氧化物载体对Ni-V催化剂催化燃烧二氯甲烷的影响

以Al₂O₃,TiO₂,ZrO₂ 3种氧化物为载体,通过溶胶凝胶法制备以Ni-V双金属氧化物为活性组分催化剂,在固定床反应器上研究了催化剂的二氯甲烷（DCM）催化燃烧性能.并通过XRD、BET、FTIR-Pyridine和H₂-TPR表征分析催化剂的物理化学特性,结果表明催化剂的氧化还原性能与酸性存在一定的协同能力促进DCM的催化氧化.10% Ni-V/Al₂O₃和10% Ni-V/TiO₂催化剂表面大量的酸性位点和强氧化性使得催化剂在催化燃烧DCM时拥有较好的活性,其中10% Ni-V/Al₂O₃在252℃时就有90%的转化率,但其在低温时易产生含氯有机副产物的CH₃Cl,并且50h连续稳定性测试发现其有失活现象.而10% Ni-V/TiO₂催化剂达到90%转化率时温度为274℃,且其在DCM降解中并没有CH₃Cl的产生,稳定性测试中也没有失活现象发生,这可能是与其拥有更多中强度B酸以及较强氧化还原能力有关.     

Removal of arsenic (V) from aqueous medium using manganese oxide coated lignocellulose/silica adsorbents

Arsenic (V) adsorption on manganese oxide coated rice wastes was investigated in this study. The modified adsorbents were characterized by Fourier-transform infrared spectroscopy, scanning electron microscopy, and pH measurements to determine the point of zero charge. Batch adsorption equilibrium experiments were conducted to study the effects of pH, contact time, and initial concentration on arsenic removal efficiency. The adsorption capacity of rice waste was significantly improved after modification with permanganate. The Langmuir isotherm model fitted the equilibrium data better than the Freundlich model which confirms surface homogeneity of the adsorbent. Maxima adsorption capacities are determined as 10 and 12 mg/g at pH 3 for manganese oxide coated rice husk and straw, respectively. The adsorption energy indicates that the adsorption process may be dominated by chemisorption. Pseudo-second-order rate equation described the kinetics sorption of arsenic with good correlation coefficients, better than a pseudo-first-order equation. Manganese oxide coated rice husk and straw appear to be promising low cost adsorbents for removing arsenic from water.     

氧化石墨烯存在下铜离子对大型溞的毒性研究

氧化石墨烯(graphene oxide,GO)作为一种具有独特物理化学性质的新型纳米材料被广泛应用,其进入环境后可能对传统污染物的毒性造成影响。选取大型溞为受试生物,研究了GO的存在对Cu在大型溞体内的富集、毒性和抗氧化系统的影响。结果表明,GO对Cu~(2+)具有良好的吸附效果,大幅降低了试验液中Cu~(2+)浓度。1 mg·L~(-1)和2 mg·L~(-1)GO存在下,大型溞暴露于19.2μg·L~(-1)Cu~(2+)溶液72 h后,体内的金属Cu富集量由360μg·g-1干重分别降低为308μg·g-1和215μg·g-1干重。GO的存在降低了Cu~(2+)对大型溞的毒性,Cu~(2+)对大型溞的72 h-LC50值由19.2μg·L~(-1)升高至56μg·L~(-1)。Cu~(2+)单独作用时,大型溞体内SOD活性和GSH含量表现为先诱导后抑制,而MDA含量逐渐升高;当GO存在时,大型溞体内酶活性的变化趋势与上述现象类似,但含量总体低于Cu~(2+)单独暴露时的活性和含量。研究表明GO的加入减少了大型溞体内Cu的富集量,降低了Cu~(2+)对大型溞的氧化损害,对Cu~(2+)的毒性存在一定的减轻效果。     

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.     

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.