{MoOS_3Cu_3(PPh_3)_3Cl}的合成及晶体结构

本文合成并测定了{MoOS_3Cu_3(PPh_3)C1}的晶体结构,簇合物属正交晶系,空间群为P_(212121)晶胞参数:a=12.833(5)×10~(-10)m,b=17.552(5)×10~(-10)m,c=22.778(7)×10~(-10)m;Z=4。结构用直接法解出,经最小二乘法修正,偏离因子R=0.069.

水溶液中甘氨酰替亮氨酸与Ho(ClO_4)_3和Yb(ClO_4)_3相互作用的NMR研究(英文)

本文用~(13)C NMR方法研究了水溶液中三价顺磁性稀土离子Ho~(3+)和Yb~(3+)与二肽甘氨酰替亮氨酸之间的相互作用。对稀土诱导位移中的接触位移和偶极位移进行了分离。实验表明,与羧基相连的碳核所受的接触作用很大,因此不能把镱诱导的位移直接用于肽的构象分析。在水溶液中,肽通过羧基与稀土离子配位,在弱酸性条件下肽键和氨基均不参与配位。根据结构因子确定了肽在溶液中的构象,结果表明,分子片段C1-C2-C5-C6,C2-N-C3-C4和C2-C5-C6-C8为反式,而C2-C5-C6-C7和C1-C2-N-C3成旁式。

甲基膦酸二甲庚酯与伯胺N1923对Cd(Ⅱ)的协同萃取

本文研究了甲基膦酸二甲庚酯(P_(350),以 B 表示)与伯胺 N_(1923)(以RNH_2表示)的正庚烷溶液,在(Na,H)C1介质中对 Cd(Ⅱ)的协同萃取。用等摩尔系列法和斜率法确定二元协萃配合物组成为(RNH_3C1)_2·CdC1_2·B;求得协萃反应平衡常数1gK_(Bc)=2.08,协萃配合物的生成常数1gβ=0.70;计算了协萃反应的热力学函数△H=-14.56kJ/mol,△G=-12.07kJ/mol 和△S=-8.22J/mol·K;还讨论了协萃配合物的 IR 和NMR 谱。

用于膜蒸馏的疏水聚偏氟乙烯不对称微孔膜的制备及其形态结构的研究

利用相转换法以无机盐Li C1为添加剂制备了用于膜蒸馏的疏水聚偏氧乙烯不对称微孔膜。研究了铸膜液组成,特别是添加剂LiC1对膜形态结构的影响。以LiC1为添加剂制得的膜兼有指状孔结构和海绵状孔结构。与一般情况不同,所得膜的孔径控制层为下表层及靠近下表层的海绵状结构而不是上表层。

