Histopathological studies and oxidative stress of synthesized silver nanoparticles in Mozambique tilapia (Oreochromis mossambicus)

To evaluate the potential environmental effects of engineered nano metals, it is important to determine the adverse effects of various nanomaterials on aquatic species. Adult tilapia (Oreochromis mossambicus) were maintained in 10 L glass aquaria, and exposed to a graded series of synthesized silver nanoparticles (Ag-NPs) at 25, 50 and 75 mg/L for eight days. The LC₅₀ value was 12.6 mg/L. Reduced activities of antioxidant enzymes and the contents of antioxidants were lowered in the gills and liver of fishes treated with Ag-NPs, which resulted in heavy accumulation of free radicals. Histopathological results imply that the balance between the oxidative and antioxidant system in the fish was broken down during Ag-NPs exposure. The principal concern related with the release of nanomaterials and their smaller particle may change the materials transport and potential toxicity to aquatic organisms compared to larger particles.     

纳米Pd/Fe催化甲醇/水中2,2',4,4'-四溴联苯醚(BDE-47)还原脱溴

构建了纳米Pd/Fe催化还原甲醇/水中2,2’,4,4’-四溴联苯醚(BDE-47)反应体系,常压下采用单因素实验系统考察了纳米Pd/Fe催化还原甲醇/水中2,2’,4,4’-四溴联苯醚(BDE-47)的主要影响因素,并分析了BDE-47还原反应的中间产物及终产物.结果表明,纳米Pd/Fe的反应活性随Pd负载率的提高而先升后降;甲醇-水体积比高于50∶50后,BDE-47去除率随甲醇-水体积比升高而降低;在25～40℃内,BDE-47去除率随反应温度的升高而升高,随BDE-47初始浓度的增加而降低,增加纳米Pd/Fe量可提高反应速率;酸性及弱碱性条件有利于BDE-47还原.BDE-47还原主要为脱溴反应,是一个从n溴到(n-1)溴联苯醚的逐步脱溴过程,反应进行90min后,BDE-47分子中溴原子完全被脱除,反应终产物为二苯醚.     

不同pH条件下赤铁矿纳米粒子的聚集和再分散行为研究

纳米粒子的聚集和再分散行为是影响纳米粒子在环境中归趋的重要因素.选取赤铁矿纳米粒子作为研究对象,用Zeta电位和粒径测定仪系统研究其在不同pH条件下的聚集和再分散过程.结果表明,当pH在7.0～8.7之间时,赤铁矿纳米粒子发生较快的聚集(如当pH为8.2时平均粒径在400s内由31nm增加到1400nm).当pH≤6.3时,赤铁矿纳米粒子几乎不发生聚集.不经老化聚集的赤铁矿纳米粒子均能发生再分散,但是再分散过程并不完全可逆,而是呈现一定的非线性.老化使得更多的赤铁矿纳米粒子发生不可逆的聚集,在等电点处老化后的样品不发生再分散.当pH为7.0和8.9时,老化的样品再分散后的平均粒径(约500nm)大于不老化的样品(约250nm).纳米粒子聚集-再分散过程的非线性对预测其在环境中的存在状态和生态效应带来了大的困难.     

人工纳米颗粒在水体中的行为及其对浮游植物的影响

人工纳米颗粒(engineered nanoparticles,ENPs)因其特殊的尺寸效应及良好的光学、磁学等性质,已被广泛应用于医药、生物成像以及工业产品等领域.在生产、使用和排放的过程中,ENPs通过不同途径不可避免地进入水体,因此ENPs在水体中的行为和生物安全性也引起了人们的极大关注.在水生生态系统中,浮游植物作为初级生产者,为自身以及其他营养级生物提供营养物质、能量和氧气,因此受到ENPs的影响是难以估算的.近年来已有大量的研究证实ENPs对生物有毒性效应,但ENPs进入浮游植物体内的机制以及ENPs在浮游植物体内的生物运输和转化的报道较少,并且这方面的机制仍不甚明确.本文重点介绍了纳米材料进入水体的途径,在水体中的行为以及对浮游植物的生物效应的最新研究进展,但这方面的机制研究需要进一步深入.     

Process development for recovery of copper and precious metals from waste printed circuit boards with emphasize on palladium and gold leaching and precipitation

A novel hydrometallurgical process was proposed for selective recovery of Cu, Ag, Au and Pd from waste printed circuit boards (PCBs). More than 99% of copper content was dissolved by using two consecutive sulfuric acid leaching steps in the presence of H₂O₂ as oxidizing agents. The solid residue of 2nd leaching step was treated by acidic thiourea in the presence of ferric iron as oxidizing agent and 85.76% Au and 71.36% Ag dissolution was achieved. The precipitation of Au and Ag from acidic thiourea leachate was investigated by using different amounts of sodium borohydride (SBH) as a reducing agent. The leaching of Pd and remained gold from the solid reside of 3rd leaching step was performed in NaClO-HCl-H₂O₂ leaching system and the effect of different parameters was investigated. The leaching of Pd and specially Au increased by increasing the NaClO concentration up to 10 V% and any further increasing the NaClO concentration has a negligible effect. The leaching of Pd and Au increased by increasing the HCl concentration from 2.5 to 5 M. The leaching of Pd and Au were endothermic and raising the temperature had a positive effect on leaching efficiency. The kinetics of Pd leaching was quite fast and after 30 min complete leaching of Pd was achieved, while the leaching of Au need a longer contact time. The best conditions for leaching of Pd and Au in NaClO-HCl-H₂O₂ leaching system were determined to be 5 M HCl, 1 V% H₂O₂, 10 V% NaClO at 336 K for 3 h with a solid/liquid ratio of 1/10. 100% of Pd and Au of what was in the chloride leachate were precipitated by using 2 g/L SBH. Finally, a process flow sheet for the recovery of Cu, Ag, Au and Pd from PCB was proposed.     

