STUDIES ON ORGANOLANTHANIDE COMPLEXES .40. SYNTHESIS AND X-RAY STRUCTURE OF BIS (2-METHOXYETHYLCYCLOPENTADIENYL) YTTRIUM AND YTTERBIUM TETRAHYDROBORATES

New bis (2-methoxyethylcyclopentadienyl) yttrium and ytterbium tetrahydroborates (Ln = Y, 1; Yb, 2) have been synthesized in good yield by the reaction of bis (2-methoxyethylcyclopentadienyl) lanthanide chlorides (Ln = Y, Yb) with sodium borohydride in THF at room temperature. The title complexes were characterized by elemental analyses, MS, H-1 NMR and IR spectra. The crystal structures of 1 and 2 have been determined by X-ray diffraction. 1 crystallizes from THF-n-Hexane in space group Pna2(1) with unit cell parametert: a = 1.2390(3), b = 1.1339(2), c = 1.1919 (2) nm and V = 1.6745(6) nm3 with z = 4 for D(c) = 1.39 g.cm-3.The structure was solved by direct method and refined to final R = 0.061 (for 1730 observed reflections). The Space group of 2 is Pna2(1) with unit cell parameters: a = 1.2399(6), b = 1.1371(5), c = 1.1897(2) nm and V = 1.6773(1) nm3 with z = 4 for D(c) = 1.72 g.cm-3, R = 0.038 (for 2157 observed reflections). The X ray structures and IR reveal the bidentate yttrium and ytterbium tetrahydroborate complexes with the intramolecular coordination bonds between lanthanide metal and ligand oxygen atoms.

杂多化合物催化性能的研究 在相转移条件下Na_2HPW_(12)O_(40)在苯乙烯氧化反应中的催化作用

杂多化合物既有配合物和金属氧化物的结构特征,又有强酸性和氧化还原性。它是具有氧化还原和酸催化功能的双功能催化剂。另外,它还具有结构确定、再生速度快、活性高、不腐蚀设备和污染少等优点,被认为是继分子筛之后,最有研究价值和开发前景的催化剂之一。

固熔体60%NaAlSi_2O_6-40%CaMgSi_2O_6在高温高压下的相图的研究

在1.0～5.0GPa、700～1750℃条件范围内,对固熔体0.6NaAlSi_2O_6-0.4CaMgSi_2O_6进行了研究,探讨了该固熔体在高温高压下的存在行为,研究了由非晶态玻璃向翡翠转化过程中γT作用的相图,得到的透辉石翡翠的晶胞参数为α=0.9439nm,b=0.8573nm,c=0.5233nm,β=107.28°和V=0.41702nm~3。本实验中合成的宝石级翡翠为色泽温润,具有玻璃光泽,半透明的极富观赏性的透辉石翡翠。

杂多酸盐K_4H(SiMo_(11)VO_(40))·14H_2O的合成及晶体结构

杂多酸是种类多,应用广的重要的无机化合物。其中有一类是12-系列化合物Z,(XM_(12-n)M_n′O_(40))·mH_2O,中心离子X可以是过渡元素或非过渡元素;M常是Mo、W;M′为V_(5+)、Mn_(2+)、CO_(2+)等;n=0,1,2…;Z为H~+或一价阳离子;y=1,2,…。它们同其相应氧化型化合物比较具有引人注目的特性,但迄今尚未见到还原型化合物晶体结构文章,只是

杂多酸盐K_4H[SiMO_(11)VO_(40)]·18H_2O 1和K_4H_2[PMo_9V_3O_(40)]·18H_2O 2的晶体结构

杂多酸是种类多,应用广的重要的无机化合物。其中有一类是12-系列化合物Z,(XM_(12-n)M_n′O_(40))·mH_2O,中心离子X可以是过渡元素或非过渡元素;M常是Mo、W;M′为V_(5+)、Mn_(2+)、CO_(2+)等;n=0,1,2…;Z为H~+或一价阳离子;y=1,2,…。它们同其相应氧化型化合物比较具有引人注目的特性,但迄今尚未见到还原型化合物晶体结构文章,只是

K_4H_2[PMo_9V_3O_(40)]·10H_2O的合成及其晶体结构

采用低温技术,用 X 射线单晶衍射法测定了标题化合物的结构.晶体属 P4/mnc 空间群,a=12.515(3),c=17.636(7),Z=2.用788个独立可观测反射精修所有结构参数得 R=0.061.钼钒磷杂多酸阴离子中,PO_4四面体是无序的,P—O 键长1.54.M(Mo,V)是6配位,M—O 键长1.62—2.48.K 是7配位,K—O 键长2.84—3.10.

