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。     

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。     

矿物之间的元素和同位素平衡:地质测温和等时线定年的热力学和动力学控制

在特定的地质事件过程中,矿物等时线放射体系是否达到并且保持了平衡是变质岩Sm-Nd和Rb-Sr同位素年代学中的一个重要问题。在这个问题上矿物对O同位素测温与矿物等时线定年相似,因此两者之间可以相互制约。在岩浆岩和变质岩中,矿物中Sm-Nd、Sr和O之间的扩散速率在无水的条件下一般具有可比性,因此矿物之间O同位素的平衡状态可以用来对Sm-Nd和Rb-Sr定年的有效性进行检验。对大别-苏鲁造山带超高压变质岩的Sm-Nd和Rb-Sr等时线矿物进行O同位素测温,得到Sm-Nd等时线有时给出三叠纪年龄,有时给出非三叠纪年龄;对应的矿物O同位素分馏分别处于平衡和不平衡状态。对于引起非三叠纪等时线年龄的原因,一方面可以是由于榴辉岩相变质过程中同位素体系没有达到平衡,另一方面则可能角闪岩相退变质作用打破了平衡。等时线矿物中初始同位素比值的均一化速率主要受慢扩散矿物的影响,而矿物等时线时钟的启动主要受高母/子比值矿物控制。因此在变质作用过程中,只有当高母/子比值矿物同时具有快的放射成因同位素扩散速率,才可能得到有效的矿物等时线来用于变质年龄的测定。根据不同矿物中不同元素在扩散速率上的差异,能够定量估计大陆碰撞过程中榴辉岩相变质的持续时间。应用增量方法和离子孔隙度经验模型,不仅分别能够从理论上准确计算所有固体矿物的氧同位素分馏系数和获得不同矿物中元素的扩散参数,而且分别能够定量预测热力学平衡条件下共生矿物之间的¹⁸O富集顺序和相同条件下矿物中元素扩散速率的相对快慢。     

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。     

南岭地区花岗岩类的痕量元素分配特征

本文选择区内4个花岗岩体,对其中REE、Rb、Sr、Ba、Sc等痕量元素的分配特征进行研究。这些岩体产于不同地区,形成不同时代,大致可以代表区内主要类型的花岗岩类岩石。研究表明,在四类花岗岩中,随着岩石SiO_2含量和分异系数DI值的增大,岩石的Rb/Sr值相应增大,LREE/HREE、La/Yb、K/Rb值相应减小,意味着岩石的痕量元素分配与岩石的主元素成分间具有一定的相关关系。对比清湖和扶溪岩体REE在矿物之间的分配特征得知,除矿物的晶体化学性质是决定REE分配的主要因素外,REE在矿物之间的分配与矿物的晶出顺序也有关系。     

胶南榴辉岩矿物氧同位素平衡及其Sm-Nd年代学制约

对苏鲁地体中的胶南榴辉岩进行了矿物氧同位素分析，并与同一手标本矿物的Sm-Nd内部等时线定年和Nd-Sr同位素分布进行了对比。研究表明，石榴子石与绿辉石之间的氧同位素平衡与否能够对矿物Sm-Nd同位素体系的平衡状况和内部等时线定年结果的有效性给予直接制约。合理的石榴子石＋绿辉石Sm-Nd内部等时线年龄产于两矿物之间达到并在峰变质条件下保持氧同位素平衡的样品中，而两矿物之间处于氧同位素不平衡的样品不能给出正确的Sm-Nd内部等时线年龄。同一矿物在手标本尺度出现显著的O-Nd-Sr同位素不均一性，据此对这些元素在石榴子石和绿辉石中的扩散速率顺序进行了估计，不仅得到了与实验扩散系数相吻合的结果，而且由此估计出在峰变质条件下达到矿物内部同位素均一化所需要的时间应大于10Ma。     

长白山地区新生代火山岩的岩石化学及Sr、Nd、Pb同位素地球化学研究

通过主元素、稀土元素、Sr、Nd、Pb同位素地球化学特征并结合板块俯冲模式来讨论长白山地区新生代火山岩系的形成和演化。大部分样品都进入上地幔Sr演化范围,具低Sr高~(87)Sr/~(86)Sr特点;∑Nd介于-2.3—+2.9之间;不同岩性熔岩的Pb同位素组成变化不大。主元素、REE模式和同位素的资料都证实区内火山岩是源自上地幔的同源岩浆分异演化而成,并有地壳物质的混染。     