黄海太平洋磷虾种群生态学研究

太平洋磷虾（Euphausia pacifica Hansen）作为目前已开发利用的6种主要磷虾资源之一，广泛分布于北太平洋北部及其临近近岸海域。在黄海，太平洋磷虾是黄海海洋生态系统中大型浮游动物的优势种和重要功能群的组成种类，它还是黄海生态系统中鱼类等上层营养级生物的重要饵料。太平洋磷虾的种群组成以及数量变化会直接影响到黄海经济鱼类的资源动态，从而影响到整个黄海海洋生态系统的变化。 本论文依托国家重点基础研究发展计划项目（973-II）——“我国近海生态系统食物产出的关键过程及其可持续机理”和国家自然科学基金40306021号——“黄、东海太平洋磷虾种群补充机制研究”，在2006年4月到2007年8月的八个黄海调查航次中，通过网采固定样品和现场培养实验相结合的方法，对黄海海域太平洋磷虾的种群生态分布和补充、繁殖和发育策略、以及成体的摄食、代谢进行了较为全面、细致的研究。 种群生态分布：本文根据2006年4月（春季）和10月（秋季）两次黄海大面调查和2006年9月－2007年8月六次黄海断面调查所获得的样品，研究了太平洋磷虾在南黄海的种群生态分布和补充机制，并探讨了其生态分布与环境因子的关系。 春季，南黄海太平洋磷虾种群主要分布在33 °N－36 °N、50 m-75 m等深线之间的海域，种群总丰度（不包括卵）为152.90 ind. m-3，卵丰度非常高，成体丰度较低，仅占种群总数量的8.72%。调查海域的平均成体丰度为0.35 ind. m-3。种群组成以幼体为主，占到种群的90.85%。春季是太平洋磷虾种群补充的高峰期。秋季，种群主要分布在黄海冷水团海域，种群总丰度（不包括卵）为335.38 ind. m-3，成体丰度显著高于春季，调查海区成体的平均丰度为7.73 ind. m-3。成体和未成体以99.5%的总比例在种群中占绝对数量优势，卵和幼体都非常少。秋季太平洋磷虾种群处于稳定期。春季成体的体长显著大于秋季，春季成体全长以13-18 mm为主，而秋季成体的全长主要是9-13 mm。 春季，太平洋磷虾成体具有昼夜垂直迁移行为，白天主要停留在底层水域，夜间少部分成体会上升到中上层水域，但是大部分成体仍然停留在深层。幼体从C3期开始就具有一定昼夜垂直迁移行为，F2—F5期幼体的昼夜垂直迁移行为已经非常明显。由于从表层到底层叶绿素a浓度逐渐降低，因此，太平洋磷虾的昼夜垂直迁移行为可能与摄食有关。 太平洋磷虾成体的分布是与海水温度紧密相关，南黄海太平洋磷虾成体比较适宜生活的水温是8-16 °C。春、冬季水温较低，成体分布范围较广。夏、秋季表层水温急剧升高到20 °C以上，太平洋磷虾成体主要分布在黄海冷水团海域，丰度也达到一年中的最高值。另外，秋季在近长江口的北部海域有大量成体分布。 繁殖和发育：自2006年9月到2007年8月的一年内，在黄海进行了七个航次的太平洋磷虾现场培养产卵实验，结果表明：在南黄海，太平洋磷虾在3月—6月份都具有产卵行为，4月份达到产卵高峰期。单个雌体的最大产卵量为617 egg female-1，出现在4月份。8月、9月和12月在南黄海均未发现太平洋磷虾的产卵行为。太平洋磷虾具有二次产卵行为，并且第一次产卵量要高于第二次。太平洋磷虾的产卵行为与其干湿重紧密相关。成体干重低于5.0 mg，湿重低于26.0 mg，均不具有产卵能力。在产卵高峰期，太平洋磷虾的干湿重达到一年中的最高值。 在南黄海，太平洋磷虾的幼体发育主要遵循下面的发育途径：卵 → 无节幼体 → 后期无节幼体 → 原溞状幼体 → 溞状幼体F1（0' 7, 1' 7） → 溞状幼体F2（1' 4'' 7, 3' 1'' 7） → 溞状幼体F3（5'' 7） → 溞状幼体F4（5'' 5） → 溞状幼体F5（5'' 3） → 溞状幼体F6（5'' 1）。太平洋磷虾在15 °C下的幼体发育速度明显快于4 °C。15 °C下幼体发育到C1期只需5.6 d，而4 °C下则需要16.1 d。 摄食和代谢：2006年9、10、12月和2007年3、8月，在南黄海的五个断面调查航次中，在S1-4站进行了太平洋磷虾成体摄食实验，结果表明：太平洋磷虾在8月和9月份对水体中浮游植物的摄食率比较低，主要摄食水体中的微型浮游动物，从而由于营养级级联作用，致使水体中叶绿素a浓度升高。12月和3月，太平洋磷虾对水体中浮游植物有着很强的摄食活动，使得水体的叶绿素a浓度大量降低，当然太平洋磷虾也可能会同时摄食水体中微型浮游动物。 2006年9、12月和2007年3月，在南黄海的三个断面调查航次中，在S1-4站进行了太平洋磷虾现场耗氧率和排氨率实验，结果表明：太平洋磷虾在3月份的耗氧率是172.92 μg ind.-1 d-1，是9月份和12月份的6倍还要多。太平洋磷虾在9月和12月的耗碳率和体碳日损耗量相近，且都较低。3月份太平洋磷虾的代谢非常旺盛，体碳日损耗量达到2.70 % d-1，每日的耗碳率为62.9 µg C ind-1 d-1。9月和12月份太平洋磷虾代谢的氧氮比都较低，分别是11.3和7.0，太平洋磷虾成体的主要代谢基质是蛋白质。3月份的氧氮比为35.1，太平洋磷虾成体代谢主要以脂肪及碳水化合物为主。

