纳米材料在土壤重金属污染修复中的应用

重金属污染土壤的修复一直是国内外环境研究者关注的重点环境问题之一.近年来,纳米材料在土壤重金属污染修复中的应用也受到了越来越多的关注.综述了主要纳米材料及其改性材料修复土壤重金属的应用、纳米材料的组合技术应用以及影响纳米材料修复土壤重金属效果的主要因素,提出了今后该领域应重点加强研发新的纳米材料,同时提高其在土壤中的扩散能力,研究从室内实验到田间实验的应用;进一步深入探讨了纳米材料在土壤中的环境行为及相关机理等,以期充分理解并进一步推动纳米材料在土壤重金属污染修复中的应用.      

Experimental study of the mechanical properties of expansive soil with added nanomaterials

The main purpose of this paper is to describe ways to improve the microstructure of expansive soil by adding nanomaterials. Mechanical tests were done to explore the changes in shear strength and compression index of expansive soil that was modified by adding different amounts of two kinds of nanomaterials (nano-alumina and nano-silica). The test results show that adding 1.2% nano-alumina and about 2% nano-silica to expansive soil provides the optimal compression index. The test results show that adding 1.2% nano-alumina and about 1.5% nano-silica to expansive soil provides the optimal unconfined compression stress. Scanning electron microscopy of the microstructure of expansive soil modified by nanomaterials provided a deeper understanding of the effects of nanomaterials on improving expansive soil.     

Nanotechnology,global development in the frame of environmental risk forecasting. A necessity of interdisciplinary researches

Interdisciplinarity is of first importance to evaluate the risks associated with nanotechnology. The reasons are that nanomaterials are very new materials that combine nano-sizes and new reactivities. The complexity comes from the very low concentrations of nanomaterials in the environmental medium, the transformations of the nanomaterials due to the reactivity of the surface, the transfer in the environmental media, particularly in the presence of liquid water (soils, sediments, surface water), which implies an association with natural colloids (organic or minerals) and blockage in some compartments. These properties govern the hazard that strongly depends on exposure and speciation.     

纳米地球科学:内涵与意义

纳米地球科学是纳米科技与地球科学的结合,是一门高度综合的交叉学科,很难划分出经典意义上的单科性研究.纳米地球科学的研究对象主要分为纳米物质与纳米孔隙,二者成因多样、尺度效应明显、广泛分布,对于前者,主要通过各类图像表征手段观察其形态、大小、聚集方式,通过各类谱学方法研究其晶体结构、分子结构等;对于后者,则主要通过图像表征手段、流体注入方法与数值模拟的结合来表征孔隙形态、孔径分布、连通性等特征.纳米地球科学的学科内涵主要体现于:在各传统地球科学学科研究的基础和框架上,针对地球不同圈层中纳米尺度微粒形成、运移、聚集和存在形式以及孔隙形成与演化等亟待解决的科学问题开展系统研究,从而加深对矿物、岩石、构造、地化以及资源、灾害、环境等分支学科纳米尺度特性的认知.纳米地球科学的产生与发展使人类在认识和改造自然方面进入了一个新层次,是地球与行星科学发展的必然途径,为矿床勘探、资源开发、新能源利用、环境污染和地质灾害的预防与治理等问题提供了新的理论依据,有着不可估量的科学意义和应用价值.      

改善金刚石工具性能的方法

介绍了提高金刚石具性能的主要方法,包括;添加稀土元素,自蔓延高温合成技术的应用,采用预合金胎体金属粉末,采用活化烧结方法,设计合理的结构,金刚石表面的金属化,采用超细或纳米级材料等。     

Ingestion of Carbon Nanotubes and Mesoporous Silica Nanospheres by Caenorhabditis Elegans

The toxic effects to microorganism induced by nanomaterials have received considerable attentions in the past decades [1]. Herein, two diverse nanomaterials i.e. multi-walled carbon nanotubes (MWCNTs) and mesoporous silica nanospheres (MSNs) were prepared to investigate their deleterious effects on Caenorhabditis. elegans (C. elegans)[2-3]. As shown in Figure 1A, histidine functionalized MWCNTs (his-MWCNTs) were in length of ⁵00 nm with outer diameter 500 nm with outer diameter ²0 nm, while fluorescein isothiocyanate dyed MSNs (FITC-MSNs) were in an average diameter of 20 nm, while fluorescein isothiocyanate dyed MSNs (FITC-MSNs) were in an average diameter of ⁷0 nm (Figure 1B). Microscopic images display his-MWCNTs having been ingested into intestine of C. elegans after co-incubation for 2 h, as arrowed in Figure 1C and 1E. In contrast, no MSNs were observed to be ingested after co-incubating in the same liquid medium. However, fluorescence microscopic images (Figure 1D and 1F) demonstrate that FITC-MSNs could be ingested by C. elegans after co-incubation for 24 h or longer time via seeding Kingagar plates with FITC-MSNs.     

