Long-term effects of silver nanoparticles on performance of phosphorus removal in a laboratory-scale vertical flow constructed wetland

Silver nanoparticles(AgNPs) have been widely used in many fields,which raised concerns about potential threats to biological sewage treatment systems.In this study,the phosphorus removal performance,enzymatic activity and microbial population dynamics in constructed wetlands(CWs) were evaluated under a long-term exposure to Ag NPs(0,50,and 200 μg/L) for 450 days.Results have shown that Ag NPs inhibited the phosphorus removal efficiency in a short-term exposure,whereas caused no obviously negative effects from a long-term perspective.Moreover,in the coexisting CW system of Ag NPs and phosphorus,competition exhibited in the initial exposure phase,however,cooperation between them was observed in later phase.Enzymatic activity of acid-phosphatase at the moderate temperature(10–20°C) was visibly higher than that at the high temperature(20–30℃) and CWs with Ag NPs addition had no appreciable differences compared with the control.High-throughput sequencing results indicated that the microbial richness,diversity and composition of CWs were distinctly affected with the extension of exposure time at different Ag NPs levels.However,the phosphorus removal performance of CWs did not decline with the decrease of polyphosphate accumulating organisms(PAOs),which also confirmed that adsorption precipitation was the main way of phosphorus removal in CWs.The study suggested that Ag NPs and phosphorus could be removed synergistically in the coexistence system.This work has some reference for evaluating the influences of Ag NPs on the phosphorus removal and the interrelation between them in CWs.     

电化学微传感器检测水中痕量铜离子

为改善微电极在阳极溶出伏安法检测重金属离子过程中低电流响应和低电催化能力的缺点,提出了一种在碳纤维微电极表面合成还原氧化石墨烯/纳米金材料制得还原氧化石墨烯纳米金修饰碳纤维微电极（rGO/AuNPs CFMEs）的方法.通过SEM表征,所制备的rGO/AuNPs CFMEs具有比表面积高、吸附能力强和催化活性好的特点,因此改性微电极适合作为方波阳极溶出伏安法（SWASV）测定水中铜离子（Cu²⁺）的工作电极.在构建微传感器测试水中痕量铜离子系统后,对pH值、电导率、富集时间和富集电位等检测条件进行了优化.在pH值为4,电导率为36.1S/m,富集时间为360s,富集电位为-1.2V的最佳条件下,铜的线性范围和检出限分别0~1.0μmol/L和2.4nmol/L.此外,微传感器的可重复性、长期稳定性以及选择性也得到了验证.     

Pt负载暴露(001)晶面Bi2WO6催化剂合成及光催化性能

通过水热法制备了暴露（001）晶面的Bi₂WO₆纳米片,利用光还原法将Pt纳米颗粒负载于其表面.选择苯甲醇氧化和罗丹明B（RhB）降解为探针反应,评价了催化剂的光催化性能.在苯甲醇氧化实验中,Pt负载暴露001晶面的Bi₂WO₆样品的苯甲醇转化率为20.7%,约为未负载样品的2倍.在RhB降解实验中,Pt负载样品在光照40min后对RhB的矿化率可达81.1%,而未负载样品RhB矿化率仅为55.8%,表明Pt负载样品具有更优的降解速率和矿化能力.催化剂性能的提升归因于高能晶面暴露和Pt负载的协同作用.Pt纳米颗粒的负载作为助催化剂增加了催化剂表面的活性位点,同时提高了晶面光生电子空穴对的分离和迁移效率.     

磁性有序介孔碳的制备及其对水中双酚A的吸附

采用水热法成功制备了磁性有序介孔碳（Fe-OMC）,用于吸附水中双酚A （BPA）.采用高倍投射电镜、X射线衍射仪、傅里叶红外光谱仪、比表面积分析仪和振动样品磁强计对Fe-OMC进行表征.结果表明,该吸附剂具备较大的比表面积、独特的有序介孔孔道结构、丰富的含氧官能团以及较强的超顺磁性.Fe-OMC能够高效地吸附去除水中的BPA,平衡吸附量可达72.62mg/g,经过外加磁场分离回收后依旧具备较好的吸附性能.随着BPA浓度从1mg/L提高到20mg/L,其平衡吸附量由8.33mg/g增至91.78mg/g.随着pH值的升高呈现出先降低后升高再降低的趋势,最高吸附量出现在pH=8（75.34mg/g）.Fe-OMC对BPA的吸附过程可用准二级吸附动力学模型和Langmuir吸附等温模型进行描述.计算的热力学参数表明,Fe-OMC对BPA的吸附过程是自发进行的放热过程.     

