Li, Be, B concentrations and δ7Li values in plagioclase phenocrysts of dacites from Nea Kameni (Santorini, Greece)

Li, Be, B and δ⁷Li SIMS analyses of plagioclase phenocrysts from the 1040–1941 Niki dacite lava (Nea Kameni, Santorini, Greece) exhibit varied processes. From their anorthite contents alone, the crystals may be segregated into four main types: type-N shows the normal decline in An during crystallisation (An_62–40); type-O has only oscillatory zoning accompanied by resorption surfaces (An_58–39); type-C is complex with high-An cores (subtype C1: An_64–58, subtype C2: An_88–73) and normal rims (An_55–42). Type-A plagioclase with high An content (An_92–82) is found within mafic enclaves. On the basis of their Li concentrations, type-O crystals may be subdivided into subtype O1 with flat Li concentration profiles and subtype O2 with decreasing Li concentration from core to rim. The concentrations of Be and B of all four types show a negative correlation with anorthite content (An), but Li concentration profiles differ amongst the different plagioclase types. Types N and O1, and the cores of type-C, are equilibrated in Li concentration. Types O2 and A, and the mantles of type-C display an initial enrichment in Li, probably from volatile influx into the melt. Consistent with the propensity towards equilibrium with the melt, these crystals display dramatic rim-ward declines in Li concentration. All analysed plagioclase crystals, except for the xenocrystic type-A, have nearly the same Li, Be and B concentrations at their rims. These coincide with the composition of plagioclase microlites in the groundmass, thereby affording estimates of plagioclase-melt partitioning for the light elements: K _Li = 0.19–0.28, K _Be = 0.24–0.38 and K _B = 0.007–0.009. δ⁷Li profiles in type-O2 and type-A phenocrysts manifest an unmistakable inverse relation to Li concentration, with variations of up to ~39 ‰, revealing preferential kinetic diffusion. This may have been driven by Li loss from the melt, most likely through degassing during decompression, perhaps in the course of magma ascent to subsequent eruption. Considering the rapid diffusion of Li in plagioclase, in situ phenocryst analyses may yield useful information about processes leading up to, or even causing, eruptions.     

Li and B Isotope Systematics of Ultrahigh-pressure Metamorphic Rocks from the Chinese Continental Scientific Drilling Program

1 Introduction Recent improvements in the precision of Li and B isotope measurements have demonstrated the potential of these elements in tracing a wide range of geological processes. The Li and B isotope systematics of ultrahigh-pressure (UHP) metamorphic rocks provides a unique opportunity to investigate the behaviour of Li and B during fluid-rock interaction at high temperatures and very high pressures and to constrain the fluid budget and the recycling of subducted crustal materials into the mantle during UHP metamorphism.     

MC-ICP-MS高精度测定Li同位素分析方法

以不同浓度Li元素标准样品和K、Ca、Na、Mg、Fe单元素标准样品的混合溶液为研究对象,采用3根阳离子交换树脂（AG 50W X8,200~400目）填充的聚丙烯交换柱和石英交换柱对Li进行分离富集,淋洗液分别为28 mol/L HCl、015 mol/L HCl以及05 mol/L HCl 30%乙醇,淋洗液体积小,仅为38 mL。分离回收率高,均大于976%。国际标样AGV 2（相对于IRMM 016）、BHVO 2（相对于IRMM 016）和IRMM 016（相对于L SVEC）的δ7Li值分别为(513±094)‰(2σ,n=10)、(408±060)‰(2σ,n=4)和(0038±073)‰(2σ,n=10),与前人分析结果吻合,分析精度与国际同类实验室水平相当。并对比了马里兰大学同位素实验室和笔者实验室对同种岩石矿物样品的分析结果,在误差范围内具有很好的一致性。此外,对美国地质调查局提供的准标样NKT 1霞石岩（相对于IRMM 016）给出了定值,δ7Li值为(871±046)‰(2σ,n=4)。因此,本方法可用于测定天然样品的Li同位素组成。     

Fractional crystallization models and B–Be–Li systematics at Mt Somma-Vesuvius volcano (Southern Italy)