Ship-board measurements and estimations of air-sea fluxes in the western tropical Pacific during TOGA COARE

Direct air-sea flux measurements were made on RN Kexue #1 at 40 degrees S, 156 degrees E during the Tropical Ocean Global Atmosphere (TOGA) Coupled Ocean-Atmospheric Response Experiment (COARE) Intensive Observation Period (IOP). An array of six accelerometers was used to measure the motion of the anchored ship, and a sonic anemometer and Lyman-alpha hygrometer were used to measure the turbulent wind vector and specific humidity. The contamination of the turbulent wind components by ship motion was largely removed by an improvement of a procedure due to Shao based on the acceleration signals. The scheme of the wind correction for ship motion is briefly outlined. Results are presented from data for the best wind direction relative to the ship to minimize flow distortion effects. Both the time series and the power spectra of the sonic-measured wind components show swell-induced ship motion contamination, which is largely removed by the accelerometer correction scheme, There was less contamination in the longitudinal wind component than in the vertical and transverse components. The spectral characteristics of the surface-layer turbulence properties are compared with those from previous land and ocean results, Momentum and latent heat fluxes were calculated by eddy correlation and compared to those estimated by the inertial dissipation method and the TOGA COARE bulk formula. The estimations of wind stress determined by eddy correlation are smaller than those from the TOGA COARE bulk formula, especially for higher wind speeds, while those from the bulk formula and inertial dissipation technique are generally in agreement. The estimations of latent heal flux from the three different methods are in reasonable agreement. The effect of the correction for ship motion on latent heat fluxes is not as large as on momentum fluxes.

浅海贝藻养殖水域沉积物再悬浮的发生机制及生态效应

沉积物再悬浮作为一个比较普遍的物理现象，对浅海生态系统污染物的生物地球化学循环具有强烈的干扰作用。本研究以我国北方重要养殖海湾——桑沟湾为研究对象，从物理、化学、生物三个角度出发，研究了沉积物再悬浮的发生过程以及再悬浮介质-沉积物的源汇转换角色及其与养殖藻类的关系，构建了波流耦合模型和再悬浮颗粒物浓度预测数学模型。主要研究结果如下： 1）桑沟湾的海湾动力比约为1.54，沉积物具有发生再悬浮的潜在动力条件；推导出波流耦合切应力的计算公式。 2）悬浮颗粒物浓度（SSC）与浊度（NTU）之间符合线性方程SSC=15.908×ln（NTU）+7.0888（n＝33，R2＝0.7209）；碎屑有机碳库是桑沟湾养殖生态系统中最大的有机碳库，占总POC库储量的81.87%。 3）沉积物再悬浮的临界切应力在0.059 N/m2左右，耦合切应力与悬浮颗粒物浓度符合方程= 238.06 SSC + 25.215（n=25，R2 = 0.7298）；最大剪切深度可达8.81 cm；桑沟湾沉积物再悬浮通量的数量级在10-5~10-6 kg·m-2·s-1之间，再悬浮临界风速约为5.51 m/s，全年约有171天沉积物处于再悬浮状态；构建了沉积物再悬浮颗粒物浓度预测数学模型。 4）桑沟湾表层沉积物总氮的含量范围313.09~1094.44µg/g，有机氮是总氮的主要形态，平均占总氮的60.86%；交换态氮是无机氮的主要形式，平均占无机氮的71.40%，交换态氮中NO3--N的含量最大；桑沟湾表层沉积物的TOC/TN比值为9.38，表明沉积物中有机质具有混合来源的特征；无机磷是桑沟湾表层沉积物中磷的主要形态，平均占总磷的73.33%，钙结合磷是无机磷的主要赋存形态；表层沉积物中潜在生物有效性磷的含量占总磷的86.54%，具有很强的释磷潜力。桑沟湾重金属的潜在生态危害指数RI约为36.17，表明重金属的潜在生态危害轻微。 5）再悬浮过程中沉积物春季表现为氮磷源，释放溶解无机氮和磷酸盐；夏、秋季表现为氮汇磷源，释放磷酸盐而吸附溶解无机氮；冬季表现为氮磷汇，吸附磷酸盐和溶解无机氮。

