电感耦合等离子体质谱和光谱分析方法研究

本论文的出发点是ICP—MS的谱干扰及其校正和基体效应研究。以ICP—MS测定贻贝标准参考物质中的痕量元素以及生物样品中的稀土元素为例，研究了基体元素C、Ca、Cl、K、Na和P的多原子离子对一些元素的测量同位素以及Ba及轻、中质量稀土元素的氧化物离子对部分中、重质量稀土元素的同位素的干扰程度，确定了干扰元素的允许浓度比，建立了ICP—AES和ICP—MS测定贻贝标准参考物质中的主量和痕量元素以及ICP—MS测定生物样品中稀土元素的新方法，首次报出了贻贝标准参考物质中全部稀土元素的含量。考查了ICP—MS测定高纯镉中的杂质元素时，镉的多原子离子可能产生的谱干扰并比较了干扰程度的大小，研究了仪器工作参数变化对镉基体的多原子离子~(106)CdH~+、~(110)Cd~(16)O~+和~(112)Cd~(16)O_2~+以及~(116)Cd~(2+)信号的影响。研究了乙醇、丙醇、丙三醇、乙酸、乙二胺和三乙醇胺等与水互溶的有机试剂对不同质量和不同电离电位无素信号的影响。首次发现，溶液中加入少量乙二胺或三乙醇胺对Hg信号有10倍以上的增强，对Pb和Sr等的信号起抑制作用，探讨了乙二胺和三乙醇胺对Hg信号增强的机理，建立了一个测定生物样品中Hg的新方法。研究了FI小体积进样时ICP—MS的基体效应，并与连续进样作了比较。流动注射小体积(100 μ1)进样时，电离电位大于9 eV的As和Au基体对分析元素的信号表现为增强效应，而电离电位较小的Cu、In、Li、Na和Pb基体对分析元素的信号表现为抑制效应。与连续雾化相比，FI小体积进样的抑制效应较小而增强效应较大。

Direct patterning of negative nanostructures on self-assembled monolayers of 16-mercaptohexadecanoic acid on Au(111) substrate via dip-pen nanolithography

Both bare and self-assembled monolayer (SAM) protected gold substrate could be etched by allyl bromide according to atomic force microscopy (AFM), x-ray photoelectron spectroscopy (XPS) and inductively coupled plasma mass spectrometric (ICPMS) analysis results. With this allyl bromide ink material, negative nanopatterns could be fabricated directly by dip-pen nanolithography (DPN) on SAMs of 16-mercaptohexadecanoic acid (MHA) on Au(111) substrate. A tip-promoted etching mechanism was proposed where the gold-reactive ink could penetrate the MHA resist film through tip-induced defects resulting in local corrosive removal of the gold substrate. The fabrication mechanism was also confirmed by electrochemical characterization, energy dispersive spectroscopy (EDS) analysis and fabrication of positive nanopatterns via a used DPN tip.

稀土离子跨红细胞膜作用

利用动物实验、采用ICP MS及NMR技术对稀土离子跨红细胞膜的作用进行了研究 .结果表明 ,给兔一次性注射不同剂量的稀土硝酸盐 ,经不同时间取血 ,在红细胞内没有观察到稀土 .取兔红细胞做体外实验 ,稀土硝酸盐浓度在 0 .0 1mg/mL以下没有观察到稀土离子过膜的现象 ;稀土硝酸盐浓度在 0 .0 1mg/mL以上 ,已有部分红细胞溶血 .并且 ,随浓度增加和温育时间的延长 ,红细胞溶血量也有所增加