陆源碎屑沉积作用对化学元素配分的制约——兼论五台地区前寒武纪碎屑沉积岩示踪源区陆壳成分的意义

为探讨粒度分选沉积作用对沉积物化学成分配分的影响,对比研究了五台群中石英岩、长石石英岩、粉砂岩和粘土岩等不同粒度沉积岩的化学成分特征,结果表明:不同粒度沉积岩的主元素及微量元素均具有较大的变化范围,SiO_2与Al_2O_3及TFe_2O_3之间呈线性负相关关系,这种负相关关系还表现在SiO_2与REE,Rb,Sr之间,这种特征可以用石英的稀释作用进行解释;铁族元素Cr,Ni,Co和REE,Rb,Sr等大离子亲石元素与Al_2O_3呈正相关关系,表明这些元素易在富铝的粘土岩中聚积。不同粒度成分沉积岩的稀土     

大沟谷钠长石岩型金矿床Pb、S、Sr同位素特征初探

大沟谷金矿床产于震旦系乐晶峡群钠长石岩带底部陡倾斜钠长石岩中。金矿床铅同位素组成变化大^206Pb/^204Pb17.356-19.306,^207Pb/^204Pb15.330-15.862,^208Pb/^204Pb37.532-39.957。u值在8.23-10.6之间，黄铁矿δ^34S值在5.1‰-13.4‰之间，铅同位素组成具线性相关关系，^206Pb/^204Pb与^207Pb/^204Pb线性方程y=0.24x 11.19,r=0.83,^206Pb/^204Pb与^208Pb/^204Pb方程为y=1.3x 14.8,r=0.93，黄铁矿铅硫同位素组成具负相关关系，钠长石岩Rb、Sr含量较低，^87Sr/^86Sr值为0.72263-0.73150，平均0.72595。综合铅、锶、硫同位素特征，可以认为大沟谷金矿床成矿物质主要来自高u值基底碎屑沉积岩及钠化基性火成岩。     

峡东地区南华纪-寒武纪地层风化过程元素及Sr-Nd同位素演化特征及其地球化学意义

以峡东地区南华纪、震旦纪和寒武纪标准地层泥岩、冰碛泥岩、砂岩、灰岩和白云质灰岩及对应的风化土壤为研究对象, 分析了地层风化成土过程中不同元素的迁移行为, 根据剖面样品的Sr-Nd同位素组成变化, 探讨了其同位素体系的封闭性特征与应用意义.结果表明: (1) 不同岩性基岩在成土过程中的蚀变强度有明显的差异, 在相似地表条件下, 碳酸岩风化剖面的风化程度高于泥质岩和砂岩; (2) 通过对比稳定高场强Ti元素在基岩和风化剖面中的含量变化, 计算出土壤样品在风化过程中体积相对基岩发生的改变量, 进而计算出不同岩性基岩在风化过程中微量元素的绝对含量变化以探讨这些元素的活动规律.结果表明, 灰岩和白云质灰岩的风化剖面元素含量变化明显, 而在泥质岩风化过程中大多数元素保持了相对稳定, 说明沉积岩风化过程中元素的活动性特征明显地受到了原岩矿物组成的制约.风化过程中, 不同性质的元素的活动性差异明显, 其中亲硫元素(Cu、Zn、Pb、Mo) 和大离子亲石元素(Rb、K、Sr、Ba) 在不同岩性的风化剖面中均表现出明显的元素含量变化, 而高场强元素(Zr、Hf、Nb、Ta) 含量则相对稳定; (3) 泥质岩风化形成的土壤层REE含量变化较小, 而碳酸岩风化土壤层REE含量发生了明显下降, 且其风化形成的土壤表现出LREE和HREE相对于MREE的富集.无论是碳酸岩或泥质岩风化形成的土壤, 均出现了明显的Eu负异常和Ce的正异常, 但在其原岩中这些异常并不存在或不明显; (4) 基岩与土壤剖面间Sr同位素组成和Rb/Sr比值存在明显差异, Rb-Sr同位素组成发生了明显的开放.所形成土壤层的Sr同位素组成受到2种因素的约束: 原岩性质和外来组成的Sr同位素比值.因此在总体上, 风化土壤的Sr同位素组成已不能代表基岩的Sr同位素组成; (5) 沉积岩风化过程中, 碳酸岩和泥质岩形成的风化土壤基本保持了原岩的Sm-Nd同位素组成特点, 由其组成所获得的Nd同位素亏损地幔模式年龄等能反映其原岩信息, 而近源沉积形成的砂岩和含砾冰碛泥岩所形成的土壤, 其Nd同位素组成则存在不同程度的改变.      

