水热溶剂对Cu/CeO2-TiO2催化CO2加氢制甲醇反应性能的影响

以高暴露（001）面锐钛矿TiO₂为载体,使用3种不同溶剂（甲醇、乙二醇和丙三醇）水热负载CeO₂,进而以CeO₂-TiO₂为载体采用硼氢化钠还原法负载Cu,合成Cu/CeO₂-TiO₂催化剂用于催化CO₂加氢制甲醇.XRD、SEM、BET、ICP-OES、XPS、H₂-TPR、EPR和CO₂-TPD等表征表明,以 甲醇/水为混合溶剂合成的CeO₂-TiO₂（CT-M）载体中CeO₂粒径较小、Ce³⁺浓度较高,更有利于Cu的负载与分散,形成紧密接触的三相界面;其负载Cu的催化剂CCT-M经焙烧、还原后形成的CuCeTi三相界面相互作用更强,可产生更多的表面Ce³⁺、氧空位和体相Ti³⁺,表面Ce³⁺、氧空位和体相Ti³⁺等缺陷有利于CO₂的吸附活化,较小粒径的Cu则可加速氢解离,因此,CCT-M具有更多的CO₂加氢反应活性位点,表现出最优的CO₂加氢产甲醇活性.     

Cd2+、Cu2+和Zn2+对人工湿地反硝化作用的影响

实验室研究了 3种重金属离子 Cd²⁺、Cu²⁺、Zn²⁺对人工湿地反硝化作用的影响 .以 100、500、1000 mg/kg剂量的 Cd²⁺、Cu²⁺、Zn²⁺处理人工湿地土壤样品 ,检测其 N₂O的产生 .结果表明 ,3种金属离子的 500、1000mg/kg处理组土样 N₂O的产生均显著降低 ,各金属离子抑制 N₂O产生的程度顺序为 Cd²⁺>Zn²⁺>Cu²⁺,这与 3种金属离子在土样中的有效态浓度顺序是一致的 ,反硝化微生物在处理过程中逐步产生了对重金属离子的耐受性 ,500、1000mg/kg处理组样品的 NH⁺₄- N浓度较对照组显著升高提示部分 NO^-₃- N由于反硝化过程的抑制而异化性还原为 NH⁺₄-N.     

应用四膜虫刺泡发射评价加氯水体中有机浓集物的致突变性

应用致突变阴性、阳性对照（Cu^2＋,丝裂霉素MMC和环磷酰胺CP）评价四膜虫刺泡发射试验方法的可行性,并应用该方法检测养殖水体加氯消毒后的有机浓集物对四膜虫刺泡发射的影响效应．结果表明,水体加氯后的有机浓集物可引起四膜虫刺泡发射,且各处理浓度与刺池发射率呈良好的相关性,表明这些有机物中含有致突变性物质．     

Reduction of NO by CO using Pd-CeTb and Pd-CeZr catalysts supported on SiO2 and La2O3-Al2O3

The catalytic activity of Pd catalysts supported on Ce_0.73Tb_0.27O_x/SiO₂, Ce_0.6Zr_0.4O_x/SiO₂, Ce_0.73Tb_0.27O_x/La₂O₃-Al₂O₃ and Ce_0.6Zr_0.4O_x/La₂O₃-Al₂O₃ was studied using the reduction of NO by CO. The catalysts were characterized by X-ray fluorescence, surface area, X-ray diffraction, temperature-programmed reduction, CO chemisorption and oxygen storage capacity. Temperature-programmed reduction results indicated that Tb or Zr incorporation improves the reducibility and oxygen storage capacity. CO chemisorption data suggested the presence of large PdO particles due to the low CO/Pd ratio. No significant differences were obtained in light off temperatures (T_{Light off}) for all Pd catalysts and the most active was 1.5%Pd/Ce_0.6Zr_0.4O_x/SiO₂.     

CeO2-La2O3/γ-Al2O3稀土氧化物混合物催化还原SO2的实验研究

在La₂O₃ 中加入变价稀土氧化物CeO₂,组成一种稀土氧化物的混合物,以这种混合物作为CO还原SO₂的催化剂.采用连续流动固定床反应器,在反应气体SO₂和CO按SO₂∶CO = 1∶3,载流气体为N₂,气体流量为1000 mL/min的条件下,实验研究了该催化剂的活化过程以及温度和反应物浓度配比对活化反应的影响,用XRD和XPS对反应前后催化剂进行了表征,分析了相结构的变化.结果表明:CeO₂和La₂O₃ 2种稀土氧化物的混合物,在CO还原SO₂的催化反应中,活化温度比单个的CeO₂或La₂O₃氧化物下降了50℃～100℃,而且具有更高的活性.这可能是CeO₂和La₂O₃氧化物之间存在着某种协同作用所致.     

