新型纳米结构铈锰复合氧化物的磷吸附行为与机制研究

采用共沉淀法制备了一种新型铈锰复合氧化物吸附剂,对其进行了表征,并对磷吸附行为与机制进行了研究.表征结果分析表明,此氧化物由纳米级颗粒组成;铈锰复合氧化物中的铈氧化物有类似水合氧化铈的无定形结构;BET比表面积为157 m2·g-1,等电点为6.5.吸附实验结果表明,Langmuir吸附等温线模型可以更好地拟合铈锰复合氧化物对磷的吸附,最大吸附量为28.6 mg·g-1(p H=7.0);铈锰复合氧化物对磷具有较高的吸附速率,更符合准二级动力学模型;溶液p H对铈锰复合氧化物吸附磷的影响较为明显,随p H升高,吸附量降低;离子强度则影响不大;共存阴离子对吸附影响的大小顺序为Si O2-3CO2-3Cl-≥SO2-4.通过对铈锰复合氧化物吸附磷前后Zeta电位和红外谱图(FTIR)分析,可以推断磷在铈锰复合氧化物表面发生了特性吸附,磷酸根主要通过取代复合氧化物表面的金属羟基而被吸附去除.     

Cu–Mn–Ce ternary mixed-oxide catalysts for catalytic combustion of toluene

Cu–Mn, Cu–Mn–Ce, and Cu–Ce mixed-oxide catalysts were prepared by a citric acid sol–gel method and then characterized by XRD, BET, H₂-TPR and XPS analyses. Their catalytic properties were investigated in the toluene combustion reaction. Results showed that the Cu–Mn–Ce ternary mixed-oxide catalyst with 1:2:4 mole ratios had the highest catalytic activity, and 99% toluene conversion was achieved at temperatures below 220°C. In the Cu–Mn–Ce catalyst, a portion of Cu and Mn species entered into the CeO₂ fluorite lattice, which led to the formation of a ceria-based solid solution. Excess Cu and Mn oxides existed on the surface of the ceria-based solid solution. The coexistence of Cu–Mn mixed oxides and the ceria-based solid solution resulted in a better synergetic interaction than the Cu–Mn and Cu–Ce catalysts, which promoted catalyst reducibility, increased oxygen mobility, and enhanced the formation of abundant active oxygen species.     

长期暴露下纳米二氧化钛对典型淡水藻体砷累积与生物转化的影响

以铜绿微囊藻(Microcystis aeruginosa)和斜生栅藻(Scenedesmus obliquus)为研究对象,通过室内培养实验,研究了长期暴露下纳米二氧化钛(nano-TiO_2)对五价砷[As(Ⅴ)]在典型淡水藻体中累积与生物转化的影响.结果表明不同藻类对无机砷的吸收和转化能力差异很大.长期暴露下斜生栅藻累积的砷(As,以DW计,下同)高达(819.66±11.25)μg·g-1,比铜绿微囊藻累积的As[(355.95±8.31)μg·g-1]高2倍多.Nano-TiO_2可增加藻体对As的吸收累积,降低了培养基中As的含量.同时,nano-TiO_2可增加藻体对As(Ⅴ)的生化转化;其中,铜绿微囊藻中有机砷以二甲基砷(DMA)为主,而斜生栅藻中有机砷以一甲基砷(MMA)为主.另外,长期暴露下nano-TiO_2处理的铜绿微囊藻和斜生栅藻向培养基释放的甲基砷小于对照组,表明长期暴露中的nano-TiO_2不能促进藻体内甲基砷的释放.研究结果可促进nano-TiO_2与As相互作用时生态风险的理解.     

