treated saline acid water is caused by major contaminants represented by aluminum and sulphates in a high concentration, as well as by microcontaminants like As, Be, Cd, Cr, Cu, Ni, U, V, and Zn. Laboratory batch experiments proved a significant decrease in concentrations of all the monitored pollutants due to an increase in pH and a decrease in oxidation-reduction potential related to an application of nZVI. The assumed mechanisms of contaminants removal include precipitation of cations in a lower oxidation state, precipitation caused by a simple pH increase and co-precipitation with the formed iron oxyhydroxides. The possibility to control the reaction kinetics through the nature of the surface stabilizing shell (polymer vs. FeO nanolayer) is discussed as an important practical aspect.     

Comparison of manufactured and black carbon nanoparticle concentrations in aquatic sediments

In this paper, we show that concentrations of manufactured carbon-based nanoparticles (MCNPs) in aquatic sediments will be negligible compared to levels of black carbon nanoparticles (BCNPs). This is concluded from model calculations accounting for MCNP sedimentation fluxes, removal rates due to aggregation or degradation, and MCNP burial in deeper sediment layers. The resultant steady state MCNP levels are compared with BCNP levels calculated from soot levels in sediments and weight fractions of nanosized fractions of these soot particles. MCNP/BCNP ratios range from 10⁻⁷ to 10⁻⁴ (w:w). This suggests that the often acclaimed effect of MCNPs on organic pollutant binding and bioavailability will likely be below the level of detection if natural BCNPs are present, even if binding to MCNP is one to two orders of magnitude stronger than to BCNPs. Furthermore, exposure and toxic effects of MCNPs in sediments and soils will be negligible compared to that of BCNPs.     

Aggregation and ecotoxicity of CeO₂ nanoparticles in synthetic and natural waters with variable pH, organic matter concentration and ionic strength

The influence of pH (6.0-9.0), natural organic matter (NOM) (0-10 mg C/L) and ionic strength (IS) (1.7-40 mM) on 14 nm CeO₂ NP aggregation and ecotoxicity towards the alga Pseudokirchneriella subcapitata was assessed following a central composite design. Mean NP aggregate sizes ranged between 200 and 10000 nm. Increasing pH and IS enhanced aggregation, while increasing NOM decreased mean aggregate sizes. The 48 h-E_rC20s ranged between 4.7 and 395.8 mg CeO₂/L. An equation for predicting the 48 h-E_rC20 (48 h-E_rC20 = −1626.4 × (pH) + 109.45 × (pH)² + 116.49 × ([NOM]) − 14.317 × (pH) × ([NOM]) + 6007.2) was developed. In a validation study with natural waters the predicted 48 h-E_rC20 was a factor 1.08-2.57 lower compared to the experimental values.     

海洋酸化与重金属、有机污染物和人工纳米颗粒的联合毒性效应研究进展

由于大量人类活动的影响,大气CO_2浓度持续增加,其中约1/3被海洋吸收,导致表层海水pH值降低和碳酸盐平衡体系波动,即"海洋酸化"现象。污染物的海洋环境效应一直是全球环境科学领域研究的热点。在实际环境中,海洋酸化往往与污染物共同存在并作用于海洋生态系统,且海洋酸化极有可能改变污染物的海洋环境行为从而影响其毒性效应。但现有研究大多针对海洋酸化或者污染物单独作用下的毒性效应展开,对海洋酸化与污染物的联合毒性效应的研究不足、亟待加强。为此,综述了近年来海洋酸化与典型污染物(重金属、有机污染物)及新型污染物(人工纳米颗粒)的相关文献,重点阐述了海洋酸化对污染物环境行为的影响和海洋酸化与污染物对海洋生物的联合毒性效应,指出当前的研究不足,并对未来的研究方向进行了展望。     

Ecotoxic Effect of Photocatalytic Active Nanoparticles (TiO2) on Algae and Daphnids (8 pp)

