中国海岸风成沙ESR测年的研究

介绍ＥＳＲ测年的基本原理，并讨论风成沙Ｇｅ心测年的可行性、风成沙Ｅ＇心的特征、测年误差及可靠性等问题。１９９２－１９９３年在渤、黄、东、南海沿岸采集的１００余个风成沙样品ＥＳＲ测年实验表明，绝大部分海岸风成沙的年龄为１－７万年。     

Monte Carlo simulation of mixing in Ca3Fe2Ge3O12–Ca4Ge4O12 garnets and implications for the thermodynamic stability of pyrope–majorite solid solution

Static lattice energy calculations, based on empirical pair potentials, were performed for a large set of structures differing in the arrangement of octahedral cations within the garnet 2 × 2 × 2 supercell. The compositions of these structures varied between Ca₃Fe₂Ge₃O₁₂ and Ca₄Ge₄O₁₂. The energies were cluster expanded using pair and quaternary terms. The derived ordering constants were used to constrain Monte Carlo simulations of temperature-dependent mixing properties in the ranges of 1,073–3,673 K and 0–10 GPa. The free energies of mixing were calculated using the method of thermodynamic integration. The calculations predict a wide miscibility gap between Fe-rich (cubic) and Fe-pure (tetragonal) garnets consistent with recent experimental observations of Iezzi et al. (Phys Chem Miner 32:197–207, 2005). It is shown that the miscibility gap arises due to a very strong cation ordering at the Fe-pure composition, driven by the charge difference between Ca²⁺ and Ge⁴⁺ cations. The structural and thermodynamic analogies between Ca–Ge and Mg–Si systems suggest that a similar miscibility gap should exist between pyrope and Mg–Si-majorite.     

会泽铅锌矿床中自然锑的发现及伴生元素的分布特征

文章对会泽铅锌矿床的主要矿体进行了系统观察、采样，对其矿石进行了岩矿鉴定、化学分析(包括部分单矿物)和电子探针分析，并对其成矿作用做了探讨。首次在矿石中发现了自然锑，初步查明整个矿床中Ag，Cd，Ge，Cu，Sb等伴生元素的平均含量(wB／10^-6)分别为121．77、660．99、62．10、203．78和169．87，认为它们是晚成矿阶段形成的。     

P–T–t evidence for mechanisms of vertical tectonic motion in a contractional orogen: north-western US and Canadian Cordillera

The >1800 km long Coast Mountains–North Cascades orogen of the Canadian Cordillera and north-western US developed as a continental magmatic arc. Metamorphic rocks in the orogen contain widespread evidence for burial of supracrustal rocks to depths of c. 40 km, followed by nearly isothermal decompression to depths of <10 km. Near many shallowly-emplaced, mid-Cretaceous plutons, low-pressure contact metamorphic effects were overprinted by high-pressure regional metamorphic minerals and textures, as evidenced by kyanite±staurolite pseudomorphs after andalusite in metapelitic rocks. Therefore, near-pluton rocks record the loading history of the orogen. Metapelitic rocks not associated with plutons only preserve evidence for high-pressure conditions and/or high-temperature decompression, as indicated, for example, by sillimanite and cordierite after kyanite and garnet, respectively. Petrological evidence for burial and decompression is therefore recorded in different rocks. Various regions of the orogen differ in timing of metamorphism, the overall shape of P–T paths and the relative timing and regional extent of the high-pressure event, but most of these data and observations are consistent with thrusting and/or pure shear thickening as primary loading mechanisms throughout the orogen, as opposed to magma-dominated loading. This interpretation is further supported by comparison with thermal models, which demonstrate that the P–T paths are consistent with simultaneous thrusting and folding at a high initial geothermal gradient (35–40 °C km^?1) in much of the orogen. A high geothermal gradient supports tectonic models invoking intra-arc contraction and suggests that magmatism played an important role in regional temperature-time paths. This tectonic-thermal history may be typical of other contractional orogens and illustrates the importance of large vertical displacement of crust in magmatic arcs.     

