Assembly of the transition metal substituted polyoxometalates ZnW11M(H2O)O-39(n-) (M = Mn, Cu, Fe, Co, Cr, Ni, Zn) on 4-aminobenzoic acid modified glassy carbon electrode and their electrochemical study

Through layer-by-layer assembly, a series of undecatungstozincates monosubstituted by first-row transition metals, ZnW11M(H2O)O-39(n-) (M=Cr, Mn, Fe, Co, Ni, Cu. or Zn) were first successfully immobilized on a 4-aminobenzoic acid modified glassy carbon electrode surface. The electrochemical behaviors of these polyoxometalates were investigated. They exhibit some special properties in the films different from those in homogeneous aqueous solution. The Cu-centered reaction mechanism in the ZnW11Cu multilayer film was described. The electrocatalytic behaviors of these multilayer film electrodes to the reduction of H2O2 and BrO3- were comparatively studied.

Fractal roughness characterization of super-ground Mn-Zn ferrite single crystals

The surface of superground Mn-Zn ferrite single crystal may be identified as a self-affine fractal in the stochastic sense. The rms roughness increased as a power of the scale from 10(2) nm to 10(6) nm with the roughness exponent alpha = 0.17 +/- 0.04, and 0.11 +/- 0.06, for grinding feed rate of 15 and 10 mu m/rev, respectively. The scaling behavior coincided with the theory prediction well used for growing self-affine surfaces in the interested region for magnetic heads performance. The rms roughnesses increased with increase in the feed rate, implying that the feed rate is a crucial grinding parameter affecting the supersmooth surface roughness in the machining process.

2-氨基-6-乙氧基苯并噻唑类偶氮染料及其金属鏊合物的合成及光学热学性能研究

合成了2-（2-氨基-6-乙氧基苯并噻唑基偶氮）-5-（N,N-二乙基氨基）三氟甲基磺酰苯胺偶氮染料（EBTDATFS）及其与乙酸镍、乙酸钴、乙酸铜、乙酸锌等金属盐鏊合的金属鏊合物。通过红外光谱、紫外-可见吸收光谱和MALDI质谱等对染料及其金属鏊合物进行了结构表征;使用旋涂方法在K9玻璃和抛光的单晶硅基片上制备薄膜;研究了镍金属鏊合物的热学性能;使用椭偏仪研究了Ni和Zn鏊合物的光学常数。结果表明：4种金属鏊合物薄膜最大吸收光谱为621-629nm,且长波边吸收峰陡峭;TGA-DSC测试结果表明镍金属鏊

北京市土壤--植物系统重金属硫的分布迁移相互间关系和主成份分析

本文选择了北京市香山北京植物园、北京动物园、长安街和北京化工厂4个功能区和国槐（Sophora japonica (L) Beauv)、毛白杨 (populus tomentosa Carr)、丁香(Syringa Oblata)、野牛草(Buohloe dactyloides (Nutt) Engelm)4种植物;采集植物样品105个、土壤样品40个;测定了各样品的镍(Ni)、锌(Zn)、铜(Cu)、镉(Cd)、铅(Pb)、铬 (Cr)、硫(S)7种元素含量;通过对样品元素含量的直观分析、回归分析、主成份分析(PCA)，得出以下结论：各样品各元素含量的最高值或异常值多出现在化工厂内，其次是长安街、动物园、北京植物园无;各功能区各样品各元素含量大小顺序多是：化工厂><长安街>动物园><北京植物园：表明化工厂内土壤、植物受污染的程度较重，其次是长安街，动物园稍轻，北京植物园则较洁净。土壤中7种元素分布特征是：S > Zn > Pb > Cr > Cu > Ni > Cd;植物中7种元素分布特征是：S > Zn >< Cu > Pb > Cr >< Ni >< Cd。7种植物样品对S、Zn、Cu、 Cd具较大的富集系数;对Ni、Pb、Cr具较小的富集系数;说明前者比后者在土壤—植系统中较易迁移。7种植物样品对S均具积累效应;毛白杨叶对zn，毛白杨叶、枝、国槐皮对Cd，野牛草对Cu也都具积累效应。国槐各器官元素含量分配是：皮含量>叶含量>枝含量;毛白杨各器官元素含量分配是：叶含量>枝含量;表明植物各器官中，枝元素含量较低。对元素含量回归分析，发现植物各器官元素含量间具显著性正相关系;植物中元素含量与土壤中元素含量绝大多数呈正相关。前者说明植物各器官生长发育的正相关性;后者说明土壤条件与植物生长发育的正相关性。对元素含量的主成份分析和样品排序，揭示出采自同一功能区的样品大都可形成一集团，但尚存在交叉、重叠和过渡的样品;化工厂集团多处在排序图Z1轴左边，长安街集团多处在Z2轴上方，北京植物园集团多处在Z1轴右边或Z2轴下方。可明确得出，化工厂土壤、植物污染较重（元素含量较高），其次是长安街;动物园污染稍轻，北京植物园较洁净的结论。还可知，化工厂、长安街某些样点污染较轻;而北京植物园、动物园某些样点污染较重。