Rare earth elements, yttrium and H, O, C, Sr, Nd and Pb isotope studies in mineral waters and corresponding rocks from NW-Bohemia, Czech Republic

The sparkling waters from the area of Kyselka near Karlovy Vary at the western slope of the Doupovske hory, Bohemia (Czech Republic), and CO₂-poor waters from two underground boreholes at Jachymov, Krusne hory, Bohemia, have been studied with the aim of characterizing the distribution of rare earth elements, yttrium, and H, O, C, Sr, Nd, Pb isotopes during the low-temperature alteration processes of the host rocks. Additionally, leaching experiments were performed at pH 3 on the granitic and basaltic host rocks from Kyselka and the granite of Jachymov. All REE patterns of the granite- and the basalt-derived waters from the Kyselka area are different from those of their source rocks and the leachates of the latter. This elucidates the inhomogeneous distribution of REE and Y among the solid phases in the altered magmatic rocks. The Eu and Ce anomalies in granite-derived waters are inherited, the Y anomaly is achieved by fluid migration. Yttrium is always preferentially leached by mineral waters, whereas Y/Ho ratios of rocks and their leachates are very similar. The REE abundances in waters from the wells in Jachymov are derived from rocks intensely leached and depleted in easily soluble REE-bearing minerals, whereas the granites and basalts from Kyselka still contain soluble, REE-bearing minerals. A comparison of REE/Ca patterns of the experimental leachates with those of the mineral waters elucidate the high retention of REE in rocks during water–rock interaction. In strongly altered rocks Sr isotope ratios of mineral waters and rocks differ widely, whereas the corresponding Nd isotope ratios are very similar. ²⁰⁷Pb/²⁰⁸Pb, ²⁰⁶Pb/²⁰⁸Pb and ²⁰⁶Pb/²⁰⁷Pb ratios in mineral waters are independent from U/Th ratios in the rocks. ²⁰⁶Pb/²⁰⁸Pb and ²⁰⁶Pb/²⁰⁷Pb are lower in mineral waters than in their source rocks and their leachates, which indicates that Pb is primarily derived from solid phases that do not contain significant contents of leachable U and Th. Thus, mineral waters, although CO₂ rich, only interact with surface films on minerals and not with the bulk of the minerals as in the leaching experiments.Calculation of mixing ratios of waters from the granitic and basaltic sources of the waters from the Kyselka area yield about 40% of water from the underlying granite in water recovered from the basalt, whereas the granite-derived water is mixed with only about 5% of the water from the basalt.     

陕西省华阳川铀铌铅矿床碳酸岩岩石学及地球化学特征

陕西省华阳川铀铌铅矿床是小秦岭成矿带中成矿特征最为独特的矿床,碳酸岩脉的破碎带是重要的成矿空间。未矿化的碳酸岩中矿物以方解石为主,其他矿物很少;发育铀矿化的碳酸岩脉中矿物种类繁多,大部分为方解石,其次为角闪石、金云母、榍石、褐帘石、铌钛铀矿、重晶石、磷灰石、石英、磁铁矿、碱性长石等矿物。碳酸岩的LREE含量异常高,δ13CV-PDB和δ18OV-SMOW值显示典型的火成碳酸岩特征。基于碳酸岩脉的Sr、Nd、Pb同位素比值(87Sr/86Sr-206Pb/204Pb、207Pb/204Pb-206Pb/204Pb-143Nd/144Nd-87Sr/86Sr)的关系图,初步判断华阳川铀铌铅碳酸岩脉是源于EMI的碱性硅酸盐-碳酸盐熔体-溶液结晶分异的产物。     

Redistribution of trace elements during prograde metamorphism from lawsonite blueschist to eclogite facies; implications for deep subduction-zone processes