镉处理对大豆幼苗生长及激素含量的影响

采用室内培养试验,通过测定植株生理生化指标,研究了不同浓度Cd²⁺处理对大豆幼苗生长及激素含量的影响.结果表明:①不同浓度Cd²⁺处理对大豆幼苗地下部生长素(IAA)和赤霉素(GA₃)的合成有抑制效应,对地上部生长素(IAA)和赤霉素(GA₃)的合成具有低浓度下的刺激效应和高浓度下的抑制效应;对地下部、地上部玉米素(Z)和脱落酸(ABA)的合成均有刺激效应.②Cd²⁺处理84h对大豆幼苗根系活力、叶绿素a和叶绿素b的合成有刺激效应,对类胡萝卜素的合成无影响.③Cd²⁺处理对过氧化物酶(POD)活性和丙二醛(MDA)含量具有低浓度下的抑制效应和高浓度下的激活效应,且随着Cd²⁺浓度的增加激活效应逐渐加强.④短时间、低浓度Cd²⁺胁迫可刺激大豆幼苗的生理活性,以Cd²⁺处理浓度为0.50 mg/L时,大豆幼苗根系活力最大,IAA和GA₃含量最高,POD活性最低,植物生理活性最强.     

活性炭纤维负载氧化镧催化净化NO的实验研究

以ACF作为载体制备了负载不同质量分数La₂O₃的负载型催化剂,研究了它们催化净化NO的活性和活性的稳定性,同时对比研究了ACF、HNO₃/ACF净化NO的能力.正交实验结果表明,实验中最佳的氧气体积分数为5%,最佳空速为5 000 m³·(m³·h)^-1;催化实验结果表明,ACF的低温活性很差,HNO₃/ACF净化NO的低温活性很好,但是其活性的稳定性很差;负载了La₂O₃的ACF能大幅提升ACF净化NO的能力,其活性中心为La₂O₃,La₂O₃的最佳负载量为20%,350℃以上时,20% La₂O₃/ACF催化净化NO的效率均在95%以上,在200℃恒温条件下,其催化活性约能持续8h;催化剂的理化特征实验结果表明,ACF、HNO₃/ACF净化NO的机制与负载了La₂O₃的ACF净化NO的机制有着本质的区别.     

Role of NO and SO2 in mercury oxidation over a La2O3/Fe2O3 catalyst with high thermal stability

In this study, the thermal stability of a ferric oxide catalyst for mercury oxidation was found to be considerably promoted by doping with La₂O₃. The catalysts doped with La₂O₃ maintained a higher surface area when subjected to high-temperature calcination, with lower average pore size and a narrower pore size distribution. X-ray diffraction (XRD) results revealed that La₂O₃ doping hinders the growth of catalyst particles and crystallization of the material at high temperatures. Both NO and SO₂ inhibited Hg⁰ oxidation over the La₂O₃/Fe₂O₃ catalyst. Fourier transform infrared (FTIR) spectra revealed that SO₂ reacts with O₂ over the catalysts to form several species that are inert for mercury oxidation, such as SO₄^2?, HSO₄^?, or other related species; these inert species cover the catalyst surface and consequently decrease Hg⁰ oxidation capacity. In addition, NO or SO₂ competed with Hg⁰ for active sites on the La₂O₃/Fe₂O₃ catalyst and hindered the adsorption of mercury, thereby inhibiting subsequent Hg⁰ oxidation. Hg⁰ oxidation on the La₂O₃/Fe₂O₃ catalyst mainly followed the Eley–Rideal mechanism. Moreover, the inhibition effects of NO and SO₂ were at least partially reversible, and the catalytic activity was temporarily restored after eliminating NO or SO₂.     