Species transformation of trace elements and their distribution prediction in dyestuff residue incineration

The release of heavy metals from the combustion of hazardous wastes is an environmental issue of increasing concern. The species transformation characteristics of toxic heavy metals and their distribution are considered to be a complex problem of mechanism. The behavior of hazardous dyestuff residue is investigated in a tubular furnace under the general condition of hazardous waste pyrolysis and gasfication. Data interpretation has been aided by parallel theoretical study based on a thermodynamic equilibrium model based on the principle of Gibbs free energy minimization. The results show that Ni, Zn, Mn, and Cr are more enriched in dyestuff residue incineration than other heavy metals (Hg, As, and Se) subjected to volatilization. The thermodynamic model calculation is used for explaining the experiment data at 800 degrees C and analyzing species transformation of heavy metals. These results of species transformation are used to predict the distribution and emission characteristics of trace elements. Although most trace element predictions are validated by the measurements, cautions are in order due to the complexity of incineration systems.

我国部分地区土壤环境背景值历史动态变化规律研究

以我国南方经济开发区。东北重工业区以及内蒙古草原区主要土壤类型为研究对象，分析近半个世纪以来不同历史时期土壤中Cu、Ni、Pb、Zn、Cd、As、Hg元素的背景值及其变化规律。结果表明，近半个世纪凤来，土壤金属元素背景值普遍存在变化。海拉尔草原区暗栗钙土近30年来Cu、Pb、Cd浓度相对稳定。As浓度有增加，而Ni、Zn、Hg浓度降低。上海郊区水稻土近10年As、Pb、Hg浓度呈现降低。南京东郊黄棕壤近50年来Cd、Hg浓度降低。Zn、Ni、Pb、As浓度升高。沈阳郊区草甸土，草甸棕壤及棕壤近30年来Pb、Zn、Cd、Cu浓度多呈升高，Hg浓度下降。各地区10—50年间土壤表层金属元素年变化率以上海、沈阳地区较大，海拉尔草原区相对较小。在2Km * 2Km面积上，草甸棕壤表土17个采样点间，7种金属元素浓度变异系数（%）分别为：Cd(33.1) > Hg(31.2) > Pb(11.3) > As(8.5) > Cu(8.3) > Zn(8.1) > Ni(7.2)。距该中心处不同距离的采样点间，各元素测定结果无显著差异（α = 0.01）。

