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.     

土壤及铁锰结核中锰氧化菌的氧化特性分析

利用从土壤铁锰结核及其附近土壤中分离筛选得到的4株锰氧化菌,研究了不同pH、Mn(Ⅱ)初始浓度下菌株的锰氧化效率及生长情况,并用SEM-EDS及TEM对菌株WHS26、GY16形成的生物氧化锰及水羟锰矿进行了表征.结果表明,pH及Mn(Ⅱ)初始浓度对菌株的锰氧化效率均有影响,4株菌在pH 7~8、Mn(Ⅱ)初始浓度为10~20 mmol·L-1时,锰氧化效率最高;GY16、WHS26形成的生物氧化锰的形貌与化学合成的水羟锰矿存在明显差异,前者呈胶膜状附着在菌株表面,后者呈结晶态.该结果可为生物氧化锰应用于重金属污染修复提供技术支撑.     

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.     

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.     

Methane and nitrous oxide emissions from a subtropical coastal embayment (Moreton Bay, Australia)

Surface water methane (CH₄) and nitrous oxide (N₂O) concentrations and fluxes were investigated in two subtropical coastal embayments (Bramble Bay and Deception Bay, which are part of the greater Moreton Bay, Australia). Measurements were done at 23 stations in seven campaigns covering different seasons during 2010-2012. Water-air fluxes were estimated using the Thin Boundary Layer approach with a combination of wind and currents-based models for the estimation of the gas transfer velocities. The two bays were strong sources of both CH₄ and N₂O with no significant differences in the degree of saturation of both gases between them during all measurement campaigns. Both CH₄ and N₂O concentrations had strong temporal but minimal spatial variability in both bays. During the seven seasons, CH₄ varied between 500% and 4000% saturation while N₂O varied between 128 and 255% in the two bays. Average seasonal CH₄ fluxes for the two bays varied between 0.5 ± 0.2 and 6.0 ± 1.5 mg CH₄/(m²·day) while N₂O varied between 0.4 ± 0.1 and 1.6 ± 0.6 mg N₂O/(m²·day). Weighted emissions (t CO₂-e) were 63%-90% N₂O dominated implying that a reduction in N₂O inputs and/or nitrogen availability in the bays may significantly reduce the bays' greenhouse gas (GHG) budget. Emissions data for tropical and subtropical systems is still scarce. This work found subtropical bays to be significant aquatic sources of both CH₄ and N₂O and puts the estimated fluxes into the global context with measurements done from other climatic regions.     

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.     

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.     

河流氧化亚氮产生和排放研究综述

氧化亚氮(N2O)是仅次于二氧化碳(CO2)和甲烷(CH4)的重要温室气体.由于人类活动对土地的影响导致河流系统中氮的可利用性增加,河流生态系统的N2O排放量正日益增长.本文对国内外河流水体N2O溶存浓度和饱和度、水-气界面排放通量及沉积物-水界面交换通量等数据进行了收集,并总结和分析了河流生态系统中N2O的产生机制及主要影响因子.     

天津市滨海河流N2O扩散通量及控制因子

河流是大气温室气体重要的排放源.为了探讨天津市典型景观滨海河流N₂O释放空间特征及影响因素,以天津市6条不同土地利用类型的滨海河流为研究对象,通过顶空-气相色谱法测定了N₂O浓度、饱和度和扩散通量.结果表明,天津市不同景观河流N₂O浓度都处于过饱和状态,表现为大气N₂O的源;N₂O浓度、饱和度和扩散通量均值为（23.85±15.20）nmol·L^-1、（309.71±197.38）%和（27.04±16.46）μmol·（m²·d）^-1,范围分别为12.70～115.69 nmol·L^-1、 164%～1 502%和9.17～244.79μmol·（m²·d）^-1.天津市不同土地利用类型河流N₂O浓度和扩散通量具有较大的空间异质性,表现为：排污河>城市河流>郊区河流>农业河流.天津滨海河流N₂     

纳米氧化锌对大型溞肠道组织毒性效应及机理研究

研究了不同浓度纳米氧化锌（ZnONP）及其在水中释放的对应浓度的Zn²⁺溶液对大型溞（Daphnia magna）肠道组织显微和亚显微结构的影响,探讨了ZnONP对大型溞的肠道组织毒性效应特征和作用机理.结果表明,0.3 mg·L^-1-Zn²⁺组（Zn²⁺浓度0.170 mg·L^-1）和0.3 mg·L^-1 ZnONP溶液皆对大型溞的肠道造成损伤,主要导致大型溞中肠与直肠之间的连接处发生扭曲,其中ZnONP对肠道组织结构弯曲影响最为明显,0.3 mg·L^-1 ZnONP组引起大型溞个体最大肠道弯曲率高达42%.大型溞肠道组织HE染色结果显示,ZnONP暴露会造成大型溞肠道上皮组织断裂、胞间连接空泡化、纹状缘模糊及杯状细胞脱落等,而相对应浓度Zn²⁺组的毒性较弱.电子显微镜下对大型溞肠道组织亚显微结构观察发现,0.3 mg·L^-1 ZnONP处理组大型溞肠道上皮细胞组织出现微绒毛排列紊乱、脱落、溶解,上皮细胞松散,线粒体双层膜结构不完整,嵴溶解消失,核糖体增多等现象.0.3 mg·L^-1-Zn²⁺组大型溞肠道组织上皮细胞有损伤,但整体结构基本完整.从ZnONP和对应的Zn²⁺所产生的毒性效应特征和各组大型溞机体中Zn元素含量的测定分析,ZnONP对大型溞造成的肠道组织损伤不仅与其释放的Zn²⁺引起的毒性有关,更可能与大型溞对颗粒物摄取的方式或ZnONP在体内的积累量、排泄速率和作用的细胞器等有关.因此,ZnONP对肠道组织毒性效应产生的分子机制还需要 进一步研究.