海洋经济动物精子超低温保存的研究

从1949年以来经过近五十年的发展，超低温保存种质细胞技术已经趋于成熟，特别是在家畜推广良种化的过程中发挥重要作用。对海洋动物种质细胞保存研究的范围主要集中在鲑鳟鱼类和牡蛎等少数几种海洋生物上。本研究结合“国家自然科学基金”研究项目，进行了三种贝类和两种鱼类精子的超低温保存实验，得到了它们在液氮（－196 ℃）条件下的适宜保存条件。栉孔扇贝（Chlamys farreri）冻精解冻后复苏比例、受精率和孵化率最高可达到49.39％、42.06％和12.15睦栉孔扇贝精子超低温保存时发生冷冻伤害的温度范围在－30 ℃～－60 ℃；其低温保存的最适降温速率为20 ℃／min；使用抗冻剂二甲基亚砜（DMSO）的最适浓度为5 ℃，其保存效果优于甘油；样品保存的最佳体积为0.6ml～1ml；解冻精子的最适水温为35 ℃，50 ℃次之，20 ℃最差；用自然海水激活解冻后精子的效果好于低盐度溶液；在0 ℃进行预处理平衡时间不宜太长；在抗冻液中加入蛋黄对保存效果没有改善，并且会对冻精的孵化率有抑制作用；用20 ℃／min和5％DMSO冷冻精子，液氮中保存栉孔扇贝精子55天后其复苏比例达到42.17％。超低温保存紫贻贝（Mytilus galloprovincialis Lamarck）精子，解冻后其复苏比例、受精率和孵化率最高可达到41.63％、69.52％和54.74％。保存紫贻贝精子最适降温速率为5 ℃／min，发生冻伤的温度范围是－20 ℃～－60 ℃；使用抗冻剂DMSO的保存效果好于甘油，且使用抗冻剂DMSO的最适浓度为15％；利用自然海水激活冻精效果好于低盐度或高pH值的溶液；样品体积（在0.2～1ml之间）对保存效果没有影响；采用15％DMSO和5 ℃／min的降温速率处理精子，液氮中保存90天后复苏比例仍达到41.8％。保存菲律宾蛤仔（Ruditapes philippinarum （Adams and Reeve））精子的最适降温速率为5 ℃／min，发生冻伤的温度范围是－30 ℃～－60 ℃；抗冻剂DMSO的保存效果好于甘油，也用DMSO与甘油混合使用，使用抗冻剂DMSO的最适浓度为10％；利用自然海水激活冻精效果好于低盐度或高pH的溶液；样品体积（在0.2％～1.6ml之间）对保存效果有显著影响。冷冻保存后精子复苏比例、受精率和孵化率最高达到40.84％、68.87％和47.17％；以最适降温速率和抗冻剂浓度处理精子，并在液氮中保存36天后冻精复苏比例仍可以达到38.54％。黑鲷（Sparus macrocephalus）精子经过超低温保存后复苏率、存活率最高可以达到61.37％和61.4。保存黑鲷精子时发生冷冻伤害的温度范围是－20 ℃～－60 ℃，适宜的降温速率为20 ℃／min；使用抗冻剂DMSO的适宜浓度为20％；样品体积对保存效果有相关性；利用自然海水激活冻精效果好于低盐度或高pH值的溶液；使用20％DMSO和20 ℃／min降温速率处理，在液氮中保存黑鲷精子66天后解冻，其复苏率和存活率分别为59.81％和58.45％。在液氮中保存真鲷（Pagrosomus major）精子时发生冷冻伤害的温域为－30 ℃～－60 ℃，适宜的降温速率为20 ℃／min；使用抗冻剂DMSO的适宜浓度为20％；采用低盐度或高pH值的溶液激活冻精的效果不如自然海水。真鲷冻精的复苏率和存活率最高可达到50.73％和62.5；以20 ℃／min和20％DMSO处理真鲷精子，保存在液氮中46天后冻精复苏率和存活率为50.63％和61.02％。通过对多种贝类和鱼类精子的超低温保存实验，不仅获得超低温保存基本条件，并且通过显微镜观察结合前人的研究，对产生冻伤的原因和保护的机理提出了一个模式。