The transfer of fluid and elements from subducting crust to the overlying mantle wedge is a fundamental process affecting arc magmatism and the chemical differentiation of the Earth. While the production of fluid by breakdown of hydrous minerals is well understood, the liberation of trace elements remains generally unconstrained. In this paper, we evaluate the behaviour of trace elements during prograde metamorphism and dehydration using samples of high-pressure, low-temperature metamorphic rocks from New Caledonia. Samples examined include mafic and pelitic rock-types that range in grade from lawsonite blueschist to eclogite facies, and represent typical lithologies of subducting crust. Under lawsonite blueschist facies conditions, the low temperatures of metamorphism inhibit equilibrium partitioning between metamorphic minerals and allow for the persistence of igneous and detrital minerals. Despite this, the most important hosts for trace-elements include lawsonite, (REE, Pb, Sr), titanite (REE, Nb, Ta), allanite (LREE, U, Th), phengite (LILE) and zircon (Zr, Hf). At epidote blueschist to eclogite facies conditions, trace-element equilibrium may be attained and epidote (REE, Sr, Th, U, Pb), garnet (HREE), rutile (Nb, Ta), phengite (LILE) and zircon (Zr, Hf) are the major trace-element hosts. Chlorite, albite, amphibole and omphacite contain very low concentrations of the investigated trace elements. The comparison of mineral trace-element data and bulk-rock data at different metamorphic grades indicates that trace elements are not liberated in significant quantities by prograde metamorphism up to eclogite facies. Combining our mineral trace-element data with established phase equilibria, we show that the trace elements considered are retained by newly-formed major and accessory minerals during mineral breakdown reactions to depths of up to 150 km. In contrast, significant volumes of fluid are released by dehydration reactions. Therefore, there is a decoupling of fluid release and trace element release in subducting slabs. We suggest that the flux of trace elements from the slab is not simply linked to mineral breakdown, but results from complex fluid-rock interactions and fluid-assisted partial melting in the slab.Electronic Supplementary Material Supplementary material is available in the online version of this article at http://dx.doi.org/10.1007/s00410-003-0495-5.Editorial responsibility: J. Hoefs     

Henry's law behavior in simple systems and in magmas: Criteria for discerning concentration-dependent partition coefficients in nature

Although numerous questions still surround the topic of Henry's law (HL) as it applies to trace element partitioning, there now exist sufficient experimental data to make some generalizations regarding HL behavior in minerals. The most important of these is that the commonly-observed failure of HL at low concentration occurs at distinctly different levels even for chemically-similar elements in a single mineral. This observation in turn provides a basis for discerning effects of HL failure in natural systems: through examination of element ratios in minerals and rocks, it is possible, in principle, to distinguish HL effects from changes in partition coefficients due to variations in other magmatic parameters such as temperature and the compositions of phases. Initial applications of this approach to plagioclase/ liquid partitioning of REE and to the general behavior of $\text{Zr}\text{Hf}$ and $\text{Ba}\text{Rb}$ during basalt production suggest that HL usually does hold in nature.     

Trace element distribution in mineral separates of the Allende inclusions and their genetic implications

Concentrations of the REE, Sc, Co, Fe, Zn, Ir, Na and Cr were determined by instrumental neutron activation and mass spectrometric isotope dilution analysis for mineral separates of the coarseand fine-grained types (group I and II of Martin and Mason's classification) of the Allende inclusions.These data, combined with data on mineral/liquid partition coefficients, oxygen isotope distributions and diffusion calculations, suggest the following: (1) Minerals in the coarse-grained inclusions (group I) crystallized in a closed system with respect to refractory elements. On the other hand, differences in oxygen isotope distributions among minerals preclude a totally molten stage in the history of the inclusion. Group I inclusions were formed by rapid condensation (either to liquid or solid) in a supercooled solar nebula; extrasolar pyroxene and spinel dust were included but not melted in the condensing inclusions, thus preserving their extrasolar oxygen isotope composition. REE were distributed by diffusion during the subsequent heating at subsolidus temperatures; because oxygen diffuses much more slowly at these temperatures, the oxygen isotope anomalies were preserved. (2) The fine-grained (group II) inclusions were also formed by condensation from a super-cooled nebular gas; however, REE-rich clinopyroxene and spinel were formed early and REE-poor sodalite and nepheline were formed later and mechanically mixed with clinopyroxene and spinel to form the inclusions. The REE patterns of the bulk inclusions and the mineral separates are fractionated, indicating that REE abundances in the gaseous phase were already fractionated at the time of condensation of the minerals. (3) Pre-existing Mg isotope anomalies in the coarse-grained inclusions must have been erased during the heating stage thus resetting the ²⁶Al-²⁶Mg chronometer.     