The Yellow Sea cold bottom water - an oversummering site for Calanus sinicus (Copepoda, Crustacea)

The vertical distribution and stage-specific abundance of Calanus sinicus were investigated on three key transects in the southern Yellow Sea and the northern East China Sea in August 1999. The results showed that in summer C. sinicus shrank its distribution area to the central cold (less than or equal to10degreesC) bottom water in the Yellow Sea, i.e. the Yellow Sea Cold Bottom Water, remaining in high abundance (345.7 ind m(-3)). In the northern East China Sea on a transect from the mouth of the Yangtze River to the Okinawa trench, only a few individuals appeared in the inner side and none had been found either in the upper layer or in the deep layer of the outer shelf area. The population of C. sinicus in YSCBW consisted of mainly adults (46.83%) and C5 (37.41%). C1-C4 only accounted for 15.76%. The low proportion of the earlier copepodite stages and the high female:male ratio (11.39) indicated that the reproduction of C. sinicus in YSCBW was at a very low level due to the low temperature and low food concentration. It is concluded that the dramatic decrease of C. sinicus population in the shelf area of China seas in summer is caused by the shrinkage of its distribution area and the YSCBW served as an oversummering site.

Investigation of Extration Method for Paralytic Shellfish Poisoning Toxins in Shellfish

Me optimal conditions were established for the extraction of paralytic shellfish poisoning toxins from gonad of Chlamys nobills using acetic acid and hydrochloric acid in the concentration range of 0.04-1.0 mol/L. A 10-g portion of gonad of Chlamys nobilis was extracted by boiling for 5 min with 1.0 mL acetic acid and hydrochloric acid in a 50-mL beaker. Meanwhile, a portion of gonad of Chlamys nobilis was extracted by sonication in the solution of 0.3 mol/L HAc + 0.2 mol/L HCl for a total period of 5-30 min. The raw extract was centrifuged at 3500 r/min for 5 min and the pH of supernatant was adjusted from 2.0 to 4.0 by 0.1 mol/L NaOH or 5 mol/L HCL After passing through a Millipore ultrafiltration membrane (10000 MW cut-off), ultrafiltrate was then analyzed by HPLC. The results showed that hydrochloric acid in the concentration range of 0.25-1.0 mol/L caused a significant decrease of N-sulfocarbarnoyl-11-hydroxysulfate toxin C1 (C1), C2 and gonyautoxin 5 (GTX5) and the concomitant increase of GTX2,3. However, the amount of the three unstable toxins did not show any change using the extraction with acetic acid. Under the same concentration of acetic acid (0.3 mol/L) and hydrochloric acid (0.2 mol/L), the amount of C1 in the ultrasonic extraction was obviously lower than the boiling one, while C2 showed slightly higher than the latter.