矿物材料应用于香烟过滤嘴降害的研究现状与展望

总结了近几十年来包括活性炭、沸石、蒙脱石、海泡石、麦饭石、凹凸棒石、氧化铝、氢氧化钠、明矾、纳米材料等矿物材料作为卷烟滤嘴添加剂以去除烟气中有毒有害物质的研究和实验应用及效果。实验结果和市场调查表明,活性炭是减少卷烟危害最快、香烟市场应用增长最快的过滤嘴添加剂。从降低卷烟有害成分的比例和成本等综合因素来看,铝硅酸盐类滤嘴和多材料复合滤嘴亦有很好的应用前景和市场需求,应积极进行研制。     

不同种类纳米零价铁的毒性比较研究

纳米零价铁是一种高效的环境修复材料,可以处理多种污染物;然而,纳米粒子的尺寸效应可能导致其在自然界中存在潜在毒性风险。选择几种常用包覆型、负载型和裸露的纳米铁,通过大肠杆菌的耐受性实验,比较3种纳米铁的毒性。研究表明,负载型纳米铁的分散性最好,而裸露纳米铁最差。3种纳米铁虽然对大肠杆菌都表现出毒性,但是负载型纳米铁的毒性最小。通过毒性减缓的机理分析,说明纳米铁改性后阻止了纳米颗粒与细菌的直接接触,这是空间位阻效应的作用。研究结果进一步证实了在使用纳米材料前应充分评估潜在毒性和环境效应的重要性。     

Microscopic Observation and Stability Study on the Fe_3s_4 Nanocrystals Synthesizedunder Thermal and Humid Conditions

Fe3S4 is important magnetic mineral that widely exists in the sediments of lakes and oceans. It can not only instruct reducing environment that contains organic matter and sulfate, but also provide paleomagnetic signal for paleoenvironmet research. Simultaneously, as a new type of magnetic material, it causes attention. Because Fe3S4 generally exists as an unstable intermediate, it is stringent in preparation conditions. Although some scholars have conducted on the synthesis experiments of Fe3S4 materials, the research on its stable conditions, formation mechanism and evolution process is not yet depth. Accordingly, defining the stable conditions and revealing evolution law of Fe3S4 nanocrystals have important significance for the determination of environmental conditions and the preparation of pure Fe3S4 nanomaterials.     

纳米材料对水体中PFCs的去除行为及机制

全氟化合物（Perfluorinated Compounds,PFCs）是一类含有强极性碳氟键的阴离子表面活性剂.由于PFCs的高稳定性、高生物累积性和潜在毒性,其在水环境中的广泛存在已经对人类的生命健康造成了极大的威胁.近年来,研究者不断寻找有效的材料和处理技术去除水体中的PFCs.纳米材料因其特殊的结构和效应,比一般材料有更高的反应活性.总结了如碳纳米管、改性粘土矿物、纳米二氧化钛、氧化铟、氧化镓等新型纳米材料在物理吸附、光化学及电化学法去除PFCs中的应用,并比较了上述各材料去除PFCs的优缺点及各自的去除机制,分析了目前纳米材料去除水体中PFCs存在的主要问题并展望了今后的发展趋势.      