Background, Aim and Scope Due to their large potential for manifold applications, the use of nanoparticles is of increasing importance. As large amounts of nanoparticles may reach the environment voluntarily or by accident, attention should be paid on the potential impacts on the environment. First studies on potential environmental effects of photocatalytic TiO2 nanoparticles have been performed on the basis of widely accepted, standardized test systems which originally had been developed for the characterization of chemicals. The methods were adapted to the special requirements of testing photocatalytic nanoparticles. Materials and Methods: Suspensions of two different nanoparticles were illuminated to induce their photocatalytic activity. For testing, the growth inhibition test with the green alga Desmodesmus subspicatus and the immobilization test with the daphnid Daphnia magna were selected and performed following the relevant guidelines (algae: ISO 8692, OECD 201, DIN 38412-33; daphnids: ISO 6341, OECD 202, DIN 38412-30). The guidelines were adapted to meet the special requirements for testing photocatalytic nanoparticles. Results: The results indicate that it is principally possible to determine the ecotoxicity of nanoparticles. It was shown that nanoparticles may have ecotoxicological effects which depend on the nature of the particles. Both products tested differ in their toxicity. Product 1 shows a clear concentration-effect curve in the test with algae (EC50: 44 mg/L). It could be proven that the observed toxicity was not caused by accompanying contaminants, since the toxic effect was comparable for the cleaned and the commercially available product. For product 2, no toxic effects were determined (maximum concentration: 50 mg/L). In the tests with daphnids, toxicity was observed for both products, although the concentration effect-curves were less pronounced. The two products differed in their toxicity; moreover, there was a difference in the toxicity of illuminated and non-illuminated products. Discussion: Both products differ in size and crystalline form, so that these parameters are assumed to contribute to the different toxicities. The concentration-effect curves for daphnids, which are less-pronounced than the curves obtained for algae, may be due to the different test organisms and/or the differing test designs. The increased toxicity of pre-illuminated particles in the tests with daphnids demonstrates that the photocatalytic activity of nanoparticles lasts for a period of time. Conclusions: The following conclusions can be drawn from the test results: (I) It is principally possible to determine the ecotoxicity of (photocatalytic) nanoparticles. Therefore, they can be assessed using methods comparable to the procedures applied for assessing soluble chemicals. - (II) Nanoparticles may exert ecotoxicological effects, which depend on the specific nanoparticle. - (III) Comparable to traditional chemicals, the ecotoxicity depends on the test organisms and their physiology. - (IV) The photocatalytic activity of nanoparticles lasts for a relevant period of time. Therefore, pre-illumination may be sufficient to detect a photocatalytic activity even by using test organisms which are not suitable for application in the pre-illumination-phase. Recommendations and Perspectives: First results are presented which indicate that the topic 'ecotoxicity and environmental effects of nanoparticles' should not be neglected. In testing photocatalytic nanoparticles, there are still many topics that need clarification or improvement, such as the cause for an observed toxicity, the improvement of the test design, the elaboration of a test battery and an assessment strategy. On the basis of optimized test systems, it will be possible to test nanoparticles systematically. If a potential risk by specific photocatalytic particles is known, a risk-benefit analysis can be performed and, if required, risk reducing measures can be taken.     

Dissolution of zinc oxide nanoparticles in exposure media of algae,daphnia, and fish embryos for nanotoxicological testing

Zinc oxide nanoparticles (ZnO NPs) are being widely investigated in a bioassay due to potential negative effects to biological receptor. The dissolution of metal nanoparticles such as ZnO NPs is crucial to interpret nanotoxicity results because ZnO NPs can release toxic-free ions in exposure media. In the present study, dissolution of ZnO NPs was evaluated in three selected synthetic media for aquatic toxicological testing: Elendt M4 daphnia medium, OECD algal medium, and fish embryo rearing solution. Both media are currently recommended for OECD testing for daphnia and algae. Time-dependent dissolution of ZnO NPs has been investigated in terms of sonication time to be used for the preparation of aqueous NPs suspension, and dissolution time corresponding to exposure period in toxicity testing. Since sonication is widely applied for NPs dispersion in the most of nanotoxicological testing, the emphasis of this study was on the dissolution of NPs as a function of sonication time. We also investigated the concentration-dependent dissolution of ZnO NPs. Our results demonstrated that dissolution of ZnO NPs was significantly affected by sonication and dissolution time, as well as NPs concentration. This study showed that parameters affecting dissolution of ZnO NPs should be considered in nanotoxicological testing.     