一步法La@MgFe2O4的制备及其吸附水中磷的性能

由于磷矿资源紧张及磷污染引起的水体富营养化,迫切需要回收水体中的磷酸盐.利用铁氧体复合材料吸附回收水中的磷,由于吸附容量较大以及利用外加磁场易于从水中分离而日益得到重视.本研究利用一步共沉淀法直接制备尖晶石型La@MgFe₂O₄复合材料,将La³⁺固定在MgFe₂O₄缺陷位点上,考察La@MgFe₂O₄的吸磷尤其是低温时的吸磷能力,并采用XRD/FTIR/XPS/VSM等技术对La@MgFe₂O₄进行表征.结果表明,La³⁺离子以La（OH）₃的形式负载在MgFe₂O₄晶界缺陷上,La³⁺的加入改变了MgFe₂O₄的结晶度和形貌,并大大提高了MgFe₂O₄的吸磷能力,其饱和磁化强度为14 emu·g^-1,在外加磁场条件下可以从水中磁分离.当pH值为6时,温度降为10℃其最大吸附容量与25℃时相比几乎无降低,约为143.156 mg·g^-1.动力学研究表明,La@MgFe₂O₄能在30 min内将低磷（10 mg·L^-1）浓度转化为极低磷.吸附机制研究表明,磷通过配体交换形成内球络合物被去除.La@MgFe₂O₄对磷酸盐具有高度选择吸附性,吸附剂解吸后可多次重复使用.将其应用于中国北方低温市政污水,投加吸附剂的浓度为1 g·L^-1,可在1 h内将磷酸盐浓度降低至0.5 mg·L^-1以下,表明La@MgFe₂O₄在寒冷地区也具有良好应用前景.     

Effects of Zr substitution on soot combustion over cubic fluorite-structured nanoceria: Soot-ceria contact and interfacial oxygen evolution

Ceria is widely used as a catalyst for soot combustion, but effects of Zr substitution on the reaction mechanism is ambiguous. The present work elucidates effects of Zr substitution on soot combustion over cubic fluorite-structured nanoceria. The nanostructured CeO₂, Ce_0.92Zr_0.08O₂, and Ce_0.84Zr_0.16O₂ composed of 5–6 nm crystallites display T_m-CO2 (the temperature at maximum CO₂ yield) at 383, 355, and 375°C under 10 vol.% O₂/N₂, respectively. The size of agglomerate decreases from 165.5 to 51.9–57.3 nm, which is beneficial for the soot-ceria contact. Moreover, Zr increases the amount of surface oxygen vacancies, generating more active oxygen (O₂^? and O^?) for soot oxidation. Thus, the activities of Ce_0.92Zr_0.08O₂ and Ce_0.84Zr_0.16O₂ in soot combustion are better than that of CeO₂. Although oxygen vacancies promote the migration of lattice O^2?, the enriched surface Zr also inhibits the mobility of lattice O^2?. Therefore, the T_m-CO2 of Ce_0.84Zr_0.16O₂ is higher than that of Ce_0.92Zr_0.08O₂. Based on reaction kinetic study, soot in direct contact with ceria preferentially decomposes with low activation energy, while the oxidation of isolated soot occurs through diffusion with high activation energy. The obtained findings provide new understanding on the soot combustion over nanoceria.     

Damage to DNA of effective microorganisms by heavy metals: Impact on wastewater treatment

The research is to test the damage to DNA of effective microorganisms(EMs)by heavy metal ions As3+,Cd2+,Cr3+,Cu2+,Hg2+, Pb2+,and Zn2+,as well as the effects of EM bacteria on wastewater treatment capability when their DNA is damaged.The approach applied in this study is to test with COMET assay the damage of EM DNA in wastewater with different concentrations of heavy metal ions As3+,Cd2+,Cr3+,Cu2+,Hg2+,Pb2+,Zn2+,as well as the effects of EM treated with As3+,Cd2+,Cr3+,Cu2+,Hg2+,Pb2+,and Zn2+ on COD degradin...     

Damage to DNA of e ective microorganisms by heavy metals: Impact on wastewater treatment

The research is to test the damage to DNA of effective microorganisms(EMs)by heavy metal ions As3 ,Cd2 ,Cr3 ,Cu2 ,Hg2 , Pb2 ,and Zn2 ,as well as the effects of EM bacteria on wastewater treatment capability when their DNA is damaged.The approach applied in this study is to test with COMET assay the damage of EM DNA in wastewater with different concentrations of heavy metal ions As3 ,Cd2 ,Cr3 ,Cu2 ,Hg2 ,Pb2 ,Zn2 ,as well as the effects of EM treated with As3 ,Cd2 ,Cr3 ,Cu2 ,Hg2 ,Pb2 ,and Zn2 on COD degradin...     