Detection of smectites in ppm and sub-ppm concentrations using dye molecule sensors

Methylene blue and rhodamine 6G were used as molecular sensors for the spectrophotometric titrations of the aqueous colloids of clay minerals (montmorillonite, illite and kaolinite). The dyes adsorbed on colloid particles form molecular aggregates, which exhibit spectral properties significantly different from those of dye solutions. Spectrophotometric titrations provide the most sensitive detection of smectites in aqueous colloids (sub-ppm concentrations); and the sensitivity further increases using second derivative spectroscopy. The endpoint of spectrophotometric titrations can be used for the determination of exchange capacity of the mineral in colloids and in this way to estimate its amount. The method is selective only to expandable clays, which was proven by experiments with kaolinite and illite. Spectrophotometric titrations have promising future in the analysis of clays and can be applied in many fields of geology, mineralogy, chemistry, material sciences or in industry. Its application may expand to the analysis of other nanomaterials built from charged particles and exhibiting metachromasy in the systems with organic dyes.     

与海洋天然气水合物微纳米尺度赋存和开采储存技术有关的研究进展

天然气水合物是一类潜在的储量巨大的清洁能源.近年来,水合物的研究已经逐渐拓展至纳米、介观层面.纳米科学贯穿了水合物研究的全过程,包括上游天然气水合物成藏、开采和下游的储运、分离等水合物应用技术,其核心在于研究水合物在纳米材料表面、内部、间隙中生长和分解的传质传热过程.将以第九届国际水合物大会（ICGH9）为切入点,从水合物成藏、开采和下游技术应用几个方面综述近年来水合物研究中的纳米研究进展.目前对水合物的研究尺度并未做到全覆盖,水合物在纳米材料间隙中的传质传热过程研究较少,纳米材料的累积放大效应研究也存在空白.这正是水合物成藏、开采研究中的瓶颈问题.未来的研究应该着眼于水合物在纳米材料中生成和分解的传质传热作用,以此为主线将水合物技术和水合物成藏、开采研究中的核心问题进行统一协同研究.      

Application of nanoadsorbents for removal of lead from water

Enormous increase in the application of various heavy metals including lead for commercial and non-commercial purposes has also led to their enhanced occurrence in the effluents from industries and domestic discharge creating substantial environmental concerns. The existing techniques for removal of these contaminants such as reverse osmosis and ion exchange suffer a few disadvantages and hence, thrust to develop efficient techniques for the removal have been ever increasing. Adsorption based on the use of nanoadsorbents is promising being cost effective and based on the ease of operation. The present work furnishes a detailed overview on nanoadsorbents for removal of lead from water. The various nanoadsorbents covered in the analysis include alumina, anatase, carbon nanotubes, chitosan, copper, iron and zinc oxide, magnetite, nanoclay and zirconium nanoparticles. The review also gives an insight into the synthesis and characterization of nanoadsorbents followed by guidelines on optimum operating parameters to be used in the removal process for maximizing the extent of removal. The typical optimum conditions established based on the critical analysis of literature are pH ≤ 6, contact time ≥60 min and optimum adsorbent dose dependent on the nanomaterials. Comparison of different nanoparticles revealed that titanium oxide and hematite nanoparticles are the best, giving 100% removal efficiency for lead ions. The sequestration was mainly dependent on adsorbent dose that has to be kept optimum to yield adequate surface area and number of adsorption sites. Overall, nanoadsorbents have been established to yield efficient removal of lead from water.     

Recycled concrete aggregate coated with quaternary ammonium compounds for water disinfection

Growing demand for point-of-use water treatment including greywater recycling as well as appropriate disinfection without formation of harmful disinfection byproducts (DBPs) calls for new methods of efficient microbial control. In recent years, antimicrobial nanomaterials (NMs) have been widely studied as a potential alternative to traditional chlorine disinfection, yet concerns over their releases to environments and subsequent impacts have limited their use on a large scale. In this work, recycled concrete aggregate (RCA) was proposed as a sustainable and environmentally friendly disinfecting substrate for water disinfection by coating with a composite of silica-quaternary ammonium compound (Fixed-Quat). Two different types (gel and particle) of Fixed-Quat were applied to RCA, and their adherence and antimicrobial activities were compared each other. When using E. Coli as a model bacterial pathogen, the Fixed-Quat gel and particle coated RCA materials showed similar and effective microbial inactivation performance with a rate of 2.0 × 10^?3 (gel) and 1.82 × 10^?3 (particle) log reduction cm^?2 min^?1. By potentially eliminating regulated DBPs formation and minimizing release of NMs into the environment, the antimicrobial coated RCA would be a promising and sustainable alternative to conventional disinfection methods in engineered aquatic systems.     

