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.     

Oxidation of Cr(III) on birnessite surfaces: The effect of goethite and kaolinite

Oxidation of Cr(III) by manganese oxides may pose a potential threat to environments due to the formation of toxic Cr(VI) species. At present, it was still unclear whether the extent of Cr(III) oxidation and fate of Cr(VI) would be changed when manganese oxides co-exist with other minerals, the case commonly occurring in soils. This study investigated the influence of goethite and kaolinite on Cr(III) oxidation by birnessite under acidic pH condition (pH 3.5) and background electrolyte of 0.01 mol/L NaCl. Goethite was found not to affect Cr(III) oxidation, which was interpreted as the result of overwhelming adsorption of cationic Cr(III) onto the negatively-charged birnessite (point of zero charge (PZC) < 3.0) rather than the positively-charged goethite (PZC = 8.8). However, more Cr(VI) would be retained by the surface with the increase in addition of goethite because of its strong ability on adsorption of Cr(VI) at low pH. Moreover, either Cr(III) oxidation or distribution of the generated Cr(VI) between the solid and solution phases was not affected by kaolinite (PZC < 3.0), indicating its low affinity for Cr species. Reactions occurring in the present mixed systems were suggested, which could be partly representative of those in the soils and further indicates that the mobility and risk of Cr(VI) would be decreased if goethite was present.     

富里酸在土壤环境中的吸附研究

富里酸在土壤中的吸附影响着土壤肥力和土壤环境,本文比较了不同pH、离子强度下,富里酸对土壤环境吸附性能的影响,探究了高岭土对富里酸的吸附条件.结果表明吸附在高岭土上的富里酸可以改变高岭土的结构,与高岭土空白样相比,复合体的结构更加分散.高岭土的不同组分对富里酸的吸附容量不同,对富里酸不同官能团的亲和性也存在明显差异.富里酸在高岭土上的吸附及有机污染物在土壤环境中的吸附作用,与烷基、芳香基团呈正相关.     

外源有机酸添加对风化煤矸石污染释放及重金属有效性的影响

为评价不同类型有机酸对风化煤矸石污染释放的影响,通过在风化煤矸石中添加不同种类的外源有机酸(腐殖酸、柠檬酸、草酸、水杨酸)进行处理,分析稳定7d后煤矸石浸出液的特征污染组分及TCLP提取态重金属含量。结果表明:对照处理组的风化煤矸石浸出液具有典型的酸性矿山废水特征。添加少量柠檬酸、草酸和水杨酸能显著(p0.05)降低风化煤矸石浸出液的pH和Eh值、明显增加浸出液的盐度、亚铁、总铁和硫酸盐含量,然而腐殖酸处理对浸出液pH、EC、Eh无明显影响,且可降低浸出液硫酸盐含量。少量外源有机酸添加均能不同程度促进风化煤矸石中Fe、Mn、Cu、Zn元素溶出,其中水杨酸处理对4种金属元素的溶出量较大。然而4种外源有机酸处理则能有效抑制Pb溶出,其中柠檬酸、水杨酸处理抑制效果最明显。有机酸添加对风化煤矸石的重金属有效性影响表现为4种外源有机酸处理均能明显增加风化煤矸石中Mn元素的有效性,降低Zn元素的有效性,但对Fe元素的有效性影响不明显。4种外源有机酸添加对煤矸石中Cu元素有效性具有不同程度的影响,其中腐殖酸、草酸处理能明显降低Cu元素有效性,而柠檬酸和水杨酸处理则明显增加Cu的有效性。     

组合工艺在养猪废水处理中的工程应用研究

针对某猪场养殖废水排放所造成的严重污染问题,采用“固液分离+ UBF厌氧反应器+接触氧化+曝气生物滤池”的组合工艺,对废水中的COD、BOD、氨氮、SS去除效果明显,去除率分别为93.7％、94.4％、95％、77.1％,处理后的水质达到《国家畜禽养殖业污染物排放标准》.该工程运行费用仅为1.509元/m3,处理成本低.同时UBF池中产生的沼气可以收集并利用,猪粪和污泥可制作有机肥,实现了废物资源化利用.     

高效液相色谱-电感耦合等离子体质谱联用测定生物样品中的有机汞

建立了酸提取-高效液相色谱-电感耦合等离子体质谱联用技术(HPLC-ICP-MS)测定生物样品中甲基汞、乙基汞、苯基汞等3种有机汞的分析方法。鱼肉和贝类样品经盐酸消解,苯萃取,硫代硫酸钠溶液反萃取后,采用醋酸铵/L-半胱氨酸缓冲盐及甲醇体系组成的流动相按一定比例进行梯度洗脱,经前处理的生物样品在液相色谱中经C18柱分离后,进入电感耦合等离子体质谱检测其甲基汞、乙基汞和苯基汞的浓度。3种有机汞化合物均在0.50~50.0μg/L范围内呈现良好的线性关系,线性相关系数(r)均大于0.9998。方法检出限为0.010~0.038mg/kg;3种有机汞样品加标的RSD均小于12.2%;两个水平的加标回收率在50.8~129%。     