A late Pliocene diatom Ge/Si record from the Southeast Atlantic

As a result of both culture and sediment core studies, the ratio of germanium (Ge) to silicon (Si) in diatom shells has been proposed as a proxy for monitoring whole-ocean changes in seawater Ge/Si, a ratio affected by changes in continental weathering. However, because of the difficulties of extracting and cleaning diatom frustules from deep-sea sediments, only samples from highly pure diatom oozes in the Antarctic region have been previously analyzed. Here we present data on diatom Ge/Si ratios, (Ge/Si)_opal, for the time interval between 3.1 and 1.9 Ma from a mid-latitude, coastal upwelling area where significant terrigenous sediment input complicated the sample processing and analyses. In general, our (Ge/Si)_opal values show the same decreasing trend after 2.6 Ma than previously measured in Antarctic sediments (Shemesh et al., 1989. Paleoceanography 4, 221–231), but with a noisier background that may reflect the local imprint of proximal continental input superimposed upon global changes in the ocean reservoir. The time of initiation of large-scale North Hemisphere glaciation at 2.6 Ma is characterized by a declining pattern of diatom Ge/Si ratios, which could have resulted from a global increase in the input of riverine Si due to enhanced silica weathering and/or equatorward (northward) intrusions of subantarctic waters enriched in silica. High (Ge/Si)_opal ratios are associated with high opal contents from the same sediment samples and with warm climate as indicated by depleted benthic foraminiferal δ¹⁸O values from the North and Equatorial Atlantic. Cold periods signified by enriched benthic δ¹⁸O values, on the contrary, are associated with lower (Ge/Si)_opal ratios. We interpret diatom Ge/Si values to reflect the prevailing weathering state on the continents, with greater chemical weathering during warm and wet periods of the Pliocene and less during cooler and drier intervals.     

川滇黔铅锌(锗)成矿区区域地球化学测量在找锗预测中的作用

锗作为一种稀散元素,是现代信息产业最重要的金属之一,然而大多数锗资源是在综合评价煤矿床、铅锌矿床以及铁矿床的过程中发现的,缺乏专门的找锗方法。为了进一步加强锗矿找矿方法的研究,本文以川滇黔接壤处作为研究区,通过采用探索性分析方法(EDA)和基于分形理论的浓度-面积(C-A)方法以及证据权模型,分析研究区内低密度水系沉积物测量数据Zn、Ge元素的数字特征和分布规律。结果表明:(1) Ge元素分布由单个总体构成,基本符合正态分布,数值变化小(变异系数=0. 13),基本围绕地壳丰度值(1. 6×10~(-6))波动,且矿床的分布与地球化学异常之间没有明显的相关关系,因此采用以Ge找Ge的思路是行不通的,而这可能是由于Ge在表生氧化状态下的多亲和性和高度分散性造成的。(2) Zn元素分布明显不符合正态分布,且有多个峰值,数据离散程度大(变异系数=1. 14),可能至少由两个以上总体构成,且在空间上矿床的分布与地球化学异常之间有良好的相关关系,大多数矿床位于相对高值区。另外鉴于在原生状态下,Ge元素往往以类质同象的形式赋存在闪锌矿中,因此在区域上采用以Zn找Ge的思路是可行的。(3)采用累计概率法、直方图法、箱式图法、原生晕法以及基于多重分形的C-A方法,确定的异常下限分别为146. 5×10~(-6)、392. 7×10~(-6)、153. 9×10~(-6)、87. 5×10~(-6)和124×10~(-6)。通过采用证据权方法所提供的空间相关性统计量(t)进行检验,发现异常下限应当落在120×10~(-6)～130×10~(-6)的区间内。因此基于分形理论的C-A方法是最合理的,这可能是其不仅考虑了频数特征,还考虑了空间几何特征的原因。(4)在圈定地球化学块体的基础上,结合热液矿床受构造控制,且往往具有"丛聚效应"以及"鹤立鸡群"的特点,圈定黑区-赤普、大湾子-大桥边、茂租-乐红、毛坪、天宝山-小石房、猫猫厂-白蜡厂、大梁子、会泽、青山-杉树林、猴子厂-顶头山以及富乐作为寻找锗矿的潜力区,建议进一步加强这11个矿田级远景区锗资源的找矿工作。     

分散元素(Ge,Cd, Tl)稳定同位素研究

近年来,非传统稳定同位素地球化学得到了飞跃性的发展,其主要研究对象为海洋体系的演化。特别是氧化还原敏感元素(Se,Mo,Fe等)稳定同位素已经在古海洋环境的示踪研究中发挥重要的作用。相比分散元素(Ge,Cd,Tl)稳定同位素研究比较薄弱,但这些元素在海洋体系中有特殊的循环模式,这使得它们的同位素研究将可能存在很大地质潜力。海洋体系中它们的源汇简单,而且有机无机吸附过程都可能导致同位素分馏。Ge,Cd,Tl均属于挥发性元素,原始星云的形成过程可能存在较大的同位素分馏。我国南方大面积的低温成矿域,将为Ge,Cd,Tl稳定同位素的发展提供天然的平台。另外,Cd,Tl是环境污染的主要潜在元素,因此采用稳定同位素示踪还可能示踪表生环境中的污染来源。     

