Ar和H在矿物中的扩散补偿关系及其对扩散系数的预测

对现有实验扩散数据的检查发现 ,Ar和H两种元素在不同矿物中分别存在着扩散补偿关系。孔隙度作为矿物内部离子堆积密度的一种量度 ,它与Ar和H的扩散活化能之间存在负的线性相关性 ,因而可以用于预测元素在矿物中的扩散系数。文中采用离子孔隙度法预测了Ar和H在不同矿物中的扩散系数 ,得到的结果与已有的实验数据在实验误差范围内是一致的。由于扩散补偿效应 ,同一物质在不同矿物中的扩散速率在特定温度下趋于汇聚 ,Ar扩散的转折温度为 (86 0± 10 0 )℃ ,H扩散的转折温度为 (330± 50 )℃。这为地质过程中Ar和H扩散的封闭温度提供了一种借鉴 ,因此伴随Ar扩散的地质时钟在低于 86 0℃时才开始启动 ,共存矿物间的氢同位素地质温度计仅当温度低于 330℃时才是有效的。     

南秦岭东江口岩体群Pb,Sr和Nd同位素地球化学特征及其对物源的制约

以区域地球化学研究成果为基础,通过Ｐｂ、Ｓｒ、Ｎｄ同位素特征分析,揭示出东江口岩体群的Ｐｂ同位素特征与南泰岭东段基底具有耦合关系,而与其它构造单元则存在明显的差异,＾２０４Ｐｂ－＾２０７Ｐｂ／＾２０６Ｐｂ,＾２０４Ｐｂ－＾２０８Ｐｂ／＾２０６Ｐｂ图解研究表明,该岩体群为下地壳源花岗岩类,Ｎｄ同位素特征（ｔＤＮ和εＮｄ（ｔ）表明,耀岭河群最适合于作为岩体群的主要物源。该岩体群和耀岭河群的Ｓｒ同位素存     

矿物中稀土元素扩散作用的理论研究及其扩散参数的预测

矿物中的微量元素在地质环境下能否保持有效封闭,主要取决于其扩散性质,而稀土元素(REE)是探讨地质作用过程及其物理化学条件等重要的示踪剂,查明其在不同矿物中的扩散行为对于地学研究具有重要意义。本文通过分析矿物晶格结构和离子类型对元素扩散行为的制约规律,探讨了REE在不同矿物中的扩散迁移。在此基础上,利用多元统计分析方法得出扩散参数与扩散体系不同晶体化学参数之间的关系方程,建立了计算1atm、无水环境下REE在不同矿物中扩散参数的多变量模型,由此模型预测的REE在不同矿物中的扩散参数E和lnD0的值,与实验测定结果在实验误差范围内具有很好的一致性。与以往的预测模型相比,多变量模型能更全面地反映扩散体系晶体化学因素对扩散速率的制约。此外本研究结果显示,REE在矿物晶格中扩散作用的主要影响因素是阳离子,而非当前认为的阴离子。     

矿物电导率补偿效应研究及其对元素扩散性质的制约

根据已有的大量矿物电导率实验数据，我们观察到方解石、刚玉、顽火辉石、铁辉石、橄榄石、白榴石和方镁石电导率存在类似于元素扩散一样的补偿效应，即同一矿物在不同条件下测得电导率指前因子的对数lnσ0和活化能E之间有良好的线性关系，并利用橄榄石在不同时期、用不同样品得到的电导率数据进行了验证。文中还注意到同一矿物中不同导电机制或不同导电载流子产生的电导率也满足补偿效应，据此特点提出了应用矿物电导率补偿效应计算元素扩散系数中指前因子的新方法。     

Rare earth element and strontium isotope geochemistry in Dujiali Lake,central Qinghai-Tibet Plateau,China: Implications for the origin of hydromagnesite deposits