磁性氮掺石墨烯活化过硫酸钾降解水中亚甲基蓝

活化过硫酸盐产生硫酸根自由基的高级氧化技术在水环境污染物治理中引起了广泛的关注和研究.本研究采用水热法制备磁性氮掺石墨烯(M-N-G)作为催化剂.利用SEM、BET、XRD和VSM等手段表征材料,系统研究了该材料活化过硫酸盐降解亚甲基蓝的效能.结果表明:M-N-G的比表面积为94.35 m2·g-1,磁性Fe3O4分布在材料表面,能有效的活化过硫酸钾降解亚甲基蓝.当催化剂的用量为200 mg·L~(-1),过硫酸钾浓度为0.4~0.5 mmol·L~(-1)时,在p H=3~6时对10 mg·L~(-1)亚甲基蓝的降解率达90%以上.体系温度在15~32℃时,降解速率常数在0.0227~0.0488 min-1,反应活化能为33.7 k J·mol-1.EPR分析及自由基漼灭实验证明了体系中有羟基自由基和硫酸根自由基产生.TOC分析结果表明:TOC去除率可达50%.M-N-G经过简单的稀硫酸和水洗后,可高效重复利用4次.该技术方法简单、高效、无二次污染,能为有机污染物废水处理提供一种新的方法选择.     

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.     

Managing a forgotten greenhouse gas under existing U.S. law: An interdisciplinary analysis

The United States’ legal strategy for addressing climate change in recent years has relied on authority from existing legislation. This has led to measures on a number of different greenhouse gases, notably carbon dioxide, methane and hydrofluorocarbons. However, one greenhouse gas has been largely forgotten: nitrous oxide. Nitrous oxide is the third most abundantly emitted greenhouse gas in the U.S. and worldwide, as well as the largest remaining threat to the stratospheric ozone layer. In addition, the nitrogen atoms in nitrous oxide are part of the highly fluid nitrogen cycle where nitrogen atoms transform readily among different chemical forms, each with a unique environmental and human health impact – a process known as the nitrogen cascade. While the science of the nitrogen cascade has been explored for over a decade, there has been little work on the legal implications of this phenomenon. And yet the nitrogen cascade expands the legal options available for controlling nitrous oxide. This paper studies these options in a U.S. context and explores the environmental and economic impacts of enacting them. We determine that the Clean Air Act, and in particular its broad authority for controlling ozone depleting substances, is the most promising legal pathway for regulating nitrous oxide across all major sources. Invoking such authority could generate significant climate and stratospheric ozone benefits over 2015–2030, equivalent to taking 12 million cars permanently off the road, and 100 million chlorofluorocarbon-laden refrigerators out of service. The economic benefits could sum to over $700 billion over 2015–2030, with every $1.00 spent on abating emissions leading to $4.10 in societal benefits. The bulk of these benefits would come from reductions in other forms of nitrogen pollution such as ammonia and nitrate, highlighting the important and multiple co-benefits that could be achieved by abating nitrous oxide emissions. With the Paris Climate Agreement calling for limiting global temperature increases to “well below” two degrees Celsius, all mitigation opportunities across all sectors need to be considered. This paper suggests that nitrous oxide warrants more attention from policy-makers in the U.S. and around the world.     

Remarkable promotion effect of trace sulfation on OMS-2 nanorod catalysts for the catalytic combustion of ethanol

OMS-2 nanorod catalysts were synthesized by a hydrothermal redox reaction method using MnSO₄ (OMS-2-SO₄) and Mn(CH₃COO)₂ (OMS-2-AC) as precursors. SO₄^2 −-doped OMS-2-AC catalysts with different SO₄^2 − concentrations were prepared next by adding (NH₄)₂SO₄ solution into OMS-2-AC samples to investigate the effect of the anion SO₄^2 − on the OMS-2-AC catalyst. All catalysts were then tested for the catalytic oxidation of ethanol. The OMS-2-SO₄ catalyst synthesized demonstrated much better activity than OMS-2-AC. The SO₄^2 − doping greatly influenced the activity of the OMS-2-AC catalyst, with a dramatic promotion of activity for suitable concentration of SO₄^2 − (SO₄/catalyst = 0.5% W/W). The samples were characterized by X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), inductively coupled plasma optical emission spectroscopy (ICP-OES), NH₃-TPD and H₂-TPR techniques. The results showed that the presence of a suitable amount of SO₄^2 − species in the OMS-2-AC catalyst could decrease the Mn–O bond strength and also enhance the lattice oxygen and acid site concentrations, which then effectively promoted the catalytic activity of OMS-2-AC toward ethanol oxidation. Thus it was confirmed that the better catalytic performance of OMS-2-SO₄ compared to OMS-2-AC is due to the presence of some residual SO₄^2 − species in OMS-2-SO₄ samples.     