临沧锗矿床的稀土元素地球化学研究

通过对临沧锗矿床中基底花岗岩、矿化煤以及硅质岩的稀土元素地球化学研究认为盆地基底花岗提供了形成锗矿化的锗和形成硅质岩的硅；本区陆相热水成因硅质岩的Ce异常不明显，相对富集LREE；矿化煤相对富集HREE，这可能主要与矿化煤在含锗热液的相互作用过程中，煤对重烯土的优先富集有关。     

Determination of Ge, As, Se and Te in Silicate Samples Using Isotope Dilution-Internal Standardisation Octopole Reaction Cell ICP-QMS by Normal Sample Nebulisation

A method for the determination of Ge, As, Se and Te in silicate samples using isotope dilution-internal standardisation (ID-IS) octopole reaction cell (ORC) ICP-QMS by normal sample nebulisation was developed. The method does not involve either hydride generation or ion exchange. Germanium, Se and Te were determined by isotope dilution (ID), and As was determined by ID-IS. A silicate sample with an added Ge-Se-Te spike was digested with an HF-HNO₃-HBr mixture, dried, re-dissolved with HF and the supernatant liquid was directly aspirated into an ORC-ICP-QMS instrument with He or H₂ gas. No matrix effects were observed down to a dilution factor (DF) of ∼ 70 for Ge, Se and Te and DF of ∼ 1000 for As, which resulted in 3s detection limits in silicates of 2, 1, 0.1 and 4 ng g⁻¹, respectively. Advantages of the method are the simple sample introduction as well as a capability of determining S, Ti, Zr, Nb, Mo, Sn, Sb, Hf and Ta by ID-IS-ICP-QMS/SFMS from the same solution. Furthermore, the total sample solution consumption was only 0.253 ml with DF = 2000. Therefore, only a 0.13 mg test portion was required. To demonstrate the applicability of this technique, Ge, As, Se and Te in eight silicate reference materials were determined, as well as S, Ti, Zr, Nb, Mo, Sn, Sb, Hf and Ta in four carbonaceous chondrites.     

贵州半边街锗锌矿床锗的富集特征及其地质意义

锗(Ge)属于战略性关键矿产资源, 是众多高新技术领域的重要原材料。Ge主要以共/伴生形式产出于Zn、Pb和Cu等热液贱金属矿床和煤矿床中, 目前全球Ge资源主要来源于铅锌矿的副产品。近期取得较大找矿突破的半边街锌矿床(7.70Mt矿石, Zn平均品位5.1%)伴生有超大型规模的金属Ge(>900t @110×10-6), 然而Ge超常富集的机制不清。本次研究利用LA-ICPMS对闪锌矿进行了微区原位微量元素组成和Mapping分析, 以揭示Ge等元素的富集特征、赋存状态和替代方式, 探讨Ge的富集机制。分析结果表明, 半边街矿床闪锌矿中高含量(平均值>100×10-6)微量元素有Fe、Pb、Ge和Cd等, 较高含量(平均值100×10-6~10×10-6)的有Mn、Ga、Sn和Tl, 以及较低含量(平均值< 10×10-6)的有Ag、Cu、In和Sb。相比于各类型铅锌矿床, 半边街闪锌矿Ge超常富集(274×10-6~1938×10-6, 平均为1055×10-6, 达到1000倍富集)。该矿床中Ge以类质同象或纳米颗粒形式赋存于闪锌矿中。微量元素摩尔量相关性图揭示Ge替代Zn的方式以Ge4++Pb2+↔3Zn2+为主, 其次为nGe4++Mn2+↔(2n+1)Zn2+和nGe4++2Tl3+↔(2n+3)Zn2+。综合分析认为, 半边街矿床Ge可能来源于相对富Ge的前寒纪基底; 富有机质的盆地流体在Ge的搬运中发挥重要作用; Ge、Cd等稀散元素的共生分异制约了Ge的最终超常富集。因此, 半边街矿床中Ge的超常富集是"源、运、聚"复杂过程多要素耦合作用的结果。