子洲—清涧地区上古生界储层综合研究

The exploration and study in recent years shows that the upper Paleozoic in the east of Ordos Basin possesses major exploration potential, so it is necessary to have a comprehensive and synthetic research in this area. Following the guideline of T.A. Cross’s high resolution sequences stratigraphy and combined with sedimentology, the strata and sequence in the research area are divided and correlated. This paper emphasizes on the reservoir in this area and its major fruits are: Firstly, form the framework of the high sequence stratigraphy through mainly studying on the data of core, well drilling and field section combining. Then, think that the best reservoir formation mainly appears in the middle or lower part of long arising semi-cycle, and focus on A type and C1 middle sequence cycle that contributes to the development of formation. Next, think the sedimentary source mainly comes from the epimetamorphic crystalline basement in the north of the Ordoes Basin through analyzing depositional background, researching on sandstone petrography, distribution characteristics of the sedimentary system as well as researching on heavy mineral combination characteristics. Fourthly, give priority to Zizhou-Qingjian area for the first time and gain seven lithofacies paleography maps in the No.2 member of Shanxi and the No.8 member of Shihezi through using the method of isochronal lithofacies paleogeography mapping, then bring forth that Sh2 is mainly developed a type I sequence under the margin of ramp lake-basin background. Fifthly, through researching on the characteristics of reservoir petrography and diagenesis, think that all researched areas experienced compaction and cementation, and there is different types of rocks, only little of the primary pores that are made up of litharenite and lithoclastic quartz sandstone is left, while in lithoclastic quartz sandstone, there are still many primary pores Sixthly, through studying on pore types, microstructure, as well as physical property on the key formation, think that the researched area mostly appears typical low pore, low porosity and permeability, which mainly result from sedimentary and diagenesis. Lastly, through researching on classified evaluation in the key formation, productivity analysis, and combing with reservoir distribution, the researched area is divided into three parts, and think that exploration should be emphasized on formation I and II. The characteristics of sandstones distribution in Sh23 member, gas formation distribution and open flow capacity of exploitation well are all consistent properly with the results of reservoir comprehensive evaluation in this thesis proved by the gas production development in 2006.