Green synthesis of magnetic mesoporous silica nanocomposite and its adsorptive performance against organochlorine pesticides

Green synthesis of nanomaterials has received increasing attention as an eco-friendly technology in materials science. Here, we have used two types of extractions from green tea leaf (i.e., total extraction and tannin extraction) as reducing agents for a rapid, simple and one-step synthesis method of mesoporous silica nanoparticles/iron oxide nanocomposite based on deposition of iron oxide onto mesoporous silica nanoparticles. Mesoporous silica nanoparticles/iron oxide nanocomposite were characterized by X-ray diffraction, Fourier transform infrared spectroscopy, scanning electron microscopy, energy-dispersive X-ray, vibrating sample magnetometer, N₂ adsorption and high-resolution transmission electron microscopy. Mesoporous silica nanoparticles/iron oxide nanocomposite was used as a solid adsorbent for removal of lindane pesticide from aqueous solutions. The developed system possesses the advantages of silica as core that include large surface area and advantages of iron oxide (shell) that include the capability to interact with chlorinated compounds and ability to release by using external magnetic field. UV-Vis technique was used as a simple and easy method for monitoring the removal of lindane. Effects of pH and temperature on the removal efficiency of the developed mesoporous silica nanoparticles/iron oxide nanocomposite toward lindane pesticide were also investigated. Fourier transform infrared spectroscopy, high-performance liquid chromatography and gas chromatography techniques were used to confirm the high ability of mesoporous silica nanoparticles/iron oxide nanocomposite for sensing and the capture of lindane molecules with high sorption capacity (about 99%) that could develop a new eco-friendly strategy for detection and removal of pesticide and as a promising material for water treatment.     

<Emphasis Type="SmallCaps">G</Emphasis>reen zero-valent iron nanoparticles for the degradation of amoxicillin

In the last years, it has been proven that zero-valent iron nanoparticles, including those produced using green methods, are efficient remediation agents for a wide range of target contaminants. However, apart from the known advantages of these green nanomaterials, the knowledge of how they act on distinct contaminants is not yet fully understood and requires further investigation. The objectives of this work were to study the degradation of a common antibiotic, amoxicillin, in water and in a sandy soil using green zero-valent iron nanoparticles (gnZVIs) as reductants and as catalysts for the Fenton reaction. It represents the first study of the use of gnZVI, as alternative for the zero-valent iron nanoparticles produced with sodium borohydride, for the degradation of amoxicillin. The results of the performed tests indicate that gnZVIs have the potential to be used in remediation processes. In both chemical tests, the gnZVI was able to degrade up to 100% of amoxicillin in aqueous solutions, using an amoxicillin/gnZVI molar ratio of 1:15 when applied as a reductant, and an amoxicillin/H₂O₂/gnZVI molar ratio of 1:13:1 when applied as a catalyst for the Fenton reaction. The soil tests showed that the required molar ratios for near complete degradation were higher in the reduction test (1:150) than in the gnZVI-catalyzed Fenton reaction (1:1290:73). This is possibly due to parallel reactions with the soil matrix and/or limitations of the reagents to reach the entire soil sample. The degradation efficiencies obtained in these tests were 55 and 97% for the reduction and catalyzed Fenton processes, respectively.     

复杂储层多尺度数字岩石评价

复杂储层岩石矿物组成非均质性强,孔喉结构细小.储集空间有效性评价、岩石结构精细评价及流体赋存状态与运移规律评价是决定复杂储层油气勘探成效的关键.针对复杂储层的储集空间（孔喉、裂缝）、岩石结构（矿物、有机质）、流体特征3方面,建立了复杂储层多尺度数字岩石评价技术及工作流程.储集空间表征方面:二维大面积分析技术可建立跨越6~7个数量级的多尺度选取及非均质性评价;多尺度CT及FIB-SEM联用可精确刻画孔喉和裂缝的三维空间分布;电化学和显影剂技术可以有效地帮助分析微观孔隙连通性.固体组分分析方面:XRF及Qemscan联用可定量评价矿物组成与分布;三维FIB-SEM技术可以实现有机质形态和分布的定量分析.流体特性方面:荷电效应可用于微量残留有机流体的识别与表征;通过合成孔径、润湿性、表面微结构均可调控的纳米材料,开展地层条件下页岩油赋存及流动物理模拟研究,确定了单一因素对页岩油赋存及可动孔径下限的影响;利用分子模拟研究油气在无机、有机质纳米孔隙中的聚集机理与扩散潜力.复杂储层多尺度数字岩石评价技术体系和一系列具体应用可以有效地填补常规储层分析手段的不足,为页岩油气、致密砂岩油气储层以及深部油气储层等复杂储层有效性评价和含油气性定量评价提供技术支撑.      