Community structure of macrobenthos in coastal water off Rushan, southern Shandong Peninsula, and the relationships with environmental factors

To understand the present actuality of the marine ecosystem in the southern coastal water region of the Shandong Peninsula and the impact of the global change and the human activities to the marine ecosystem of the region, the macrobenthic community structure was researched based on data from 26 sampling stations carried out on four seasonal cruises from December 2006 to November 2007. The data was analyzed using PRIMER 6.0 and SPSS 15.0 software packages. The results showed that 236 macrobenthic species in total were collected from the research region by the field works. Most of the species belong to Polychaeta (76 species), Mollusca (75) and Crustacea (60). Of which, 33 species were common species by the four cruises. The dominant species were different among the four seasons, however, the polychaete species Nephtys oligobranchia and Sternaspis scutata were always dominant in the four seasons. The abundances and biomasses of the macrobenthos from the research region were variable in tire four seasons. The results of CLUSTER and MDS analysis showed that the similarities of macrobenthic structures among the stations were low, most of the similarities were at about 40% of similarity values, only that of two stations were up to 60%. In accordance with the similarity values of the macrobenthic structures, the 26 stations were clustered as six groups at arbitrary similarity level of 30%. The ABC curve indicated that the marcofauna communities in the research region had riot been disturbed distinctly. The results of BIOENV and BVSTEP (Spearman) analysis implied that the concentrations of organic matter in bottom water and heavy metal copper in sediment, water depth and temperature of bottom were the most significant environmental factors to affect the macrobentic community.

植物群落生物量和有机碳对高寒草甸土地利用变化的响应

在中国科学院海北高寒草甸生态系统定位站地区,选择高寒矮嵩草草甸及其开垦后形成的农田和一年生人工草地作为研究对象,研究了高寒草甸不同土地利用方式下生物量和植物-土壤系统固定的有机碳量的变化。结果表明：3种土地利用方式相比较,地上生物量由高到低依次为人工草地〉农田〉高寒草甸（P〈0.01）,分别为11.83、9.78和4.36 t/hm~2;3种土地利用方式下地下生物量剖面分布均呈倒金字塔形,0～40 cm地下生物量为高寒草甸〉人工草地〉农田（P〈0.01）,分别为15.74、5.61和1.24 t/hm~2。随着高寒草甸土地利用方式改变,植物群落碳素固定量也随之减小,其序列由高到低依次为：高寒草甸〉人工草地〉农田（P〈0.05）,其值分别为7.63、6.81和4.51 t/hm~2。

祁连山海北高寒湿地40～80cm土壤温度状况观测分析

海北高寒湿地土壤水分达超饱和状态,土体热容量大,因而地温在随时间进程中变化平稳,日、年较差较小. 年内季节冻土并不深厚,多维持于1 m 左右,小于高山草甸土分布区. 由于50 cm 层次年平均地温仅为1. 2 ℃,暖季的6～9 月平均为2. 8 ℃左右. 因此,按温度诊断特点来看,该类型高寒湿地土在中国土壤分类中属寒冷性土壤温度状况,仍为正常有机土.