Entomotoxic effect of silicon dioxide nanoparticles on Plutella xylostella (L.) (Lepidoptera: Plutellidae) under laboratory conditions

The use of higher dosage and repeated applications of conventional pesticides have led to the rapid development of insect resistance to pesticide and adverse effects on human health and environment. Accordingly, researchers are prompted to identify an alternative entomotoxic agent for crop protection. Nanocides are being considered as alternatives to conventional insecticides because they are expected to lessen the application rate and reduce the chances of resistance development in pests. In this study, we evaluated the entomotoxic effects of nanosilica on larvae of Plutella xylostella, in a laboratory by using dust spray, larva dipping, leaf dipping, and solution spray methods. Dust treatment showed a more highly significant effect than the other three treatments. The mortality percentage increased up to 58% and 85% at 24 and 72 h after treatment, respectively, when nanosilica was applied at a rate of 1 mg cm^?2. In all four bioassays, mortality rate increased with both increased time after nanosilica exposure and increased concentration. Light microscopy and scanning electron microscopy images showed that larval death was due to desiccation, body wall abrasion, and spiracle blockage. These results suggested that nanosilica can be an alternative to conventional pesticides if dust formulation would be properly used.     

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.     

氧化铜纳米颗粒(CuO NPs)对土壤环境因子与砷生物有效性的影响

氧化铜纳米颗粒（CuO NPs）可以通过农药和肥料施用、意外泄露或污水灌溉进入As污染农田土壤,从而对土壤环境因子和As生物有效性产生影响.本试验选取两种不同类型土壤（安徽宿松黄棕壤和黑龙江海伦黑土）进行人工As污染,添加不同浓度的CuO NPs,探究90 d淹水-落干过程中CuO NPs对As污染农田环境因子和As生物有效态的影响.结果表明,CuO NPs进入土壤后12 h内快速溶解产生Cu²⁺,且在黄棕壤中的溶解速度较黑土迅速.CuO NPs可在短时间内降低土壤pH,提高土壤氧化还原电位（E_h）,降低土壤电导率（EC）,但随着培养时间增加土壤EC逐渐提高.一定时间内CuO NPs在两种类型土壤中可降低51.0%~82.5%土壤浸出液中的As和15.7%~66.5%的As生物有效性,减少淹水时Fe （II）的含量.但在土壤落干时期产生一定的“纳米效应”从而促进了Fe （II）的产生.研究表明,CuO NPs进入As污染农田改变了土壤环境因子,一定时间内降低了土壤As生物有效性.     

Deposition and Retention of Ultrafine Aerosol Particles in the Human Respiratory System. Normal and Pathological Cases

The particle number concentration in ambient air is dominated by nanometersized particles. Recent epidemiological studies report an association between the presence of nanoparticles in inhaled air at the workplace and acute morbidity and even mortality in the elderly. A theoretical model of deposition of 20 nm particles in the human alveolus was formulated. Gas flow structure and deposition rate were calculated for alveoli with different elastic properties of lung tissue. Data obtained in the paper show increased convective effects and diffusional rate of deposition of nanoparticles for alveoli with higher stiffness of the alveolar wall. The retention of deposited particles is also higher in these pathological alveoli. Results of our calculations indicate a possibility of existence of a positive loop of coupling in deposition and retention of nanoparticles in the lung with pathological changes.