Formation of carbon nano-balls and carbon nano-tubes from northeast Indian Tertiary coal: Value added products from low grade coal

The paper reports the presence of carbon nano-balls and nano-tubes in the clean coal product during our experiments on desulfurization and deashing of northeast Indian high-sulfur Tertiary coal by molten caustic leaching (MCL) method. The Scanning Electron Microscopy (SEM), High Resolution Transmission Electron Microscopy (HR-TEM), X-ray Diffraction (XRD), Raman and Fourier Transform Infrared (FT-IR) spectroscopy analyses revealed the formation of varied sizes of carbon nanomaterials in the clean coal product (MCL product). The nano-balls are in the range of 5–10 nm with nominal areas in the range of 40–100 nm², 160–220 nm², and 550–650 nm². The diameters of the carbon nano-tubes (CNTs) formed are in the range of 18–24 nm. The diameters of the branch carbon nano-tubes (BCNTs) are in the range of 35–92 nm. It is further observed that the alkaline treatment followed by acid treatment favored the formation of the carbon nano-balls, carbon nano-tubes (CNTs), and branch carbon nanotubes (BCNTs) in the coal product. The low-grade coals could also be used for the preparation of nano-carbon-based high value added products.     

Photocatalytic activity evaluation of TiO<Subscript>2</Subscript> nanoparticles based on COD analyses for water treatment applications: a standardization attempt

Evaluation of the photocatalytic activities of TiO₂ nanomaterials based on the chemical oxygen demand (COD) analyses under identical experimental conditions was not previously reported. In this work, COD has been selected as an adequate industrial water quality measure toward the establishment of a representative standard test method. The initial COD values of six organic pollutants representing dye, surfactants, phenols and alcohol were set at 30 ± 2 mg/L. Ten of different commercial and synthesized TiO₂ samples representing anatase, rutile and mixed phases were used and characterized. The data of photocatalytic processes were compared to that obtained using the commonly widespread Degussa-P25 TiO₂ (TD). The COD of all pollutants was completely removed by TD at UV exposure dose ≤9.36 mWh/cm². Consequently, the maximum irradiation dose was set at this value in all experiments. The percentages of COD removal as well as the values of the accumulated UV doses required for complete removal of pollutants were measured using the different TiO₂ samples. TiO₂ samples show different performance abilities toward the various pollutants compared to TD. Based on the obtained data, TiO₂ photocatalysts were divided into two categories according to the hydroxyl radical formation rates. Comparison with previous studies reveals that the photocatalytic efficiency evaluation depends on the method of measurement. COD is recommended to be used as an adequate technique of analysis that meets the purpose of water treatment applications.     

Toxicity effects of four typical nanomaterials on the growth of <Emphasis Type="Italic">Escherichia coli</Emphasis>, <Emphasis Type="Italic">Bacillus subtilis</Emphasis> and <Emphasis Type="Italic">Agrobacterium tumefaciens</Emphasis>

To offer an insight into the toxicity of nanomaterials (NM) on the growth of bacteria, Escherichia coli (E. coli), Bacillus subtilis (B. subtilis) and Agrobacterium tumefaciens (A. tumefaciens) were exposed to nano-Au, nano-Ag, nano-Fe and fullerene (C₆₀) in this study. As an effective bactericide, nano-Ag induced high toxicity on these three bacteria; C₆₀ could inhibit their growth; however, B. subtilis and E. coli could recover as exposure time extended. Nano-Au and nano-Fe had hardly any effect on three bacteria. A. tumefaciens showed the lowest resistance and slowest growth rate during exposure. Images obtained by scanning electron microscope (SEM) revealed that nano-Ag could cause damage to the cell structure of three bacteria at 1 μg/mL. Slight damage on E. coli was found when exposed to C₆₀, whereas no obvious physical damage was found after exposure to nano-Au or nano-Fe. It is assumed that surface activities of NM might be responsible for the different toxic effects on these bacteria.