中国东海陆架盆地构造-热演化研究

East China Sea Shelf Basin (ECSSB), as a basin with prospect of oil & gas resource and due to its special geological location on the west margin of the west Pacific, attracts a lot of attention from many geologists in the world.Based on systematic temperature measurements, bottom hole temperature (BHT) and the oil temperature data, the geothermal gradients in the ECS SB are calculated and vary from 25 to 43°C/km, with a mean of 32.7°C/km. The geothermal gradient in Fuzhou Sag has the higher value(40.6°C/km) in Taibei Depression than that in others. The lower value (27.2 °C/km) occurs in in Xihu Depression. The middle values occurs in Jiaojiang and Lishui sags in Taibei Depression with a mean value of 34.8 °C/km. Incorporated with the measured thermal conductivity, heat flow values show that the ECSSB is characterized by present-day heat flow around 70.6mW/m2, varying between 55 and 88 mW/m2. No significant difference in heat flow is observed between the Xihu and the Taibei Depressions. These heat flow data suggest that the ECSSB is geothermally not a modem back-arc basin.Applying the paleogeothermal gradient based method, thermal history is reconstructed using vitrinite reflectance (VR) and apatite fission track (AFT) data. The results suggest that the thermal history was different in the Taibei and the Xihu depressions. Paleo-heat flow values when the pre-Tertiary formations experienced their maximum temperature at the end of the Paleocene reached a mean of 81 mW/m2 in the Taibei Depression, much higher than the present-day value. The lower Tertiary sediments in the Xihu Depression experienced maximum temperatures at the end of Oligocene and reached a mean paleo-heat flow value of 83.4 mW/m2. The time, when the paleo-heat flow reached the maximum value, suggests that the ECSSB rifted eastward.Tectonic subsidence analysis shows that the timing of the major rifting episode was different across the ECSSB. The rifting occurred from the Late Cretaceous to the early Eocene in the Taibei Depression, followed by thermal subsidence from the late Eocene to the end of Miocene. In contrast, in the Xihu Depression the initial subsidence lasted until the early Miocene and thermal subsidence to the end of Miocene. From Pliocene to the present, an accelerated subsidence took place all along the West Pacific margin of the east Asia.The thermal lithosphere thickness is determined by temperature profile in the lithosphere, the mantle adiabat or the dry basalt solidus. It indicates that the thermal lithosphere reached the thinnest thickness at the end of Eocene in the Taibei Depression and the end of Oligocene in the Xihu Depression, respectively, corresponding with a value of 57-66km and 56-64km. In Taibei Depression, the lithosphere thickness decreased 16-22km from the end of Mesozoic to Paleocene. After Paleocene, the thickness increased 13-16km and reached 71-79 km at present-day. In Xihu Depression, From the end of Oligocene to present-day, the thickness increased 10-13km and reached 69-76km at present-day. The evolution of the lithosphere thickness is associated closely with the lithosphere stretching.Combining the reconstructed thermal history and the burial history, the maturation of the Jurassic oil-source rock shows that the main hydrocarbon generation phase was in the mid-Jurassic and a secondary hydrocarbon generation occurred at the end of Paleocene. The secondary generation was controlled mainly by the tectono-thermal background during the Paleocene.

贵阳雨水无机氮沉降的氮、氧同位素特征

雨水中氮沉降主要以铵盐(NH+4)和硝酸盐(NO-3)形式存在,这与地表生态氮循环和酸雨等环境问题直接相连.我们测定了贵阳地区雨水中的NH+4和NO-3的氮氧同位素值,讨论了氮素形态分布及其同位素组成特征,探讨了雨水中溶解无机氮的成因.雨水中的NH+4和NO-3平均值分别为0.81和o.51mg N/L;铵盐的δ15N平均值为-4.7‰,较硝酸盐的δ15N平均值负,雨水中硝酸盐δ18O值为25.2‰～40.1‰,平均值为34.2±4.3‰,季节性差别不显著.

萤石Sm—Nd同位素体系对晴隆锑矿床成矿时代和物源的制约

本文首次对黔西南晴隆锑矿床的萤石进行Sm-Nd同位素研究，来探讨该矿床的形成时间和成矿物源。研究表明，该矿主成矿期的萤石构成两组等时线，其对应的等时线年龄分别为148±8Ma和142±16Ma。显示该矿床的成矿作用发生在晚侏罗世。本次测定的成矿年龄数据远小于峨眉山玄武岩的成岩年龄，暗示该矿床与该区二叠纪的火山作用没有直接的成因联系。计算表明，在晴隆锑矿床成矿时(142Ma)，两组萤石的δNd(t)值分别为-5．72～-5．81和-3．81～-3．88，远小于峨眉山玄武岩的相应值(0．40～3．27)；两组萤石初始Nd同位素组成的差异，暗示其Nd的来源存在不均一性，这很可能与萤石沉淀环境围岩的局部差异有关。在δSr(t)-δNd(t)图解中，萤石明显分布在与赋矿围岩不同的区域，暗示该矿的成矿物质主要是来自外部(可能是下伏老地层或基底)，而不是赋矿的峨眉山玄武岩和茅口组灰岩，因此，该矿并非是前人认定的“原地改造成矿”。