川西地区几种优势苔藓植株元素含量及其时空差异性

揭示苔藓植株元素含量及其时空差异性是深入开展利用苔藓植物指示环境和筛选理想监测藓种的科学基础。采用微波消解（ICP-AES）方法对九寨沟自然遗产地原始林景点停车场周围三个采样带：I为停车场植被小岛（PS），向外约120 m半径为II带（D120），再向外距离约1,000 m为III带（D1000）和3个方向上的大羽藓和毛尖青藓2种苔藓中13种元素（A1, S, Ca, P, Cu, Fe, K, Mg, Mn, Pb, Ni,Zn和Cd）含量进行了测定和比较，并对采自边坡方向（PS-3）上2005和2007年的4种苔藓植物（南木藓、大羽藓、平藓和厚角絹藓）也进行了13种元素含量的测定和比较。同时对九寨沟自然遗产地、黄龙自然遗产地、夹金山和梦笔山的冷杉原始林4个地区的3种苔藓中（大羽藓、锦丝藓和塔藓）的A1、Ca、Cu、Fe、K、Mg、P、Zn、C和N 10种元素含量进行测定和比较。 对大羽藓和毛尖青藓2种苔藓植物内13种元素的测定发现：1）同种苔藓对不同元素的富集能力不同。A1、Ca、K、Mg和P的元素含量在苔藓中的富集较其他元素的要高。2）不同种苔藓植物对同种元素的富集能力不同，毛尖青藓较大羽藓能够监测出更多的元素；对于被检测出的元素，毛尖青藓监测出的累积量大于大羽藓，其中累积量最大的元素是Ca为10 874.286 μg.g-1.year-1，最小的是Cu元素为5.438 μg.g-1.year-1。对05年和07年的平藓、大羽藓、南木藓和厚角絹藓元素含量的测定表明：元素在两年中的积累量是不同的。综合分析表明，苔藓生物监测方法可有效监测景点停车场机动车尾气中排放出的典型元素（如Cu、Pb、Ni、Zn、Cd等）含量，而毛尖青藓较大羽藓能更可靠的监测九寨沟自然遗产地单景点汽车尾气金属元素种类及其排放量。 对4个地区3种苔藓10种元素监测发现：1）Ca、Mg、Zn、K和Cu元素在黄龙地区的含量高于在其它地区的含量；P元素在梦笔山地区的含量为最高；Fe和Al元素在夹金山地区的含量高于在其它地区的含量。2）C元素在其它因素一致的情况下，进行不同年龄间的元素含量比较，结果显示元素含量在各年龄间并不存在明显的差异性；N元素含量与年龄的差异出现在黄龙林下及林窗的塔藓、九寨沟林下的锦丝藓及塔藓和梦笔山的塔藓中，而在锦丝藓中未出现元素含量与年龄的差异性；塔藓能检测出更多的元素种类其含量与年龄间存在显著差异，锦丝藓检测到的元素种类次之；除锦丝藓（锦丝藓在林窗中几乎检测不到元素含量与年龄间的差异性）外，其他两种藓在林窗中能检测出的元素种类大于在林下的检测种类。3）元素含量与生境间存在差异性的元素分别有：黄龙大羽藓中的Ca、P和Mg元素；九寨锦丝藓中的Zn元素；夹金山塔藓中的Al、Fe和Zn元素；梦笔山大羽藓中的Al、Fe和Mg元素及锦丝藓中的Ca元素。4）区域、年龄和生境因素对苔藓植株元素含量均达到了显著水平，但两两之间及三者之间的交互作用由于元素种类的不同存在差异。综合分析表明，苔藓植物中的元素含量受年龄、区域的影响较生境的更大。 The revelation of mosses elements content and its spatiotemporal differences is the scientific foundation of moss monitoring. To determine the feasibility of moss monitoring metal depositions derived from travel bus emiss ions in scenic spot, we collected one year-growth samples of two mosses Brachythecim piligerum and Thuidium cymbifolium with different distance (island center, 120m，1000m ) and different direction (north, south and east) far from parking site island from Yuanshilin Spot at Jiuzhaigou World Nature Heritage in the Western Sichuan of China and determined thirteen element （A1, S, Ca, P, Cu, Fe, K, Mg, Mn, Pb, Ni, Zn, Cd）contents by ICP-AES analysis method. And picked 4 kinds of mosses (Macrothamnium macrocarpu m（Reinw. etHornsch.）Fleisch.，Thuidium cymbifolium，Entodon concinnus (De Not.) Par., Neckera pennata) from the direction PS-3 in 2005 and 2007, determined 13 element contents. Collected 3 kinds of moss (Thuidium cymbifo lium, Actinothuidium Hookeri (Mitt.) and Hyolcomium splendens (Hedw.) from Jiuzhaigou natural heritage, Huanglong natural heritage, Mt. Jiajin and Mt. Mengbi in primeval forest with two habitat (undergrowth and forest gap), determined element contents of A1, Ca, Cu, Fe, K, Mg, P, Zn, C and N. We found that, 1) The elements content are difference in same type of moss. Content of A1, Ca, K, Mg and P are higher than others. 2) While the contents of A1, S, Ca, P, Cu, Fe, K and Zn had significant correlation with the different distances from parking site, the nearer the distance was, the more accumulation was; 2) Comparing to Thuidium cymbifolium, Brachythecium piligerum can test more elements which contents show the significant correlation with distances. And Brachythecium piligerum can have greater element accumulation than Thuidium cymbifolium. The element contents in two years (2005 and 2007) are different. The present study found that moss can reliably bio-indicate metal deposition from traffic emissions in one scenic spot and Brachythecium piligerum is a good moss for bio-indicating element content from traffic emissions at Jiuzhaigou World natural Heritage. Determined the 10 element contents in 4 areas through 3 kinds of moss we found that, 1) Ca, Mg, Zn, K and Cu element content is higher in the Huanglong area than in other areas, The P element content in Mt. Jiajin is higher than other areas, Fe and Al element content is higher in the Mt. Jiajin than in other areas. 2) The content of C had no significant correlation with age. As for N, this significant correlation found in Hyolcomium splendens (Hedw.) with 2 habitat in Huanglong, Actinothuidium Hookeri (Mitt.) and Hyolcomium splendens (Hedw.) with undergrowth in Jiuzhai, Hyolcomium splendens (Hedw.) in Mt. Mengbi. The types of elements which content showt he significant correlation are most in Hyolcomium splendens (Hedw.) and least in Thuidium cymbifolium. Except Actinothuidium Hookeri (Mitt.), the types of elements that content had significant correlation with age in forest gap are more than in undergrowth. 3) The elements which content had significant correlation with habitat are P, Ca and Mg in Thuidium cymbifolium in Huanglong, Zn in Actinothuidium Hookeri (Mitt.) in Jiuzhai, Al, Fe and Zn in Hyolcomium splendens (Hedw.) in Mt. Jiajin, in Mt. Mengbi Al, Fe and Mg in Thuidium cymbifolium and Ca in Actinothuidium Hookeri (Mitt.). 4）The region, the age and the habitat factor has coeffect element content. The correlationship between element contents and the age, the region is closer than habitat.