Long-term effects of environmentally relevant concentrations of silver nanoparticles on microbial biomass, enzyme activity, and functional genes involved in the nitrogen cycle of loamy soil

The increasing production and use of engineered silver nanoparticles (AgNP) in industry and private households are leading to increased concentrations of AgNP in the environment. An ecological risk assessment of AgNP is needed, but it requires understanding the long term effects of environmentally relevant concentrations of AgNP on the soil microbiome. Hence, the aim of this study was to reveal the long-term effects of AgNP on soil microorganisms. The study was conducted as a laboratory incubation experiment over a period of one year using a loamy soil and AgNP concentrations ranging from 0.01 to 1?mg?AgNP/kg soil. The short term effects of AgNP were, in general, limited. However, after one year of exposure to 0.01?mg?AgNP/kg, there were significant negative effects on soil microbial biomass (quantified by extractable DNA; p?=?0.000) and bacterial ammonia oxidizers (quantified by amoA gene copy numbers; p?=?0.009). Furthermore, the tested AgNP concentrations significantly decreased the soil microbial biomass, the leucine aminopeptidase activity (quantified by substrate turnover; p?=?0.014), and the abundance of nitrogen fixing microorganisms (quantified by nifH gene copy numbers; p?=?0.001). The results of the positive control with AgNO3 revealed predominantly stronger effects due to Ag⁺ ion release. Thus, the increasing toxicity of AgNP during the test period may reflect the long-term release of Ag⁺ ions. Nevertheless, even very low concentrations of AgNP caused disadvantages for the microbial soil community, especially for nitrogen cycling, and our results confirmed the risks of releasing AgNP into the environment.     

Robust magnetic laccase-mimicking nanozyme for oxidizing o-phenylenediamine and removing phenolic pollutants

In this study, we report a novel magnetic biomimetic nanozyme(Fe_3O_4@Cu/GMP(guanosine5′-monophosphate)) with high laccase-like activity, which could oxidize toxic ophenylenediamine(OPD) and remove phenolic compounds.The magnetic laccase-like nanozyme was readily obtained via complexed Cu~(2+)and GMP that grew on the surface of magnetic Fe_3O_4 nanoparticles.The prepared Fe_3O_4@Cu/GMP catalyst could be magnetically recycled for at least five cycles while still retaining above 70% activity.As a laccase mimic,Fe_3O_4@Cu/GMP had more activity and robust stability than natural laccase for the oxidization of OPD.Fe_3O_4@Cu/GMP retained about 90% residual activity at 90℃ and showed little change at pH 3–9, and the nanozyme kept its excellent activity after long-term storage.Meanwhile, Fe_3O_4@Cu/GMP had better activity for removing phenolic compounds, and the removal of naphthol was more than 95%.Consequently, the proposed Fe_3O_4@Cu/GMP nanozyme shows potential for use as a robust catalyst for applications in environmental remediation.     

Adsorption performance of CMK-3 and C-FDU-15 in NO removal at low temperature

CMK-3 and C-FDU-15 samples were synthesized using hard-templating and evaporationinduced self-assembly(EISA) methods,respectively.The pore structures of CMK-3 and CFDU-15 as well as commercial activated carbon were characterized by means of X-ray diffraction,field emission scanning electron microscopy,transmission electron microscopy,and N_2 adsorption–desorption.Adsorption of NO was investigated by means of thermogravimetric analysis,temperature-programmed desorption of NO + O_2,and in situ diffuse reflectance Fourier transform infrared spectroscopy.The results show that the CMK-3 and C-FDU-15 materials possessed ordered and uniform structures.The coadsorption capacity of NO and O_2 decreased in the sequence CMK-3(88.6 mg/g) C-FDU-15(71.7 mg/g) AC(25.3 mg/g).There were two main adsorption species on CMK-3 and CFDU-15:nitrite and nitrate.Nitrite is converted to nitrate easily.However,the adsorption species were more complex on AC,with nitrite being the main species.Moreover,CMK-3 and C-FDU-15 exhibit excellent regeneration efficiency compared with AC.The excellent NO adsorption performance of CMK-3 and C-FDU-15 was associated with their ordered mesoporous structures and high surface areas.The research provides more options for NO adsorption in the future.     