Rare earth element (REE) and strontium isotope data (⁸⁷Sr/⁸⁶Sr) are presented for hydromagnesite and surface waters that were collected from Dujiali Lake in central Qinghai-Tibet Plateau (QTP), China. The goal of this study is to constrain the solute sources of hydromagnesite deposits in Dujiali Lake. All lake waters from the area exhibit a slight LREE enrichment (average [La/Sm]_PAAS = 1.36), clear Eu anomalies (average [Eu/Eu*]_PAAS = 1.31), and nearly no Ce anomalies. The recharge waters show a flat pattern (average [La/Sm]_PAAS = 1.007), clear Eu anomalies (average [Eu/Eu*] _PAAS = 1.83), and nearly no Ce anomalies (average [Ce/Ce*]_PAAS = 1.016). The REE+Y data of the surface waters indicate the dissolution of ultramafic rock at depth and change in the hydrogeochemical characteristics through fluid-rock interaction. These data also indicate a significant contribution of paleo-groundwater to the formation of hydromagnesite, which most likely acquired REE and Sr signatures from the interaction with ultramafic rocks. The ⁸⁷Sr/⁸⁶Sr data provide additional insight into the geochemical evolution of waters of the Dujiali Lake indicating that the source of Sr in the hydromagnesite does not directly derive from surface water and may have been influenced by both Mg-rich hydrothermal fluids and meteoric water. Additionally, speciation modeling predicts that carbonate complexes are the most abundant dissolved REE species in surface water. This study provides new insights into the origins of hydromagnesite deposits in Dujiali Lake, and contributes to the understanding of hydromagnesite formation in similar modern and ancient environments on Earth.     

“寨背式”离子吸附型稀土矿床多类型稀土矿化及其成因

赣南寨背离子吸附型稀土矿床产于寨背复式花岗岩体的风化壳中,自20世纪80年代发现以来一直以轻稀土型开采,近年在轻稀土型花岗岩风化壳中发现了重稀土矿。为了探讨轻稀土型花岗岩风化过程中重稀土元素的迁移、分馏和富集机制,本文选择了区内三个具有代表性的风化壳钻孔（ZK1、ZK2和ZK4）对其进行了全相和离子交换相稀土元素地球化学研究。结果显示：钻孔ZK4中离子交换相稀土含量介于14.90×10^-6~835.8×10^-6之间,并富集轻稀土（LREE/HREE=2.28~10.78）;钻孔ZK1中离子交换相稀土含量达1470×10^-6（9件样品均值）,具有从轻稀土型向重稀土型过渡的配分特征（LREE/HREE=1.30~1.65）,并且剖面自上而下显示轻、重稀土逐渐富集的趋势;钻孔ZK2中离子交换相稀土含量为492.4×10^-6（8件样品均值）,自上而下稀土配分类型从轻稀土型过渡至重稀土型（LREE/HREE=0.43~2.25）,且轻稀土富集在全风化层上部而重稀土则富集在下部。三个钻孔的Nb/Ta和Zr/Hf比值与寨背花岗岩过渡相的黑云母正长花岗岩比值范围相近。此类岩石的稀土配分类型具有从轻稀土型（LREE/HREE>3.20）向过渡型转变的特征（LREE/HREE=1.45~2.65,Y/REE=15%~25%,前人称之为中钇轻稀土型）。由此推测：风化壳ZK4的母岩可能是轻稀土型黑云母正长花岗岩,其稀土配分类型继承了母岩特征。风化壳ZK2和ZK1的母岩可能为中钇轻稀土型黑云母正长花岗岩。ZK2中从母岩释放出的较高浓度的重稀土向剖面下部迁移,逐渐增大了轻、重稀土的分馏程度,最终使风化壳的稀土配分类型从轻稀土型转变为重稀土型。与ZK2相比,ZK1具有较高的风化蚀变指数（CIA值）,随风化程度增加富集在风化壳上部的轻稀土逐渐向下迁移,而已富集在下部的重稀土部分从剖面中迁出至地表水从而缩小了轻、重稀土的分馏程度,剖面ZK1的稀土配分类型均为过渡型。可见,华南地区中钇轻稀土型母岩风化后可形成重稀土矿体/矿层。