Determination of ultra-trace concentrations of elements in high purity tellurium by inductively coupled plasma mass spectrometry after Fe(OH)(3) coprecipitation

In this work, a method was established for the determination of impurities in high purity tellurium by inductively coupled plasma mass spectrometry (ICP-MS) after Fe(OH)(3) coprecipitation. After comparison of coprecipitation ability and separation efficiency between Fe(OH), and Al(OH)(3), Fe(OH)(3) was chosen as the precipitate. A separation factor of 160 for 200 mg tellurium was obtained under conditions of pH 9 and 2 mg of Fe3(+). The 13 elements, such as Bi, Sn, Pb, In, Tl, Cd, Cu, Co, Ni, Zn, Ti, Be and Zr, could be almost completely coprecipitated under these conditions. In addition, Te memory effect imposed on the ICP-MS instrument was assessed, as well as Te matrix effect that caused the low recovery of Ga, As, Sb and V in real sample was discussed. Finally, the method was evaluated through recovery test and was applied to practical sample analysis, with detection limits of most of the elements being below 0.15 mug g(-1) and R.S.D. below or at approximately 10%, which indicated that this method could fully satisfy the requirements for analysis of 99.999% similar to 99.9999% high purity Te.

The luminescence of Eu2+ in mixed phase system

The dependence of the structure of the hosts on the M ion radius in MMgAl10O17 (M = Be, Mg, Ca, Sr, Ba, Pb, Eu, Mn, Fe, Co, Ni, Zn, Cd, Sn) system was studied and the luminescence of Eu2+ the mixed phase system was discussed. When M ion radius is less than 0.10 nm, the system MMgAl10O17 constructs by the mixed phases consisting of manegtoplumbite and spinel, alpha-alumina or spinel and alpha-alumina. In the mixed phase of manegtoplumbite and spinel and alpha-alumina, Eu2+ ion preferentially occupies lattice site of the cations in manegtoplumbite well matched with the radius and charge of Eu2+. There exists only d-->f transition emission of Eu2+ and no characteristic emission of Eu3+ occurs in those hosts. In the mixed phase of spinel and alpha-alumina, Eu2+ can enter the lattice site of Mg2+ ion or Al3+ ion and the d-->f and f-->f transition of Eu2+ can been observed respectively. Meanwhile, since the radius and charge of matrix lattice ions substituted by Eu2+ do not match with those of Eu2+, the valence state of Eu2+ is unstable. Eu2+ is partly changed into Eu3+ and the emission of Eu3+ is obviously observed even under the condition of reduction atmosphere. If reaction temperature is more than 1 150 degrees C, Al2O3 forms alpha-Al2O3 structure, the f-->f transition of Eu2+ appears. If reaction temperature is less than 1 150 degrees C, a mixed phase of alpha-Al2O3 and gamma-Al2O3 is formed, the f-->f transition of Eu2+ disappears and a new band emission from d-->f transition of Eu2+ occurs.

立方钙钛矿型复合氟化物晶体的化学键和离子行为

本文利用键子式方程和有效价电子电荷的概念详细计算了立方钙钛矿型KMF_3(M=Mg、Mn、Co、Ni、Zn)晶体的化学键参数,键性,晶体中离子的半径及离子的电子极化率,结果发现,F离子在晶体中产生形变,形变行为和F的极化率以及化学键的共价性有相同的规律。