铂族元素分析方法研究及其在有关地质问题中的应用

Characterization of Platinum Group Elements (PGE) has been applied to earth, space and environmental sciences. However, all these applications are based on a basic prerequisite, i.e. their concentration or ratio in the research objects can be accurately and precisely determined. In fact, development in these related studies is a great challenge to the analytical chemistry of the PGE because their content in the geological sample (non-mineralized) is often extremely low, range from ppt (10~(-12)g/g) to ppt (10~(-9)g/g). Their distribution is highly heterogeneous, usually concentrating in single particle or phase. Therefore, the accurate determination of these elements remains a problem in analytical chemistry and it obstructs the research on geochemistry of PGE. A great effort has been made in scientific community to reliable determining of very low amounts of PGE, which has been focused on to reduce the level of background in used reagents and to solve probable heterogeneity of PGE in samples. Undoubtedly, the fire-assay method is one of the best ways for solving the heterogeneity, as a large amount of sample weight (10-50g) can be hold. This page is mainly aimed at development of the methodology on separation, concentration and determination of the ultra-trace PGE in the rock and peat samples, and then they are applied to study the trace of PGE in ophiolite suite, in Kudi, West Kunlun and Tunguska explosion in 1908. The achievements of the study are summarized as follows: 1. A PGE lab is established in the Laboratory of Lithosphere Tectonic Evolution, IGG, CAS. 2. A modified method of determination of PGE in geological samples using NiS Fire-Assay with inductively coupled plasma-mass spectrometry (ICP-MS) is set up. The technical improvements are made as following: (1) investigating the level of background in used reagents, and finding the contents of Au, Pt and Pd in carbonyl nickel powder are 30, 0.6 and 0.6ng/g, respectively and 0.35, 7.5 and 6.4ng, respectively in other flux, and the contents of Ru, Rh, Os in whole reagents used are very low (below or near the detection limits of ICP-MS); (2) measuring the recoveries of PGE using different collector (Ni+S) and finding 1.5g of carbonyl nickel is effective for recovering the PGE for 15g samples (recoveries are more than 90%), reducing the inherent blank value due to impurities reagents; (3) direct dissolving nickel button in Teflon bomb and using Te-precipitation, so reducing the loss of PGE during preconcentration process and improving the recoveries of PGE (above 60% for Os and 93.6-106.3% for other PGE, using 2g carbonyl nickel); (4) simplifying the procedure of analyzing Osmium; (5)method detection limits are 8.6, 4.8, 43, 2.4, 82pg/g for 15g sample size ofRu, Rh, Pd, Ir, Pt, respectively. 3. An analytical method is set up to determine the content of ultra-trace PGE in peat samples. The method detection limits are 0.06, 0.1, 0.001, 0.001 and 0.002ng/mL for Ru, Rh, Pd, Ir and Pt, respectively. 4. Distinct anomaly of Pd and Os are firstly found in the peat sampling near the Tunguska explosion site, using the analytical method. 5. Applying the method to the study on the origin of Tunguska explosion and making the following conclusions: (1) these excess elements were likely resulted from the Tunguska Cosmic Body (TCB) explosion of 1908. (2) The Tunguska explosive body was composed of materials (solid components) similar to C1 chondrite, and, most probably, a cometary object, which weighed more than 10~7 tons and had a radius of more than 126 m. 6. The analysis method about ultra-trace PGE in rock samples is successfully used in the study on the characteristic of PGE in Kudi ophiolite suite and the following conclusions are made: (1) The difference of the mantle normalization of PGE patterns between dunite, harzburgite and lherzolite in Kudi indicates that they are residual of multi-stage partial melt of the mantle. Their depletion of Ir at a similar degree probably indicates the existence of an upper mantle depleted Ir. (2) With the evolution of the magma produced by the partial melt of the mantle, strong differentiation has been shown between IPGE and PPGE; and the differentiation from pyroxenite to basalt would have been more and more distinct. (3) The magma forming ophiolite in Kudi probably suffered S-saturation process.

硼及其同位素对水体污染物的示踪研究

硼的易溶性和硼化合物的广泛使用，以及污水处理过程中除硼的困难，最终导致地表地下水 体富集硼及有关污染物。海滨地下水受到海水入侵，硼含量及p(B)／p(C1)比值发生明显变化。混 合、吸附、水一岩等作用使得硼同位素发生分馏，显著区别于区域背景值。因此，结合其它同位素、水化 学等信息，硼及其同位素作为良好示踪剂为研究水圈中物质的地球化学循环过程提供了新的手段。 文中总结了部分天然水体的硼含量和硼同位素组成特征，综述了近年来用硼同位素示踪水体的污染 物来源、程度和范围等方面新的研究成果。

喀斯特森林雨水的地球化学特征——以贵州茂兰国家级自然保护区为例

贵州茂兰喀斯特原始森林地区25个雨水样品的化学组成研究表明，该区雨水的pH值为4．4～7．2，平均为5．1。雨水样品富NH4^＋、Ca^2＋和SO4^2-、C1^-。NH4^＋是最主要的阳离子，平均值为56．8／μmol／L，占阳离子组成的26％～74％，Ca^2＋次之，平均值为14．8μmol／L，NHg和Ca^2＋之和占了阳离子组成的71％～94％，SO4^2-是最主要的阴离子，平均值为39．2μmol／L，占了阴离子组成的69％～91％，CI一次之，平均值为9．5μmol／L。SO4^2-和C1-占了阴离子组成的71％～96％。与中国其他地区的雨水样品相比，茂兰地区雨水离子含量要低1～2个数量级；物质来源分析表明茂兰地区雨水中溶质主要来源于自然过程的输入，人为活动输入可以忽略不计.