长期暴露下纳米TiO2对厌氧颗粒污泥体系稳定性的影响

以厌氧颗粒污泥为研究对象,通过静态试验和连续流厌氧反应器,重点研究了长期暴露下纳米TiO_2在对厌氧产甲烷体系的影响及其在颗粒污泥中的归趋.结果表明,短期急性暴露于150 mg·g-1(以VSS计)的纳米TiO_2尽管会暂时减缓产甲烷速率,但产酸阶段及产甲烷阶段代谢产物总量不会明显受到影响,纳米TiO_2对厌氧颗粒污泥具有较低的急性毒性.反应器运行结果表明,纳米TiO_2的长期暴露可导致挥发性脂肪酸(VFAs)积累及生物气产量降低,产酸菌比产甲烷菌对纳米TiO_2的累积效应更加敏感,纳米TiO_2抑制机制可归因于"物理遮蔽"作用.出水中TiO_2的平均含量只有0.632 mg·L~(-1),绝大多数纳米TiO_2都被截留在了反应器中.FISH检测表明,厌氧颗粒污泥微生物的菌群结构有所变化,纳米TiO_2在反应器内的积累使得甲烷八叠球菌的丰度大幅增加了115.6%,其优势地位明显增强.长短期暴露试验的结果对比也说明,用短期暴露试验来说明纳米颗粒对厌氧体系的长期累积效应具有一定局限性,纳米TiO_2对厌氧颗粒污泥中微生物的负面影响需要较长时间的积累才会显现.本研究结果可为厌氧污水处理体系中纳米颗粒的潜在生态风险评价提供理论支持和参考依据.     

植物对纳米颗粒的吸收、转运及毒性效应

随着工程纳米颗粒的广泛使用,这些纳米材料不可避免地进入环境,对环境造成未知影响.植物是高等生物暴露于纳米颗粒的一条主要途径,工程纳米颗粒可能通过食物链使其在高营养水平生物中积累.植物与纳米颗粒间的相互作用应该受到关注和重视.已有的文献表明纳米颗粒能被植物选择性地吸收并引起植物毒性,但纳米颗粒进入植物体内的机制仍不明确.多数关于植物吸收纳米颗粒的研究是在理想条件如水培实验下开展,并且集中在植物的种子发芽或是幼苗生长阶段.描述纳米颗粒在植物体内的生物转化和在植物体内分配的报道较少,而且这方面的机制没有阐述清楚.目前有许多研究者关注纳米颗粒的植物毒性效应,但这方面的研究需要进一步深入.     

有序介孔碳载金/L-赖氨酸/纳米金修饰电极的制备及其对邻苯二酚、对苯二酚的检测响应研究

通过化学还原的方法合成有序介孔碳负载纳米金粒子,并构筑有序介孔碳载金/L-赖氨酸/纳米金复合膜修饰玻碳电极;利用扫描电镜观察介孔碳和介孔碳复合膜的微观结构,并用循环伏安法、电化学阻抗谱表征自组装电极的过程.在此基础上用差分脉冲伏安法研究对苯二酚和邻苯二酚混合物在该电极上的电催化氧化,研制了一种基于有序介孔碳载金/L-赖氨酸/纳米金复合膜修饰电极分别检测对苯二酚和邻苯二酚的传感器.在最优的实验条件下,该传感器在对苯二酚和邻苯二酚浓度为1×10-6～8×10-4mol·L-1的范围内具有良好的线性关系,检出限分别为3×10-7mol·L-1、7×10-7mol·L-1.