西天山造山带古生代构造演化与地壳增生—来自花岗岩和蛇绿岩的证据

The Central Asian Orogen Belt (CAOB), which is different from the subductional orogen and the collisional orogen, is known as the most important site of crustal growth in the Phanerozoic, and it has been a ‘hot spot’ for studying the orogenic belts. The Chinese West Tianshan Orogen is occupying the west-southern part of the CAOB and is of great importances to understand the orogenic processes and the continental growth in the Central Asia. The West Tianshan Orogen had undergone complex tectonic evolutional processes in Paleozoic times and large volumes granitic rocks have recorded important information about these processes. Litter is known about Phanerozoic continental growth in the Western Tianshan area so far, compared with the other areas of the CAOB, such as eastern Junggar, western Junggar, Altai and Alakol. The aim of this dissertation is to set up the chronology frame of granitoids in western Tianshan, provide new evidence for the tectonic evolution and discuss the Paleozoic continental growth in this area, on the basis of the studies on the isotopic chronology, major element, trace element and Nd-Sr isotopic geochemistry of granitoids and the isotopic chronology and geochemistry of the ophiolites in this area, especially the Kule Lake ophiolites. 25 precise SHRIMP U-Pb zircon and LA-ICPMS U-Pb zircon ages have been obtained in this dissertation. The granitic rocks in western Tianshan had been formed during two periods: the granitic gneiss with an age of 896Ma, possibly representing the forming age of the Precambrian basement; the granitic rocks with ages varying from 479Ma to 247Ma, recording the Paleozoic orogenic process of western Tianshan. The granitoids in western Tianshan are composed of intermediate-basic rocks, intermediate rocks, intermediate-acid rocks and acid rocks, mainly intermediate-acid rocks and acid rocks. They are mostly granite, granodiorite, quartz syenite and monzodiorite. Different types of granitic rocks are exposed in different tectonic units. The granitoids on the northern margin of the Yili Plate mainly formed in late Paleozoic (413Ma ~ 281Ma), those with ages varying from 413Ma to 297Ma show continental arc affinities and the magnesian calc-alkalic metaluminous diorite of 281Ma display the geochemical characteristics similar to those of granites formed during the post-orogenic period. The granitiods on the southern margin of the Yili Plate include the adakite diorite of 470Ma which was formd by partial melting of thickened lower crust, the post-collisional alkali-feldspar granite of 430Ma, the volcanic arc granite of 348Ma and the Triassic post-collisional granite. The granitoids in the Central Tianshan Plate formed in 479Ma ~ 247Ma, mainly in 433Ma ~ 321Ma. The granitic rocks with ages of 479Ma ~ 321Ma are magnesian calc-alkalic to alkalic rocks with continental arc affinities. A few post-collisional granitoids of 276Ma ~ 247Ma may have inherited the geochemical characteristics of pre-existing arc magma. The granitic rocks in Southern Tianshan (northern margin of the Tarim plate) formed two stages, 420Ma ~ 411Ma and ca. 285Ma. The magnesian calcic to alkalic granites of 420Ma ~ 411Ma may formed during the extension process of the continental margin. The granite of 285Ma includes mostly ferroan calc-alkalic to alkali-calcic rocks with high SiO2 and high alkaline contents, and obviously negative anomaly of Eu, Ba, Sr, P, Ti, similar to the geochemical characteristics of the A-type granite which is formed during post-collisional extension. The Kule Lake ophiolite in southern Tianshan shows the affinity of N-MORB. A SHRIMP zircon U-Pb age of 425±8Ma has obtained for gabbros. Some zircons have given another group of 206Pb/238U age 918Ma, which may indicate the information of the pre-exist old basement rock. The small oceanic basin represented by Kule Lake ophiolite probably developed on the split northern margin of Tarim block. A model for Paleozoic tectonic evolution of the West Tianshan Orogen has been proposed here on the basis of the new results obtained in this dissertation and the previous published data. In Early Cambrian, the Terskey Ocean occurred along the North Nalati fault (NNF), and it separated the Yili plate from the Central Tianshan plate which was probably connected with the Tarim plate. The Terskey Ocean probably subducted towards south under the Central Tianshan plate and towards north under the Yili plate simultaneously. In the early stage of Late Ordovician, the Terskey Ocean had been closed, and the Yili and Central Tianshan plates collided. Meanwhile, extension happened within the joint Central Tianshan and Tarim plates gradually and the Paleo-South Tianshan Ocean had been formed. In Early Silurian, the Paleo-South Tianshan Ocean began to subduct beneath the composite Yili-Central Tianshan plate, which was intruded by volcanic arc granitoids. In Middle Silurian, the Paleo-South Tianshan Ocean, which had reached a certain width, was subducting strongly. And this subduction may have produced voluminous granitoids in the Central Tianshan plate. In the latest stage of Carboniferous, the Paleo-South Tianshan ocean closed, and the Yili-Central Tianshan plate and Tarim plate collided. In Late Cambrian, Paleo-Junggar Ocean occurred to north of the Yili plate; and started to subduct towards south under the Yili plate in Ordovician. This subduction may have produced a magma arc on the northern margin of the Yili plate. In Late Carboniferous, the Paleo-Junggar Ocean had been closed. The Yili-Central and Junggar plates amalgamated together. The West Tianhan Orogen may undergo a post-collisional collapse since Permian. And the magmatic activities may continue to early Triassic. The initial 87Sr/86Sr ration of the granitic rocks in the western Tianshan Mountains varies from 0.703226 to 0.716343, and Nd（t）from -6.50 to 2.03. The characteristics of Sr-Nd isotope indicate that the source of granitic material is not a sole source, which may be produced by mantle-crust magma mixing. In Paleozoic time, lateral growth of the continental crust along active continental margins was dominant, whereas the vertical growth of continental crust resulted from post- collisional mantle derived magmas was not obvious.