基于两种样品前处理方法对比研究小冬克玛底冰川雪坑中痕量元素

通过对唐古拉山小冬克玛底冰川雪坑中非季风季节沉积的雪样分别进行酸化处理和消解处理后,利用高分辨扇形磁场等离子体质谱仪(ICP-SFMS)测试了样品中19种痕量元素(Ba、U、Sr、Rb、Tl、Mo、Cs、Pb、Sb、V、Cr、Mn、Fe、Co、Al、Cu、Ti、Li、As)的酸化浓度和总浓度.研究结果表明,痕量元素浓度的变化范围较大,元素Al的最大/最小浓度比为326(酸化浓度)和465(总浓度),元素Pb相应比值为27和48.雪冰中痕量元素的总浓度一般大于该元素的酸化浓度,其中,元素Pb、Fe、Sb、Ba、Al、Ti的酸化浓度占总浓度的平均比值分别为91%、76%、60%、52%、33%和21%.一般地,样品中不溶微粒含量越大,酸化浓度占总浓度的比值越小;不溶微粒含量越小,则相反.对痕量元素的富集系数(EF)分析表明,各元素总浓度EF均值小于酸化浓度EF均值,揭示了用酸化浓度计算EF存在对痕量元素人为来源影响的高估.人类排放是小冬克玛底冰川中痕量元素的来源之一,对于元素Mo和Sb,人类排放估计是主要来源.利用后向轨迹模型模拟出小冬克玛底冰川雪冰中痕量元素在非季风季节主要来源于青藏高原西部及中亚中东地区.     

Fenton法和类Fenton法降解土壤中的二苯砷酸

本文对Fenton法与类Fenton法降解土壤中的二苯砷酸(diphenylarsinic acid,DPAA)进行了研究.考察了H2O2投加量和催化剂种类(Fe2+/Fe3+)对红壤及黑土中DPAA降解效果的影响,并采用高效液相色谱-质谱联用法(HPLC-MS/MS)对降解中间产物进行了初步鉴定.结果显示,针对红壤与黑土分别采用类Fenton法与Fenton法,在H2O2投加浓度为1 mol·L-1,含铁催化剂浓度为0.25 mol·L-1,土水比为1∶3,反应时间为1h的条件下,红壤及黑土中DPAA的降解率均可达到65%以上.HPLC-MS/MS的分析结果表明,DPAA可脱苯环形成降解产物苯砷酸(phenylarsinic acid,PAA),而PAA进一步氧化生成无机砷,这可能是Fenton/类Fenton法降解DPAA的途径之一.     

Chemopreventive effects of ellagic acid against genotoxicity induced by benzo(a)pyrene

Benzo(a)pyrene (B(a)P) is a commonly used indicator for polycyclic aromatic hydrocarbons (PAHs) contamination. The use of certain phytochemicals and some polyphenolic compounds proved to be effective in blocking PAH-induced effects. The aim of the present study was to examine the possible inhibitory effects of ellagic acid (EA), present in berries and nuts, against B(a)P-mediated toxicity using in vitro and in vivo test systems. In vitro method included the Ames test, using Salmonella typhimurium tester strain TA100. In vivo experiments were based on mouse bone marrow micronucleus (MN) assay and immunoblotting. EA produced a decrease in the number of revertant colonies against B(a)P in the Ames assay. Further, there was a reduction in the mean number of micronucleated polychromatic erythrocytes in the presence of EA in the co-treatment protocol of the MN test. Western blotting results showed downregulation of CYP450 isoform CYP1A1 which prevented bioactivation of B(a)P. Thus, the present study demonstrates antimutagenic role played by EA against the mutagenic activity of B(a)P in both in vitro and in vivo systems.     

3种填料A.ferrooxidans挂膜效果及对模拟酸性矿山废水中Fe2+生物矿化能力比较

氧化亚铁硫杆菌（A.ferrooxidans）介导的生物矿化方法可促使酸性矿山废水（Acid Mine Drainage,AMD）中Fe离子向次生铁矿物转变. 采用固定化的方式来提高A.ferrooxidans密度有助于强化Fe²⁺的生物矿化能力.选取流化床19孔填料、弹性填料、悬浮球填料作为挂膜对象, 通过多批次的连续培养来考察3种填料的A.ferrooxidans挂膜能力及稳定挂膜所需周期,继而比较3种挂膜填料对模拟AMD中Fe²⁺的生物矿化能力,并估算A.ferrooxidans有效生物量.结果表明,3种填料（5.00 g）的A.ferrooxidans挂膜能力依次为弹性填料（1.76 g）＞流化床19孔填料（0.90 g）＞悬浮球填料（0.78 g）（干重）,且挂膜启动至稳定状态至少需要4批次.X射线衍射分析（X-ray diffraction,XRD）表明,3种填料表面 含矿生物膜均为施氏矿物和黄钾铁矾的混合物.以游离态A.ferrooxidans的Fe²⁺氧化速率作为参比,估算出流化床19孔填料、弹性填料、悬浮球填料生物膜中A.ferrooxidans有效生物量依次为1.67×10⁸、8.52×10⁸、1.92×10⁸ cells·g^-1 （干基）.研究还发现,等同Fe²⁺生物氧化速率下, A.ferrooxidans挂膜填料比游离态A.ferrooxidans具有更强的AMD矿化驱动能力.