石墨烯/二氧化钛降解亚甲基蓝的研究

以钛酸丁酯和氧化石墨烯为前驱物,通过水热法制备石墨烯/二氧化钛(GR/TiO2)复合光催化剂。采用XRD、TEM和FT-IR等技术手段对GR/TiO2粉体的结构和形貌进行了表征。利用对亚甲基蓝光催化降解,考察了GR/TiO2的光催化降解能力,并研究了H2O2用量和p H等因素对光催化降解速率的影响。结果表明:复合催化剂中,TiO2为锐钛型晶体,粒径为25 nm左右,分散在薄纱状的石墨烯上;复合催化剂通过紫外光下光催化性能有所提高,对可见光产生响应,具有良好的稳定性;加入适量H2O2能提高反应速率,碱性条件下,对亚甲基蓝的降解效率更高。     

Comparing the adsorption behaviors of Cd,Cu and Pb from water onto Fe-Mn binary oxide,MnO2 and FeOOH

The adsorption potential of FMBO, FeOOH, MnO₂ for the removal of Cd²⁺, Cu²⁺ and Pb²⁺ in aqueous systems was investigated in this study. Comparing to FMBO and FeOOH, MnO₂ offered a much higher removal capacity towards the three metal ions. The maximal adsorption capacity of MnO₂ for Cd²⁺, Cu²⁺ and Pb²⁺ were 1.23, 2.25 and 2.60 mmol·g^-1, respectively. And that for FMBO were 0.37, 1.13, and 1.18 mmol·g^-1 and for FeOOH were 0.11, 0.86 and 0.48 mmol·g^-1, respectively. The adsorption behaviors of the three metal ions on the three adsorbents were all significantly affected by pH values and heavy metal removal efficiency increased with pH increased. The Langmuir and Freundlich adsorption models were used to describe the adsorption equilibrium of the three metal ions onto the three adsorbents. Results showed that the adsorption equilibrium data fitted well to Langmuir isotherm and this indicated that adsorption of metal ions occurred on the three metal oxides adsorbents limited to the formation of a monolayer. More negative charged of MnO₂ surface than that of FMBO and FeOOH could be ascribed by lower pH_iep of MnO₂ than that of FMBO and FeOOH and this could contribute to more binding sites on MnO₂ surface than that of FMBO and FeOOH. The higher metal ions uptake by MnO₂ than FMBO and FeOOH could be well explained by the surface charge mechanism.     

Ecotoxicological effect of zinc oxide nanoparticles on soil microorganisms

The widespread production and use of zinc oxide nanoparticles (ZnO-NPs) in recent years have posed potential threat to the ecosystem. This study aimed to investigate the ecotoxicological effect of ZnO-NPs on soil microorganisms using laboratory microcosm test. Respiration, ammonification, dehydrogenase (DH) activity, and fluorescent diacetate hydrolase (FDAH) activity were used as ecotoxicological parameters. The results showed that in the neutral soil treated with 1 mg ZnO-NPs per g soil (fresh, neutral), ammonification was significantly inhibited during the study period of three months, but the inhibition rate decreased over increasing time. Inhibition in respiration was observed in the first month of the test. In various ZnO-NPs treatments (1 mg, 5 mg, and 10 mg ZnO-NPs per g soil), DH activity and FDAH activity were inhibited during the study period of one month. For both enzyme activities, there were positive dose–response relationships between the concentration of ZnO-NPs and the inhibition rates, but the curves changed over time due to changes of ZnO-NPs toxicity. Soil type affected the toxicity of ZnO-NPs in soil. The toxicity was highest in the acid soil, followed by the neutral soil. The toxicity was relatively low in the alkaline soil. The toxicity was not accounted for by the Zn²⁺ released from the ZnO-NPs. Direct interaction of ZnO-NPs with biologic targets might be one of the reasons. The adverse effect of ZnO-NPs on soil microorganisms in neutral and acid soils is worthy of attention.     