800MPa下泥质岩部分熔融实验研究：残留相及熔体相REE地球化学特征

利用JL-3600t压机实验研究了800MPa、不同温度条件下泥质岩部分熔融过程，利用EMPA和LA-ICPMS分别测定了熔体相和残留相中主要化学组成以及微量元素（包括REE）组成。实验结果表明，泥质岩低程度部分熔融（〈25％）形成的熔体中REE含量分布于308．8-3565μg／g较大范围内，显示较大的不均匀性，其REE球粒陨石标准化分布模式显示弱的M型REE“四分组效应”，而残留相矿物石榴子石中REE含量变化于167．5—1008μg／g范围，也显示有明显的不均匀性，其REE球粒陨石标准化分布模式显示明显的W型REE“四分组效应”，尤以第一段La-Nd最为显著；随着部分熔融程度的增加（〉30％），其形成的熔体中REE集中在523．2—1130μg／g范围，残留相石榴子石中BEE集中在288．6—512．7μg／g范围，均显示相对均匀；熔体相和残留相石榴子石矿物的REE球粒陨石标准化分布模式不发育REE“四分组效应”。实验前后Cl质量平衡计算的结果表明该实验过程中并没有产生岩浆挥发分相。上述特征表明S型花岗岩中的REE“四分组效应”现象很可能与泥质岩低程度部分熔融具有成因联系。

东海和冲绳沉积物中自生铀蓄积过程及控制机理

采用同位素稀释ICP—MS测定法，对中国东海陆架及日本冲绳海槽的6个沉积物芯中U和Th的同位素地球化学行为进行了研究，以了解氧化还原敏感元素U在近海次氧化性沉积物中的蓄积行为，并评价其在全球海洋铀平衡中的意义。东海沉积物芯中，^238U浓度及^238U／^232Th比值随深度变化不明显。但是在冲绳海槽沉积物芯中，^238U浓度及^238U／^232Th比值在沉积芯表层氧化带显示较低值，然后在次氧化层随深度增加而增加。^230Th和^232Th浓度在所有沉积物芯中基本不随深度变化。这些结果说明，冲绳沉积物中有“自生铀”的蓄积过程发生，蓄积速率约为（47±5）-（90±8）ng／（cm^2·a），与文献报道的世界其他海域次氧化性沉积区大致相当。进一步证明了U在近海次氧化性沉积区的蓄积对于全球海洋铀平衡有重要意义。“自生铀”的主要蓄积机制是海水U（Ⅵ）向沉积物迁移，在还原条件下被还原为惰性的U（Ⅳ）并被吸附在沉积物固体相上。

离子色谱-等离子体质谱联用测定热泉水样的砷形态

利用阴离子色谱与六极碰撞等离子体质谱联用的方法, 在线同时测定水样的4 种砷形态(As ( Ⅴ) , As ( Ⅲ) , MMA , DMA) , 并用于实际样品2热泉水中砷形态的测定。使用K2 HPO42KH2 PO4 为淋洗液等度淋洗, 用Hamilton PRP2X100阴离子色谱柱分离, 4 种砷形态在7 min 之内完全分离。调节淋洗液中K2HPO4与KH2 PO4 的比例可以优化峰的分离。地下水(含热泉水) 基质、样品及淋洗液中的Cl - 对砷形态的分离测定没有影响, 淋洗液中的盐份在样品锥和截取锥上的积累对测定的影响很小。检出限分别为As ( Ⅴ) 0123μgPL , As ( Ⅲ) 0130μgPL ,MMA 0126μgPL , DMA 0154μgPL 。