http://www.sciencedirect.com/science/article/pii/S1674987110000125

<正>Carbonatites are commonly related to the accumulation of economically valuable substances such as REE.Cu,and P.The debate over the origin of carbonatites and their relationship to associated silicate rocks has been ongoing for about 45 years.Worldwide,the rocks characteristically display more geochemical enrichments in Ba,Sr and REE than sedimentary carbonate rocks.However,carbonatite's geochemical features are disputed because of secondary mineral effects.Rock-forming carbonates from carbonatites at Qinling.Panxi region,and Bayan Obo in China show REE distribution patterns ranging from LREE enrichment to flat patterns.They are characterized by a Sr content more than 10 times higher than that of secondary carbonates.The coarse- and fine-grained dolomites from Bayan Obo H8 dolomite marbles also show similar high Sr abundance,indicating that they are of igneous origin.Some carbonates in Chinese carbonatites show REE(especially HREE) contents and distribution patterns similar to those of the whole rocks.These intrusive carbonatites display lower platinum group elements and stronger fractionation between Pt and Ir relative to high-Si extrusive carbonatite.This indicates that most intrusive carbonatites may be carbonate cumulates.Maoniuping and Daluxiang in Panxi region are large REE deposits.Hydrothermal fluorite ore veins occur outside of the carbonatite bodies and are emplaced in wallrock syenite.The fiuorite in Maoniuping has Sr and Nd isotopes similar to carbonatite.The Daluxiang fiuorite shows Sr and REE compositions different from those in Maoniuping.The difference is reflected by both the carbonatites and rock-forming carbonates,indicating that REE mineralization is related to carbonatites.The cumulate processes of carbonate minerals make fractionated fluids rich in volatiles and LREE as a result of low partition coefficients for REE between carbonate and carbonatite melt and an increase from LREE to HREE.The carbonatite-derived fluid has interacted with wallrock to form REE ore veins.The amount of carbonatite dykes occurring near the Bayan Obo orebodies may support the same mineralization model,i.e.that fluids evolved from the carbonatite dykes reacted with H8 dolomite marble,and thus the different REE and isotope compositions of coarse- and fine-grained dolomite may be related to reaction processes.     

CCSD主孔100-1100m榴辉岩中单矿物的原位微区微量元素地球化学研究

本文通过对CCSD主孔100～1100m范围内榴辉岩中单矿物的LA-ICP-MS分析，探讨了榴辉岩中单矿物之间的微量元素分配，发现超高压变质作用中石榴石和绿辉石之间Ti和C0的分配显著受Mg控制（如DCo^Grt/Omp=3．43DMg^Grt/Omp-0．34），而REE、Sr和Y的分配则受Ca分配所控制。绿辉石中REE、Pb和Th的含量则明显受超高压副矿物磷灰石的出现与否所控制。结合岩石学特征，对角闪石和绿辉石中微量元素的研究表明角闪石主要是绿辉石退变质的产物。但退变质矿物的微量元素组成不仅受原矿物控制，而且受退变质矿物组合类型影响。绿帘石的出现会显著降低共生角闪石中LREE和Sr的含量，而多硅白云母的分解则会增加角闪石中的Rb、Ba含量。另外，退变质过程中的流体活动也会影响退变质矿物中的LREE、Sr和Pb等。结合REE在榴辉岩各主要矿物间分配系数随温度、压力的变化，我们推测部分石榴石边部MREE的富集特征可能反映榴辉岩在折返过程中经历了短时增温作用，这可能是引起苏鲁地区榴辉岩相向麻粒岩相转变叠加现象以及超高压岩石经历部分熔融作用的重要原因。此外，榴辉岩中金红石Nb和Ta组成的高度不均一性为金红石形成于超高压变质阶段富Ti磁铁矿相变作用的成因机制提供了佐证。