A compilation of B–Be–Li data on rocks that cover the entire eruptive history of Somma-Vesuvius is presented and interpreted in the light of evolution models for the Somma-Vesuvius rocks. Using major and trace element data, fractional crystalllization models are presented for different geochemical units. These data were used to constrain the source mineralogy of the Somma-Vesuvius rocks (ol-opx-cpx-gar-amp of 0.4-0.3-0.1-0.1-0.1), the amount of sediment added (5–10%) and the melt fraction from batch partial melting computations (0.05–0.1). From the B–Li data it is inferred that the main process responsible for the B isotopic signature is sediment recycling. However, the B–Li data show a major variation in Li abundances respect to B which is explained with Li dehydration before the fluid enriched the mantle wedge that produced the arc magmas. The Somma-Vesuvius B isotope composition is intermediate between that of the Campi Flegrei and the broad field of the Eolian Island arc. A low Be isotopes in the recent volcanic rocks can be explained as: (a) the top 1–22 m of the incoming sediment is accreted, (b) large amounts of sediment erosion, (c) a slow rate of subduction which have provoked a long magmatic history for the Vesuvius magma, (d) the sediment component takes several Myr longer than the subducting plate to reach the magma source region beneath Italy.     

地质历史时期海洋Li同位素演变

Li是一种碱金属元素,由于它不受氧化还原和生物效应的影响,因此在追踪地球元素循环方面非常有利。并且Li在海洋中的留存时间远大于海水混合时间,因此海洋中的Li具有相对均一的组成,从而能够代表对应地质历史时期整体海洋情况。近年来海洋Li同位素被应用在示踪大陆风化模式领域,并取得了很多成果。笔者等在系统总结全球海洋Li循环作用和表生地质作用的Li同位素分馏机制的基础上,通过收集并整理、估算了不同时期海洋Li同位素组成,对地质历史时期海洋Li同位素组成变化与改变大陆风化模式相关的地质事件进行分析,再结合同时期碳酸盐岩C、Sr同位素数据进行对比分析,探讨Li、C、Sr同位素演化与地质事件之间的关系。最后,讨论了目前海洋Li同位素组成方面研究的不足,为后续利用海洋Li同位素记录示踪大陆风化模式的应用提供了参考。     

地质历史时期海洋Li同位素演变

Li是一种碱金属元素,由于它不受氧化还原和生物效应的影响,因此在追踪地球元素循环方面非常有利。并且Li在海洋中的留存时间远大于海水混合时间,因此海洋中的Li具有相对均一的组成,从而能够代表对应地质历史时期整体海洋情况。近年来海洋Li同位素被应用在示踪大陆风化模式领域,并取得了很多成果。笔者等在系统总结全球海洋Li循环作用和表生地质作用的Li同位素分馏机制的基础上,通过收集并整理、估算了不同时期海洋Li同位素组成,对地质历史时期海洋Li同位素组成变化与改变大陆风化模式相关的地质事件进行分析,再结合同时期碳酸盐岩C、Sr同位素数据进行对比分析,探讨Li、C、Sr同位素演化与地质事件之间的关系。最后,讨论了目前海洋Li同位素组成方面研究的不足,为后续利用海洋Li同位素记录示踪大陆风化模式的应用提供了参考。     

Geochemical Evolution and Ore-Bearing Metasomatic Rocks of the Baga-Gazryn Multiphase Massif of Rare-Metal Li–F Granites (Mongolia)

Doklady Earth Sciences - This paper considers the geochemical evolution of igneous and metasomatic rocks in the Baga-Gazryn Massif on the basis of new precision analytical data. The Baga-Gazryn...     

Multi-isotopic composition (δLi–δB–δD–δO) of rainwaters in France: Origin and spatio-temporal characterization