多接收器等离子体质谱仪测钕同位素比值的质量歧视校正初探

利用国内首次引进的Nu Plasma型MC-ICPMS,对Nd同位素测试过程的质量歧视效应特征进行了研究.发现该类仪器测试过程的质量歧视效应并不完全符合指数函数,也不符合幂函数.质量歧视引起的同位素分馏随同位素对的平均质量数变化,但不严格遵从线性关系.只是在较小质量范围内呈近似线性关系.据此,用双分馏系数校正法可以获得143Nd/144Nd的校正系数,并用来校正143Nd/144Nd值.用此方法获得的JNdi-1的143Nd/144Nd值为O.512 107±O.OOO 008(2RSD),在测量误差范围内与TIMS测定值完全吻合.

临沧锗矿床的微量元素地球化学

采用ICP—MS测定了临沧锗矿中51个含矿煤、5个无矿煤、9个硅质岩样品的微量元素含量，并与基底二云母花岗岩进行对比，探讨了含矿煤与无矿煤的微量元素地球化学及其与锗超常富集的关系，得出几点认识：a.含矿煤、无矿煤和硅质岩中的大多数微量元素来自基底的二云母花岗岩；b．热水携带了成矿所必需的锗；c．Nb可作为锗矿化的指示元素。

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。

铜同位素的分馏机制及其在矿床学研究中的应用

作为一种重要的成矿元素，铜广泛分布于不同地质体中，并广泛参与成岩成矿作用。近年来，由于同位素分析方法的改进和新一代多接收等离子质谱仪（MC-ICPMS）的应用，使得铜同位素的高精度测试成为现实，并已成为国际地学领域的一个前沿研究方向。铜同位素在自然界中具有较大的变化范围，δ^65Cu值介于-3．03‰～5．74‰之间。本文介绍和评述了铜同位素的分析方法和可能的分馏机制，并根据已发表数据，重点讨论了铜同位素组成与成矿温度、矿化阶段和成矿物质来源的关系。认为铜同位素有可能作为一种灵敏的地球化学示踪剂，对指示成矿物质来源、成矿作用过程和矿床形成机理具有重要作用。

大洋岛屿玄武岩低温蚀变作用及其对大洋过渡金属循环的贡献

用化学方法和ICP—MS方法分别对中、西太平洋海山富钴铁锰结壳产出区玄武岩的主元素、 微量元素和稀土元素(REE)含量进行了测定，结果表明，研究区玄武岩经受了强烈的洋底低温蚀 变作用，主元素成分发生了明显的变化，失去了原岩的特征．样品与新鲜大洋岛屿玄武岩(OIB) 极为相似的稀土元素配分模式和微量元素含量特征表明，所研究的岩石属典型的大洋板内玄武 岩．受洋底低温蚀变作用的影响，样品的Al O。，Fe O。，MnO、K O，P O 含量增加，MgO，FeO 的 含量降低．蚀变作用使大洋岛屿玄武岩中的镁、铁等活动组分大量流失，从而表现出相对富SiO 的特征(标准矿物计算结果中出现石英)． 由于蚀变作用，活动组分的流失使样品的REE相对富 集，而富REE铁锰氧化物在玄武岩气孔和裂隙中的沉淀不仅使样品的REE含量增大，而且引起 轻稀土元素(LREE)与重稀土元素(HREE)分馏，表现为Σf(Ce)／Σf(Yb)值增大． 以REE 富集 机制为基础，对样品中铁锰氧化物的沉淀量和单位质量新鲜玄武岩中活动组分的流失量进行了理 论计算，结果表明，因低温蚀变作用所引起的新鲜玄武岩的单位质量亏损为0．150t0．657，而单 位质量新鲜玄武岩中铁锰氧化物的沉淀量为0．006t0．042．主元素中以铁、镁的流失亏损最为明 显，新鲜玄武岩中铁、镁的流失比例分别为18．28 ～70．95 和44．50％～93．94％ ，超过了岩石 总量的流失亏损比例(15．0 ～65．7 )，因而样品相对贫铁、镁．其他元素的流失量和流失比例 都很好地印证了地球化学研究的结果．样品中铝、钾、磷负的流失量是由于沸石在岩石气孔中的充 填和岩石的磷酸盐化．理论计算结果和地球化学研究都表明，大洋岛屿玄武岩的低温蚀变向海水 提供了大量金属，这是大洋海水中金属循环的重要环节．