不同培养介质中纳米氧化铜对小麦毒性的影响

采用琼脂培养和水培方法比较了纳米氧化铜(CuONPs)在不同暴露介质中的环境化学行为及其对小麦根生长的影响,并探讨了不同培养介质对CuONPs植物毒性的影响机制.结果表明,琼脂介质相对水相(营养液)环境可以减少CuONPs的团聚,增强其分散性.在琼脂和水相中Cu离子溶出随CuONPs浓度变化规律存在明显差异,在50～1000mg CuONPs·L-(1以Cu计)范围内,CuONPs在琼脂中无论是Cu2+的溶出浓度还是溶出比率均低于其在水相中的值.CuONPs在不同介质中表现出显著的小麦毒性差异.琼脂培养下小麦根生长半抑制效应浓度EC50(以CuONPs浓度表示)为108mg·L-1,而在水培方式下为9.0mg·L-1,说明琼脂介质极大缓解了CuONPs引起的植物毒性.分析表明,Cu2+溶出浓度较CuONPs投放量与小麦根生长抑制效应之间存在更好的指数相关关系,这说明该研究体系下CuONPs小麦毒性主要是由纳米颗粒释放Cu2+引起的.此结论较好地解释了当培养介质从水相变成琼脂时,Cu2+溶出减少,纳米毒性降低的现象.该研究结果认为,当前国内外使用水培法获得的纳米材料植物毒性研究结果在外推至实际土壤状况时将高估其环境安全性风险,推荐使用琼脂作为纳米材料土壤环境风险评价的模拟介质.     

超低排放背景下煤电机组氨管控存在的问题及对策探析

近年来,我国大气污染防治成效显著,煤电机组超低排放政策实施对此做出了突出贡献。氮氧化物是煤电机组超低排放中的重要控制指标之一。然而,受现有氮氧化物排放监测和喷氨控制技术的精度、反馈时效等因素的限制,为提高脱硝效率保证性,电厂在实际运行中存在过量喷氨现象,未完全反应的氨进入大气后可能造成二次颗粒物增加。针对这一现象,本文回顾了我国火电行业氮氧化物排放标准和治理措施的演化及实施效果,对煤电机组氨排放现状和存在的问题进行了深入分析,提出在推进氮氧化物超低排放过程中应开展脱硝过量喷氨现状调研,鼓励企业开展脱硝系统优化,加强复杂烟气环境下氨监测技术研发,完善脱硝氨逃逸日常环境监管,推动氨排放全生命周期转化规律基础研究和大气环境效应评估,进一步提升煤电机组超低排放政策实施的综合环境效益,也对其他行业超低排放政策推进起到示范作用。     

氧化石墨烯-多壁碳纳米管低压膜抗污染性能研究

为提高碳纳米材料低压膜污染的可恢复性和强化其灭菌效果,本研究将氧化石墨烯(Graphene oxide,GO)与聚乙二醇(Polyethylene glycol,PEG)非共价改性后的多壁碳纳米管(Multi-walled carbon nanotube,MWCNT)以两种结构形式(共混式/嵌入式)负载到0.45 μm聚醚砜片式膜表面,制备了共混式/嵌入式GO-MWCNT低压膜.进而研究了GO-MWCNT不同结构形式对处理典型污染物(牛血清蛋白、腐殖酸、海藻酸钠)过程中膜污染情况的影响.实验结果显示,MWCNT中GO的添加,可使碳纳米材料膜孔径分布更集中,纯水通量在2.011 L·m^-2·h^-1·kPa^-1以上,属于低压膜的运行范围.在处理小尺寸牛血清蛋白的膜滤过程中,采用共混结构(M系列)的GO-MWCNT膜,缓解污染效果优于顶层嵌入结构(I系列);在处理较大尺寸的腐殖酸、海藻酸钠的膜滤过程中,采用顶层嵌入结构(I系列)的GO-MWCNT膜,缓解污染效果优于共混结构(M系列).GO的添加使得碳纳米材料低压膜的抗蛋白质黏附性能得到有效提高,在保证膜表面粗糙度不会大幅度提高的前提下,添加0.2 mg GO的抗蛋白黏附效果优于添加0.5 mg GO.共混式/嵌入式GO-MWCNT膜均可以充分发挥GO边缘切割杀菌作用,GO投加量与灭菌性能呈正相关.其中,共混结构(M系列)的GO-MWCNT膜灭菌效果优于顶层嵌入结构(I系列).     