冲绳海槽西南端中全新世以来的沉积特征及其物源与环境意义

作为大陆向大洋的过渡带，由于享有得天独厚的沉积环境，具有独特的构造特征以及与黑潮主流之间的密切关系，一直以来，冲绳海槽都是中外学者研究的重点靶区。2005年5月，由我国与法国联合主持的IMAGES 航次在台湾东北海域获取MD05-2908柱状岩芯（24º48.04′N,122 º29.35′E,水深为1275米），该柱状岩芯为一34.17米长高质量的连续沉积记录，岩性以深灰色粘土质粉砂为主，含水量较高，粘性、可塑性强，含有数层厚度不等的夹层。岩芯年龄模式依据17个AMS 14C定年数据建立，岩芯底部年代约6.8ka，为中全新世以来的沉积。在实验室对样品按照2cm的间隔进行分割后分别进行了粒度分析、粘土矿物提取与测试、碎屑矿物提取与鉴定、常微量元素和稀土元素分析等实验。 粒度分析结果显示，MD05-2908岩芯沉积物粒度垂向上总体比较均一，以细颗粒的粘土与粉砂质为主，但不同层位也稍有差别，表现为底部层位粒度较粗，含砂量较高，说明底部沉积环境比较复杂。粘土粒级（<2µm）矿物主要由四种粘土矿物和少量石英、长石碎屑组成。其中，粘土矿物相对含量变化中，伊利石（～68％）与绿泥石（～17%）构成主要成分，含有蒙皂石（～10％）和高岭石（～5％）。结合台湾东北外海表层沉积物的研究，利用粘土矿物伊利石/蒙皂石和绿泥石/高岭石比值得出岩芯粘土矿物主要为陆源碎屑粘土矿物，其源岩主要为台湾中央山脉的变质岩与台湾东部的沉积岩。重矿物分析共选取了41个层位，对63~250μm粒级的样品在实体镜和偏光显微镜下进行鉴定，结果显示，岩芯重矿物主要由绿泥石（29%）、普通角闪石（22%）、白云石（10%）、黑云母（8%）、绿帘石（7%）、白云母（7%）、褐铁矿（5%）等组成。稳定矿物少，矿物成熟度低。碎屑矿物风化程度低，磨蚀不明显，分选较差，表明沉积物来自于近源，后期改造作用不明显。常量元素分析结果表明，SiO2 、Al2O3和Fe2O3是岩芯沉积物中的最主要组分，这三种组分占沉积物总量的82%左右。 整个岩芯自下而上各常量组分变化不大，其平均值与东海陆架沉积物基本接近。微量元素变化比较明显， Ba、Cr、Cu、Zn元素的含量比东海陆架沉积物中的含量要高，而Sr的含量明显低于东海陆架。对常微量元素的R型因子分析表明，常量元素SiO2、Al2O3、Fe2O3、MgO和K2O，微量元素Cr、Cu、Ni、Zn、Pb、Rb和Mn可代表陆源物质；常量元素CaO和微量元素Sr、Ba可代表生物源物质。岩芯沉积物以陆源物质为主，生源物质的贡献起次要作用。岩芯沉积物中稀土元素总量平均为169.87×10-6，并且轻稀土含量均高于重稀土，LREE/HREE平均值为10.14，表明了轻稀土对稀土总量的贡献远高于重稀土，沉积物富集轻稀土，反映了沉积物的陆源特征。 岩芯MD05-2908中全新世以来平均5m/ka的高沉积速率主要源于丰富的物质供应和适宜的沉积环境。岩芯细粒级沉积物中，地球化学特征表明沉积物主要来源于陆源碎屑物质，粘土矿物特征与台湾东部陆源物质相同；粗粒级沉积物中，重矿物含量及矿物特征也表明岩芯沉积物粗颗粒组分主要来自于近源沉积。台湾宜兰境内的兰阳溪每年携带约一千万吨冲积物入海成为研究区重要的物质来源。由于受到黑潮的强烈影响，逆时针涡流及底层反向流的存在是岩芯高沉积速率重要控制因素。因此，利用动力分选的粉砂组分可以用来示踪古洋流强度，结果显示，6.8ka以来黑潮的强弱波动频繁，并表现出一定的旋回性变化，频谱分析表明，其具有的千年尺度周期（1500a）、百年尺度周期（604a、242a、192a、153a、133a）与十年尺度周期（22a）的周期性变化均与太阳辐射量变化有密切关系，因此，黑潮的强弱变化在大背景上是由太阳活动所控制的。 根据测年资料可以识别出岩芯存在5期快速堆积事件，这与区域性降水增加有关，降雨量增加导致陆源物质输入的增加。另外，岩芯位于大陆斜坡区，附近存在有三支海底峡谷，并且地震活动频繁，沉积在宜兰陆架及东海陆架处的浅海沉积物由于受到地震、风暴等活动的影响而受扰动崩塌、因重力作用而向低处输送，产生二次侵蚀并经由海底峡谷搬运到冲绳海槽南段堆积,使得沉积环境更为复杂，但同时也为冲绳海槽提供了丰富的物质供应。