稀土金属离子对梨形四膜虫的24小时生长影响

应用４种方法（细胞直计计数法、中性红试验、重蛋白及核酸含量测定）研究不同浓度稀土金属离子Ｌａ＾２＋、Ｓｍ＾３＋、Ｙ＾３＋、Ｇｄ＾３＋处理２４ｈ后，对梨形四膜虫的生长影响，结果表明，在低浓度时Ｌａ＾３＋、Ｓｍ＾３＋、Ｙ＾３＋，对四膜虫具有刺激生长的作用。随着浓度的升高，４种稀土金属离子均表现出毒性效应；高浓度时，抑制生长艇特别明显。计算Ｌａ＾３＋、Ｓｍ＾３＋、Ｙ＾３＋、Ｇｄ＾３＋的半数抑制浓度（ＩＣ     

6种重金属的发光菌毒性效应及其海洋生物物种敏感度分析

以明亮发光杆菌(Photobacteriumphosphoreum)为受试生物,采用微孔板毒性测试法,测定6种重金属化合物的发光抑制毒性并对毒性数据进行非线性拟合和预测,结果表明ZnSO47H2O、K2Cr2O7、HgCl2、CdCl22.5H2O和Pb(NO3)25种重金属化合物的毒性作用关系均可以用Weibull模型有效描述,CuSO45H2O的毒性作用关系可用Logistic模型有效描述。几种重金属的毒性顺序为K2Cr2O7 CuSO45H2O CdCl2 Pb(NO3)2 ZnSO47H2O HgCl2。明亮发光杆菌对6种重金属离子的EC50值分布在由其它海洋生物毒性效应值拟合的物种敏感度分布模型范围内。与海洋鱼类、蚤类、贝类和虾蟹类相比,明亮发光杆菌对Cu2+的毒性灵敏度较差,但是对Cd2+、Pb2+、Hg2+、Zn2+、Cr6+5种重金属离子的毒性灵敏度较高,多数海洋生物对6种重金属的毒性响应顺序与明亮发光杆菌一致,说明发光菌毒性测试法对于海洋环境重金属污染的生态毒理效应具有重要预测价值。     

Fractionation of rare earth and other trace elements in crabs, Ucides cordatus, from a subtropical mangrove affected by fertilizer industry

Fractionation of rare earth elements (REE) and other trace metal concentrations (Th, U, Cd, Cr, Cu, Ni, Pb, and Zn) between mangrove sediments and claw muscles and shells of male crabs (Ucides cordatus) from a subtropical estuary highly impacted by fertilizer industry activities was investigated. This is the first record of REE distribution in these organisms, and the results showed higher accumulations of these metals, U and Th in shells, probably related to the replacement of Ca during molting. Contents of Cd, Cr and Ni were similar in both tissues, but Cu, Zn and Pb were mostly accumulated in the claw muscle with concentrations above those considered safe for human consumption according to the Brazilian legislation. REE fractionation was different in the analyzed tissues being softer in the shells. The results provided evidences that the water absorbed during molting controls the chemistry of REE in shells. In contrast, the chemistry of REE in the claw muscle, in which was observed preferential absorption of light REE, is controlled by diet. REE fractionation obtained for the claw muscles was closely correlated to the observed in the contaminated substrate and in materials related to the production of phosphate fertilizers (contamination source), which supports their transference to this Ucides cordatus tissue without fractionation by the ingestion of sediments. Our results showed the potential use of crab tissues for monitoring REE and trace element sources in mangrove areas, with claw muscle exhibiting the contaminant source fingerprint.     