四川西部呷村银多金属矿床稀土地球化学研究

呷村矿床是我国典型的含金富银多金属海相火山岩型块状硫化物矿床。通过对该矿床岩石及矿石的稀土地球化学研究，结合硫铅同位素的工作，提出成矿热液为高温酸性、富C1溶液，其稀土特征为富轻稀土，具明显正铕异常。在蚀变过程中，流体／岩石比值相对较主，稀土元素在成矿流体－围岩间具有明显的带进或带出。正铕异常产生最可能的来源是该区深部火山岩富含长石，热水溶液与火山岩发生水岩反应使长石释放出铕，使热水溶液具正Eu异常，这方面也反映该矿床成矿物质与深部火山岩有密切关系。弱负铈异常是成矿流体继承海水Ce亏损的结果。层状矿石中Eu异常变化较大，且其中LREE的含量变化大于HREE。主要原因可能是矿石中矿物组成和形成条件的变化。呷村矿床的成矿模式可以认为是火山喷发过程中产生了岩浆热液，并带出了硫和金属元素，并在海底附近快速沉淀形成。成矿后为正常深海沉积岩覆盖。

临沧锗矿褐煤的稀土元素地球化学

采用ICP—MS测定了临沧锗矿中51件古矿煤、5件无矿煤的稀土元素和锗含量，并与含矿煤层中热水成因燧石及基底白云母花岗岩进行对比．探讨了古矿煤与无矿煤的稀土元素地球化学及其与锗超常富集的关系，得出几点初步认识：c1)无矿煤和含矿煤的稀土元素主要来自基底白云母花岗岩：(2)无矿煤属正常沉积产物，含矿煤组成叠加了热水活动产物；【3)形成临沧锗矿的锗可能主要由热水活动带来。

滇西北中旬普朗斑岩铜矿流体包裹体初步研究

普朗斑岩铜矿位于三江地区义敦岛弧南端的中甸弧，是在晚三叠世甘孜．理塘洋盆向西俯冲过程中形成的一个大型．超大型矿床。通过显微测温学和激光拉曼谱学研究，发现普朗斑岩铜矿含矿石英脉中广泛发育富液相包裹体、含CO2三相／两相包裹体、含子晶多相包裹体。子晶种类复杂，盐类矿物主要有石盐、钾盐、方解石、石膏，金属矿物主要为黄铜矿和赤铁矿。流体包裹体中发现有4种流体，即高盐度岩浆流体、含CO2低盐度流体、中等盐度流体以及少量低盐度水溶液。高盐度岩浆流体的均-温度范围457，245℃，均一压力范围（259．33～25．43）×10^5 Pa，盐度为34％-54％NaCl，密度为1．12—1．07g／cm^3，富含Na、K、Ca、Cu、Fe、CO2、C1、S等成分。原始岩浆流体可能是由中酸性岩浆上升至中间岩浆房后直接出溶而成，并汇聚在岩浆房的顶部。在甘孜一理塘洋盆的俯冲过程中，岩浆流体在流体内压和洋盆俯冲所产生的主压应力场的共同作用下，可以间歇性地从岩浆房上涌，为早期岩浆活动（226±3）～（2284-3）Ma所形成的岩浆一热液系统提供了持续的矿质和热源。含CO2低盐度流体与高盐度岩浆流体的相分离作用是导致普朗斑岩铜矿主成矿期网脉状-浸染状矿化的主要原因。

卤素在银成矿中的作用—以额仁磁勒盖大型银矿床为例

通过对额仁套勒盖银矿床卤素和Ag的研究，发现卤素在银矿床中具有明显的水平和垂直分带现象，地表和近地表矿石相对富C1和I，深部矿石相对富F；矿体中相对富C1和I，近矿围岩中相对富F。卤素与Ag有密切的关系，但是矿石类型不同，卤素与Ag的关系也不同，F与Ag多为负相关，C1与Ag，I与Ag多为正相关。表明卤素在银的活化、溶解、长距离迁移和沉淀富集过程中可能起着非常重要的作用。