     

湖南香花铺钨矿床含钙矿物的稀土元素地球化学

香花铺矿床是湘南地区唯一的萤石-白钨矿型矿床。本文利用高精度LA-ICP-MS对该矿白钨矿和方解石中的稀土元素进行了原位分析。结果表明,该矿的白钨矿表现为LREE富集和正Eu异常特征,方解石则具有LREE富集型和相对平坦型两种稀土配分模式,且均呈现负Eu异常特征。该矿属于与岩浆活动有关的热液矿床,成矿流体在还原环境下的运移过程中,首先结晶出白钨矿和LREE富集型方解石,而后沉淀形成了具有相对平坦型REE模式的方解石。此外,稀土元素在该区矿物中的分布存在明显的不均一现象,在不同微区REE的含量、配分模式以及分异程度等均可能存在差异,其原因除了结晶过程中水动力学条件的变化,还可能与矿物结晶后颗粒外表层受流体作用的改造有关。     

Pb and rare earth element diffusion in xenotime

Diffusion of Pb and the rare earth elements Sm, Dy and Yb have been characterized in synthetic xenotime under dry conditions. The synthetic xenotime was grown via a Na₂CO₃–MoO₃ flux method. The sources of diffusant for the rare earth diffusion experiments were REE phosphate powders, with experiments run using sources containing a single REE. For Pb, the source consisted a mixture of YPO₄ and PbTiO₃. Experiments were performed by placing source and xenotime in Pt capsules, and annealing capsules in 1 atm furnaces for times ranging from 30 min to several weeks, at temperatures from 1000 to 1500 °C. The REE and Pb distributions in the xenotime were profiled by Rutherford Backscattering Spectrometry (RBS).The following Arrhenius relations are obtained for diffusion in xenotime, normal to (101):

Diffusivities among the REE do not differ greatly in xenotime over the investigated temperature range, in contrast to findings for the REE in zircon [Cherniak, D.J., Hanchar, J.M., Watson, E.B., 1997. Rare earth diffusion in zircon. Chem. Geol. 134, 289–301.], where the LREE diffuse more slowly, and with higher activation energies for diffusion, than the heavier rare earths. In zircon, these differences among diffusion of the rare earths are attributed to the relatively large size of the REE with respect to Zr, for which they likely substitute in the zircon lattice. With the systematic increase in ionic radius from the heavy to lighter REE, this size mismatch becomes more pronounced and diffusivities of the LREE are as consequence slower. Although xenotime is isostructural with zircon, the REE are more closely matched in size to Y, so in xenotime this effect appears much smaller and the REE diffuse at similar rates. In addition, the process of diffusion in xenotime likely involves simple REE^+ 3 → Y^+ 3 exchange, without charge compensation as needed for REE^+ 3 → Zr^+ 4 exchange in zircon. This latter factor may also contribute to the large activation energies for diffusion of the REE in zircon (i.e., 691–841 kJ mol^− 1, [Cherniak, D.J., Hanchar, J.M., Watson, E.B., 1997. Rare earth diffusion in zircon. Chem. Geol. 134, 289–301.]), in comparison with those for xenotime.For Pb, the following Arrhenius relation is obtained (also normal to (101)):

These measurements suggest that Pb diffusion in xenotime is quite slow, even slower than Pb diffusion in monazite and zircon, and considerably slower than diffusion of the REE in xenotime. Xenotime may therefore be even more retentive of Pb isotope signatures than either monazite or zircon in cases where Pb isotopes are altered solely by volume diffusion. However, because the activation energy for Pb diffusion in xenotime is lower than those for monazite and zircon, Pb diffusion may be somewhat faster at many temperatures of geologic interest in xenotime than in monazite or zircon.     