我国城市污水处理厂污泥中重金属分布特征及变化规律

对由中国知网数据库和维普中文科技期刊全文数据库报道的近30年来我国城市污水处理厂污泥中重金属分布特征和年代变化规律进行了分析. 结果表明:近30年来城市污水处理厂污泥中w(Cd)、w(Pb)、w(Cr)、w(As)、w(Hg)、w(Cu)、w(Ni)、w(Zn)平均值或中位值均符合GB 18918─2002《城镇污水处理厂污染物排放标准》中污泥农用时污染物控制标准限值,但数据离散且呈偏态分布. 依据GB 18918─2002,1980─1989年我国城市污水处理厂污泥中重金属质量分数75%分位值中有w(Cd)、w(Cu)、w(Ni)、w(Zn)超标,90%分位值中有w(Cd)、w(Pb)、w(Hg)、w(Cu)、w(Zn)、w(Ni)超标;1990─1999年城市污水处理厂污泥中重金属质量分数75%分位值中w(Ni)超标,90%分位值中除w(As)外其他重金属均超标;2000─2010年城市污水处理厂污泥中重金属质量分数75%分位值中w(Ni)超标,90%分位值中w(Cd)、w(Cr)、w(Hg)、w(Cu)、w(Zn)、w(Ni)超标. 从年代变化看,我国城市污水处理厂污泥中w(Cd)、w(Cu)随年代逐渐下降,但w(Hg)、w(As)、w(Cr)、w(Zn)、w(Ni)、w(Pb)呈波动趋势. 近10年数据表明,我国城市污水处理厂污泥中w(Ni)、w(Cd)、w(Hg)超标倍数最高,在进行污泥处置时需要优先关注.      

浙北海域表层沉积物中重金属的含量特征、来源和污染评价

为了解浙北海域表层沉积物中重金属的含量和分布特征,本研究以浙北海域64个站位的沉积物为研究对象,检测了Cu、Zn、Cr、Ni、Pb、As、Cd和Hg共8种重金属的含量,并分析了其主要来源和生态风险。结果表明,Cu、Zn、Cr、Ni、Pb、As和Hg（除了s112）的含量均未超过一类海洋沉积物质量标准,68.8%的已检出站位Cd的含量达到三类质量标准。Cu、Zn、Ni和As 4种元素呈现出由近岸向外海浓度逐渐降低的趋势（p < 0.01）。溯源分析表明,Cu、Zn、Cr、Ni和As主要来自陆源的工农业和生活污水,Pb和Cd主要来自船舶废气、海水养殖和工业污染。地积累指数表明8种重金属的污染程度由高到低依次为:Cd > Ni > Cu > Hg > Cr > Zn > Pb > As,只有Cd在所有检出站位中最低浓度也呈现出偏中度污染。潜在生态风险系数评价表明,Hg在3.1%站位存在强生态风险,Cd在所有检出站位中最低浓度也呈现出强生态风险。综合评价8种重金属,发现浙北海域21.87%的采样点存在强生态风险,其中Cd对潜在生态风险指数（RI）的贡献达到84.71%。     

Zn2+、Cd2+、Cu2+、Cr6+和Se4+对褶牡蛎急性毒性效应研究

金属污染对水生底栖滤食性动物的危害,一直是普遍关注的水产养殖及水产品安全性热点问题之一。本文采用半静态法研究了Zn2+、Cd2+、Cu2+、Cr6+、Se4+对褶牡蛎(Crassostrea plicatul)的急性毒性效应(LC50)。结果表明,Zn2+、Cd2+、Cu2+、Cr6+、Se4+对褶牡蛎48 h- LC50分别为1447.00、28.16、12.25、1098.00、22.89 mg/L;72h- LC50分别为231.62、12.24、4.23、539.02、9.12 mg/L;96 h- LC50分别为81.84、8.83、2.59、378.06、4.10 mg/L,安全浓度(SC)分别为0.81、0.08、0.03、3.78、0.04 mg/L,五种金属对褶牡蛎的毒性依次为:Cu2+ Se4+ Cd2+ Zn2+ Cr6+,其中褶牡蛎对Cd2+、Zn2+、Cr6+耐受性较强,分别为渔业水质标准(GB11607-89)的17.60、37.81、8.18倍。     

盐城北部潮间带表层沉积物重金属分布特征及污染评价

对采自盐城北部潮间带的241个表层沉积物样进行测试分析,探讨了沉积物中重金属(Cu、Pb、Zn、Cr、Cd、As、Hg)空间分布特征及各元素相关关系,并采用Hakanson潜在生态风险指数法进行了污染评估。结果表明:1)研究区重金属Zn、Pb、Hg含量均符合国家规定的一类沉积物标准,Cr、Cd、Cu、As含量在大部分站位也都低于一类沉积物标准,其中Cr仅在个别站位处达到二类沉积物标准,Cd、Cu、As在少数站位达到二类沉积物标准。2)研究区Cu、Pb、Zn、As四种元素在物源或迁移累积特征上具有相似性,Cd元素不受元素粒度控制律控制。3)研究区重金属总体污染和潜在生态危害处于低风险级别,重金属潜在生态危害系数由大到小依次为:CdAsCuPbCrZnHg。