不同铁氧化物对小麦幼苗镉积累的影响

小麦富镉（Cd）问题受到广泛关注,铁氧化物具备降镉潜力.通过盆栽小麦幼苗实验,分析了三氧化二铁（Fe₂O₃）、氢氧化铁[Fe（OH）₃]及拜耳法赤泥（B-RM）3种铁氧化物的降镉能力.结果显示3种铁氧化物中,Fe（OH）₃可显著降低小麦幼苗茎叶Cd含量,与对照相比降幅为16.3%~27.7%,投加量为0.5%时降Cd效果最优.Fe（OH）₃能够显著降低小麦幼苗根部向茎叶的Cd转运,投加量为10%时富集系数及转运系数最低.小麦幼苗根际土壤Fe/Cd、Cu/Cd及Zn/Cd是影响小麦幼苗茎叶Cd积累的关键因子,当Fe/Cd>25000、Cu/Cd > 50或Zn/Cd > 100时,根际土壤元素比与茎叶镉含量呈显著负相关.该比值的确定对于大田应用中钝化剂材料投加量的确定具有指导意义.     

中国农业源甲烷和氧化亚氮排放的影响因素

基于清单方法对中国的甲烷（CH₄）及氧化亚氮（N₂O）等农业源非二氧化碳（CO₂）温室气体（GHG）排放情况进行核算研究,通过引入Tapio弹性脱钩理论和对数平均迪氏指数（LMDI）方法研究了中国农业源CH₄和N₂O排放的影响因素.结果表明：①1980—2018年中国农业源CH₄和N₂O排放量由0.56×10⁹ t CO₂-eq上升至0.73×10⁹ t CO₂-eq;②1980—2018年中国农业源CH₄和N₂O排放随着农业总产值增长而缓慢增加,整体呈弱脱钩状态,但其脱钩状态稳定性较差;③从LMDI因素分解角度看,经济因素和人口规模因素对中国农业源CH₄和N₂O排放呈正效应,经济因素影响最大;效率因素和结构因素均对中国农业源CH₄和N₂O排放有减缓作用,其中,效率因素为主要抑制因素;④结构因素、效率因素和人口规模因素对脱钩努力的影响程度为效率因素>结构因素>人口规模因素.     

Hydrophilic/underwater superoleophobic graphene oxide membrane intercalated by TiO2 nanotubes for oil/water separation

GO/TiO₂ membrane was prepared by assembling GO nanosheets and TiO₂ nanotubes. The intercalation of TiO₂ nanotubes enlarged the space of GO interlayers and modified the surface morphology. Hydrophilic/underwater superoleophobic property of GO/TiO₂ membrane was obtained. Water permeability, hydrophilicity, oleophobicity and antifouling ability of GO-based membrane were all enhanced by intercalating TiO₂ nontubes. Membrane technology for oil/water separation has received increasing attention in recent years. In this study, the hydrophilic/underwater superoleophobic membrane with enhanced water permeability and antifouling ability were fabricated by synergistically assembling graphene oxide(GO) nanosheets and titanium dioxide (TiO₂) nanotubes for oil/water separation. GO/TiO₂ membrane exhibits hydrophilic and underwater superoleophobic properties with water contact angle of 62° and under water oil contact angle of 162.8°. GO/TiO₂ membrane shows greater water permeability with the water flux up to 531 L/(m²·h·bar), which was more than 5 times that of the pristine GO membrane. Moreover, GO/TiO₂membrane had excellent oil/water separation efficiency and anti-oil-fouling capability, as oil residual in filtrate after separation was below 5 mg/L and flux recovery ratios were over 80%.The results indicate that the intercalation of TiO₂ nanotubes into adjacent GO nanosheets enlarged the channel structure and modified surface topography of the obtained GO/TiO₂ membranes, which improved the hydrophilicity, permeability and anti-oil-fouling ability of the membranes, enlightening the great prospects of GO/TiO₂ membrane in oil-water treatment.     

催化脱除氮氧化物研究进展

消除氮氧化物污染是环境保护中的一项重要课题。催化脱除氮氧化物一直是人们解决上述课题应用的主要方法。本文对催化脱除法中应用的各种催化剂的研究进展状况作一回顾和总结