广西大厂锡多金属矿床方解石的REE地球化学特征

方解石是广西大厂锡多金属矿床矿石中重要的脉石矿物.对不同产状矿体中方解石的REE地球化学特征研究表明方解石在不同类型矿体中REE含量、有关参数和稀土配分模式等均变化较大,但在地球化学特征上具有连续变化规律,显示同源不同阶段的产物;矿床的成矿流体具有岩浆来源的特征,不排除地幔来源的可能;成矿环境表现为还原向氧化环境的变化.     

桂东北黄关萤石矿床稀土元素和氢氧同位素特征

桂东北地区热液脉状萤石矿床数量众多,但萤石矿床的成矿流体性质和矿质来源不甚清楚。本文以黄关萤石矿床作为研究对象,在详细野外地质调查的基础上开展了萤石稀土元素测试及氢氧同位素研究,并与都庞岭花岗岩的全岩稀土元素特征进行对比。结果显示：萤石ΣREE = 38.08×10^-6~83.23×10^-6,花岗岩围岩ΣREE = 122.02×10^-6~199.56×10^-6,围岩花岗岩与萤石的稀土元素配分曲线均呈右倾型,具有同步性,表明矿物形成与围岩花岗岩关系密切;Eu无明显异常,Ce弱负异常或异常不明显,指示萤石在相对氧化的环境下形成;氢氧同位素测试结果显示,δD_V-SMOW介于-50.4‰~-34.7‰,δ¹⁸O_V-SMOW介于-9.8‰~-5.5‰,认为成矿流体以大气降水为主。矿床成矿物质F来自于都庞岭花岗岩体,Ca主要来自地层,部分来自岩体。

     

湛江湾海域表层沉积物稀土元素特征及其物源指示意义

通过对湛江湾近海海域表层沉积物样品粒度和稀土元素(RE E)测试分析,系统地研究海域沉积物稀土元素地球化学特征并探讨其物质来源.结果表明,研究区沉积物的稀土元素含量变化较大,平均值为163.23μg/g,湾外的REE含量(168.61μg/g)高于湾内的REE含量(142.17μg/g);不同类型沉积物的稀土元素含量存...     

桌子山中奥陶统克里摩里组下段稀土元素特征与沉积介质分析

鄂尔多斯盆地西缘北部的内蒙古桌子山地区奥陶纪地层出露完整,沉积类型丰富,是研究鄂尔多斯盆地西缘奥陶纪沉积的关键地区。该区在中奥陶世时位于从浅海向深海的转换部位,达瑞威尔期沉积的克里摩里组由深灰色薄层状石灰岩和灰黑色泥岩组成,是研究鄂尔多斯盆地西缘奥陶纪深水氧化-还原条件的一个较为理想的层位。本文在详细的野外观察基础上,测试克里摩里组薄层细粉晶-泥晶石灰岩和灰黑色泥岩的稀土元素（REY）和其他与氧化-还原条件相关的微量元素,主要包括V、Cr、Ni、Co等,着重分析探讨其形成时的氧化-还原条件。结果表明：1）石灰岩和泥岩稀土总量（REE）分别为28.18×10^-6和100.37×10^-6,轻、重稀土比值分别为9.60和9.69;2）石灰岩和泥岩稀土元素Y/Ho、（La/Yb）_N、（La/Sm）_N、（La/Nd）_N值分别为29.01、1.35、0.92、0.95和25.72、1.21、0.96、1.02;3）石灰岩无Ce负异常或具有微弱的正异常,同时具有明显的Eu正异常,泥岩具有明显的Ce负异常和较弱的Eu正异常;4）石灰岩和泥岩的其他微量元素比值V/Cr、V/（V+Ni）、Ni/Co分别为1.10、0.62、7.75和3.54、0.89、5.15。依据本文研究结果,结合沉积特征和前人研究成果可以推测,克里摩里组沉积于风暴浪基面之下,远离海岸,但同时又受淡水影响,其中石灰岩形成于氧化环境,泥岩形成于还原环境,同一沉积背景下这种氧化与还原环境的交替是由等深暖流造成的,可称为水动力氧化环境。