石墨烯材料去除重金属及放射性核素的研究

石墨烯及其改性材料具有比表面积大、吸附能力强、抗辐射性能好、耐高温、耐酸碱等优点,近年来在去除重金属和放射性核素领域得到了广泛关注.本文简要介绍了石墨烯的合成及改性方法,综述了石墨烯材料去除水中重金属离子和放射性核素的研究进展,包括吸附容量、影响因素、吸附动力学、吸附热力学模型和吸附机理,分析了该研究领域目前存在的问题,探讨了今后的研究方向.     

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.     

磺化石墨烯对小麦幼苗生长及生理生化指标的影响

随着石墨烯生产量和使用量的不断增大,其对生态环境的风险逐渐引起了环境学家的关注。采用水培试验,探究了磺化石墨烯(SGO)对小麦幼苗的生长、抗氧化酶活性及脂质过氧化的影响。结果表明:在培养10 d后,低浓度磺化石墨烯对小麦根系的生长有显著促进作用(P0.05),200 mg·L-1浓度处理与对照处理相比提高了84.3%,随着浓度增加促进作用逐渐减弱,1 000 mg·L-1时与对照相比提高了19.9%。但对小麦地上部的生长没有影响。磺化石墨烯处理的小麦幼苗根系和叶片组织中超氧化物歧化酶(SOD)、过氧化氢酶(CAT)、过氧化物酶(POD)及丙二醛(MDA)都呈现先下降后上升的趋势。当磺化石墨烯浓度低于200 mg·L-1时,处理组小麦抗氧化酶的活性及MDA含量相对于对照处理大都有所降低,说明低浓度时磺化石墨烯没有对小麦的生长产生氧化胁迫,这与磺化石墨烯可能具有一定的抗氧化能力有关,而高浓度时由于产生氧化胁迫使各项生理生化指标逐渐上升。本实验结果为石墨烯材料对植物的毒理学研究提供了基础数据。     

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.     

化肥减量配施秸秆对双季稻田固氮微生物群落的影响

基于3 a田间定位试验,研究了双季稻田化肥减量配施秸秆后第3 a对水稻产量、土壤肥力属性和固氮微生物群落结构特征的影响.设置了3种施肥模式：常规施化肥（CF）、化肥减量配施3 t ·hm^-2干重秸秆（CFLS）和化肥减量配施6 t ·hm^-2干重秸秆（CFHS）.结果表明,在化肥减量配施秸秆后第3 a,CFLS和CFHS在没有显著减少水稻籽粒产量（P>0.05）的情况下显著中和土壤酸化并提高土壤微生物量碳和氮、可溶性有机碳和有机碳含量（P<0.05）,同时显著减少了土壤氧化还原电位、铵态氮和硝态氮含量（P<0.05）,更有利于提高土壤氮素利用率.与CF处理相比,CFLS和CFHS的天然固氮功能群由于土壤碳储量增加和酸化程度降低等条件的改善而增加了Shannon、PD和Evenness指数（P<0.05）.化肥减量配施秸秆使Ferrigenium、硫氧化菌属（Sulfurivermis）、甲基单胞菌属（Methylomonas）、Methylovulum、外硫红螺菌属（Ectothiorhodospira）和念珠藻属（Nostoc）等固氮、固碳和植物促生功能微生物类群相对丰度显著提高（P<0.05）.综上所述,化肥减量配施3 t ·hm^-2和6 t ·hm^-2秸秆是改善土壤固氮微生物群落结构和提高土壤固氮潜力的有效措施.     

Responses of a soil bacterium, Pseudomonas chlororaphis O6 to commercial metal oxide nanoparticles compared with responses to metal ions

The toxicity of commercially-available CuO and ZnO nanoparticles (NPs) to pathogenic bacteria was compared for a beneficial rhizosphere isolate, Pseudomonas chlororaphis O6. The NPs aggregated, released ions to different extents under the conditions used for bacterial exposure, and associated with bacterial cell surface. Bacterial surface charge was neutralized by NPs, dependent on pH. The CuO NPs were more toxic than the ZnO NPs. The negative surface charge on colloids of extracellular polymeric substances (EPS) was reduced by Cu ions but not by CuO NPs; the EPS protected cells from CuO NPs-toxicity. CuO NPs-toxicity was eliminated by a Cu ion chelator, suggesting that ion release was involved. Neither NPs released alkaline phosphatase from the cells’ periplasm, indicating minimal outer membrane damage. Accumulation of intracellular reactive oxygen species was correlated with CuO NPs lethality. Environmental deposition of NPs could create niches for ion release, with impacts on susceptible soil microbes.