一氧化氮合酶途径参与SO_2胁迫下蚕豆气孔运动调节

以蚕豆为材料,研究一氧化氮合酶(NOS)途径在SO2诱发气孔运动中的作用.研究发现:浓度7.5~200μmol·L-1的SO2衍生物处理后,蚕豆叶面气孔开度减小,气孔开度与SO2衍生物浓度呈负相关;SO2衍生物处理组叶组织中NOS活性增强;加入NO清除剂c-PTIO或NOS抑制剂L-NAME可抑制SO2衍生物诱发的气孔关闭;SO2衍生物处理组保卫细胞内NO和Ca2+水平升高,用c-PTIO降低胞内NO水平后Ca2+水平随之下降.结果表明,SO2衍生物胁迫可诱发保卫细胞内NO合成增加,NO通过调节胞内Ca2+水平升高,激活下游信号转导途径,调节气孔运动;NOS途径介导的NO合成参与了SO2胁迫下蚕豆气孔运动的调节.     

氧化石墨烯对亚甲基蓝和铜离子的共吸附行为研究

氧化石墨烯(GO)具有高比表面积和丰富的含氧官能团,表面存在着大量的吸附点位,被认为是去除水体污染物的高效吸附剂,而其在有机物-重金属复合污染环境中的吸附行为却鲜有报道.因此,本文采用改良Hummers法制备出GO,通过扫描电镜(SEM)、透射电镜(TEM)、红外光谱(FTIR)、拉曼光谱(Raman)和X射线衍射(XRD)等物理表征方法对GO的形貌结构和表面官能团进行了表征.随后,侧重研究了GO对有机物及重金属污染物的单独和共吸附行为,选取亚甲基蓝(MB)与Cu(Ⅱ)作为复合污染水体的特征污染物,探讨了不同浓度Cu(Ⅱ)对MB及不同浓度MB对Cu(Ⅱ)的吸附性能的影响.结果表明,不同类型的污染物单独存在时,GO对MB和Cu(Ⅱ)的吸附量分别为29.13和424.16mg·g-1;而当上述两种污染物共存时,GO对MB和Cu(Ⅱ)的吸附性能均明显下降,这说明MB与Cu(Ⅱ)在GO表面的吸附点位存在着竞争吸附关系,并且MB对Cu(Ⅱ)吸附的抑制作用明显高于Cu(Ⅱ)对MB吸附的影响.     

Water chemistry controlled aggregation and photo-transformation of silver nanoparticles in environmental waters

The inevitable release of engineered silver nanoparticles (AgNPs) into aquatic environments has drawn great concerns about its environmental toxicity and safety. Although aggregation and transformation play crucial roles in the transport and toxicity of AgNPs, how the water chemistry of environmental waters influences the aggregation and transformation of engineered AgNPs is still not well understood. In this study, the aggregation of polyvinylpyrrolidone (PVP) coated AgNPs was investigated in eight typical environmental water samples (with different ionic strengths, hardness, and dissolved organic matter (DOM) concentrations) by using UV–visible spectroscopy and dynamic light scattering. Raman spectroscopy was applied to probe the interaction of DOM with the surface of AgNPs. Further, the photo-transformation and morphology changes of AgNPs in environmental waters were studied by UV–visible spectroscopy, inductively coupled plasma mass spectrometry, and transmission electron microscopy. The results suggested that both electrolytes (especially Ca^2 + and Mg^2 +) and DOM in the surface waters are key parameters for AgNP aggregation, and sunlight could accelerate the morphology change, aggregation, and further sedimentation of AgNPs. This water chemistry controlled aggregation and photo-transformation should have significant environmental impacts on the transport and toxicity of AgNPs in the aquatic environments.