Catalytic hydrogenation rate of polycyclic aromatic hydrocarbons in supercritical carbon dioxide containing polymer-stabilized palladium nanoparticles

Catalytic hydrogenation of polycyclic aromatic hydrocarbons (PAHs) with up to four fused benzene rings over high-density-polyethylene-stabilized palladium nanoparticles in supercritical carbon dioxide via in situ UV/Vis spectroscopy is presented. PAHs can be efficiently converted to saturated polycyclic hydrocarbons using this green technique under mild conditions at 20 MPa of CO₂ containing 1 MPa of H₂ at 40-50 °C. Kinetic studies based on in situ UV/Vis spectra of the CO₂ phase reveal that the initial hydrogenation of a given PAH and the subsequent hydrogenations of its intermediates are pseudo-first-order. The hydrogenation rate of the latter is always much smaller than that of the former probably due to increasing steric hindrance introduced by the hydrogenated benzene rings of PAHs which impedes the adsorption process and hydrogen access to PAHs on catalyst surfaces.     

Hemoglobin (Hb) immobilized on amino-modified magnetic nanoparticles for the catalytic removal of bisphenol A

Catalytic removal of bisphenol A from aqueous solution with hemoglobin immobilized on amino-modified magnetic nanoparticles as an enzyme catalyst was reported. The amino-modified magnetite nanoparticles were firstly prepared by the coprecipitation of Fe²⁺ and Fe³⁺ with NH₃·H₂O and then modified by 3-aminopropyltriethoxysilane. The immobilization process was optimized by examining enzyme concentration, glutaraldehyde concentration, cross-link time, and immobilization time. The optimum conditions for the removal of bisphenol A with immobilized hemoglobin were also investigated. Under the optimality conditions, the removal efficiency of bisphenol A was about 80.3%. The immobilization had a beneficial effect on the stability of hemoglobin and conversions of bisphenol A. According to the proposed breakdown pathway and the intermediates, the enzyme-catalytic removal of bisphenol A by the immobilized hemoglobin is considered to be an effective method.     

Release of silver nanoparticles from outdoor facades

In this study we investigate the release of metallic silver nanoparticles (Ag-NP) from paints used for outdoor applications. A facade panel mounted on a model house was exposed to ambient weather conditions over a period of one year. The runoff volume of individual rain events was determined and the silver and titanium concentrations of 36 out of 65 runoff events were measured. Selected samples were prepared for electron microscopic analysis. A strong leaching of the Ag-NP was observed during the initial runoff events with a maximum concentration of 145 μ Ag/l. After a period of one year, more than 30% of the Ag-NP were released to the environment. Particles were mostly <15 nm and are released as composite colloids attached to the organic binders of the paint. Microscopic results indicate that the Ag-NP are likely transformed to considerably less toxic forms such as Ag₂S.     

TiO2晶体的微波水热法制备及光催化性能研究

以TiSO4和尿素为主要原料,EDTA为控制剂,采用微波水热法制备纳米TiO2光催化剂,并分析了纳米TiO2晶粒的最佳形成条件。利用XRD、TEM等技术对制备产物进行表征。结果表明,TiSO4和尿素混合物在微波水热条件下晶化150min后,产物为锐钛矿型TiO2,且产物粒径小、大小均匀。在紫外光照射下,以自制的锐钛矿型纳米TiO2为催化剂,酸性橙为降解目标物,进一步研究了其光催化性能。结果表明,该TiO2在紫外光照射下表现出稳定的光催化活性。     

水培实验中不同粒径纳米TiO_2对芦苇种子发芽和植株生长和生理的影响

纳米二氧化钛(TiO_2-NPs)是目前应用最为广泛的纳米材料之一,进入到天然湿地和人工湿地中的TiO_2-NPs会在湿地生物、基质、水体之间进行迁移转化和归趋。目前针对TiO_2-NPs对湿地植物芦苇的毒性研究很少。本文采用水培实验方法,研究了不同粒径TiO_2对芦苇种子发芽和植株生长的影响,解析了TiO_2-NPs对芦苇的生态毒理效应。研究结果表明:几种粒径的TiO_2-NPs在较低浓度(≤200 mg·L~(-1))下对芦苇种子发芽均具有一定的促进作用,高浓度处理会抑制芦苇种子发芽;当TiO_2-NPs浓度为500 mg·L~(-1)时,处理后的芦苇种子的发芽指标较空白对照均出现显著降低,4 nm和20 nm的TiO_2-NPs对芦苇种子发芽的半数有效浓度(EC50)分别为1 075 mg·L~(-1)和1 680 mg·L~(-1)。TiO_2-NPs对芦苇植株的毒害作用表现为植株生长速度减缓甚至停滞、叶片失绿、植株萎焉或枯死、芦苇倒二叶面积增长率降低,并且TiO_2-NPs的粒径越小、浓度越高毒害作用越明显。随TiO_2-NPs浓度升高,处理后芦苇叶片的叶绿素含量和植株体内的Mg含量均降低,根系的超氧化物歧化酶(superoxide dismutase,SOD)活性、丙二醛(malondialdehyde,MDA)均升高,而且越小粒径的TiO_2-NPs对芦苇的处理效果越明显。3种粒径的TiO_2-NPs均能进入芦苇体内,粒径越小、浓度越高进入的量越多,但是TiO_2-NPs比较难以从根迁移转运至茎和叶。