In the present work, the first results are reported for both Li and B isotope ratios in rainwater samples collected over a long time period (i.e. monthly rainfall events over 1 a) at a national scale (from coastal and inland locations). In addition, the stable isotopes of the water molecule (δD and δ¹⁸O) are also reported here for the same locations so that the Li and B isotope data can be discussed in the same context. The range of Li and B isotopic variations in these rainwaters were measured to enable the determination of the origin of these elements in rainwaters and the characterization of both the seasonal and spatio-temporal effects for δ⁷Li and δ¹¹B signatures in rainwaters. Lithium and B concentrations are low in rainwater samples, ranging from 0.004 to 0.292 μmol/L and from 0.029 to 6.184 μmol/L, respectively. δ⁷Li and δ¹¹B values in rainwaters also show a great range of variation between +3.2‰ and +95.6‰ and between −3.3‰ and +40.6‰ over a period of 1 a, respectively, clearly different from the signature of seawater. Seasonal effects (i.e. rainfall amount and month) are not the main factors controlling element concentrations and isotopic variations. δ⁷Li and δ¹¹B values in rainwaters are clearly different from one site to another, indicating the variable contribution of sea salts in the rainwater depending on the sampling site (coastal vs. inland: also called the distance-from-the-coast-effect). This is well illustrated when wind direction data (origin of air masses) is included. It was found that seawater is not the main supplier of dissolved atmospheric Li and B, and non-sea-salt sources (i.e. crustal, anthropogenic, biogenic) should also be taken into account when Li and B isotopes are considered in hydrogeochemistry as an input to surface waters and groundwater bodies as recharge. In parallel, the isotopic variations of the water molecule, vector of the dissolved B and Li, are also investigated and reported as a contour map for δ¹⁸O values based on compiled data including more than 400 δ¹⁸O values from throughout France. This δ¹⁸O map could be used as a reference for future studies dealing with δ¹⁸O recharge signature in relation to the characterization of surface waters and/or groundwater bodies.     

Composition and evolution of accessory mineralization of Li–F granites in the Far East as indicators of their ore potential

The ore potential of Pacific Li–F granites is considered on the basis of original and published data on composition of these granites and related metasomatic rocks in the Badzhal (Amur region) and Kuiviveem–Pyrkakai (Chukchi Peninsula) ore districts. The accessory mineralization in rare-metal granites is compared with that in W–Sn deposits. The main features in evolution of magmatic and hydrothermal mineralization are pointed out. A conclusion on the similarity between mineralization of the zwitter–tourmalinite type and accessory minerals in Li–F granites is drawn. It is established that magmatic and hydrothermal types of mineralization belong to the same evolutionary sequence. Genetic links between Li–F granites and the large ore deposits in the East Asian tungsten–tin zone are suggested.     

顽火辉石中Li同位素扩散与分馏

顽火辉石作为斜方辉石晶系的重要Mg端元矿物,是地球上地幔主要组成矿物之一。Li同位素作为重要的地幔地球化学示踪剂,在主要地幔矿物中(如橄榄石,辉石等)的扩散分馏相关性质的研究显得尤为重要。我们通过经典力学的方法,计算模拟了原子尺度下Li同位素在顽火辉石晶格以2种不同的迁移机制(填隙机制和取代空位机制)迁移的活化能和其在不同晶格位上不同温度条件下的分馏作用程度。计算结果表明,Li同位素易以填隙位机制在顽火辉石中迁移。重同位素~7Li会更多的进入晶格填隙位中,而6Li相对更多进入Mg位。温度是影响这种分馏作用的1个关键因素,相应的结果可用来解释地幔Li同位素组成特征及冷却条件下的同位素分馏等科学问题。     

Zn—Li硅酸盐的晶体结构和相转变

无色透明的人造 Zn(Zn_(0.1)Li_(0.6)Si_(0.3)SiO_4的室温形体(a)具有单斜对称,a=6.340(1),b=10.516(2)、C=5.011(1)A,β=90.50(2)°,空间群 P2./n,Z=4。大约在400℃,转变为斜方晶系的高温形体(β),a=6.406(3),b=10.520(8),C=5.043(2)(?),空间群 Pmnb,Z=4。根据室温和450℃的×—射线强度数据,用三维图象分析法,确定了两种形体的晶体结构。用最小二乘法分别按照最终加权 R=0.068(未加权的 R=0.068)和0.064(未加权的 R=0.070)精选了室温和高温结构。高温结构是一种具有共用系数为3的四面体架状结构。有两种不同的四面体位置:T_1,8次配位位置;T_2,4次配位位置。T_1位置包含了全部的 Zn 和 Li 以及某些 Si;T_2位置全部是 Si。T_1四面体构成平行于(010)的折曲层,这种层是由共顶角的四面体链组成,这些链是平行于[100]的。与辉石族矿物不同,所有四面体都位于链轴的同一侧。这些层按反向平行排列堆积,并由 T_2四面体将这些层交叉连接而组成架状结构。在低于转换温度条件下,8次配位的 T_1位置变为两种独立对称的4次配位位置 T_1(0)和 T_1(m),其对称从 Pmnb 变为 P_2_1/n。Zn 原子在 T_1(0)是完全有序的。转变时,Zn 原子可能集中在两种 T_1位置的某一位置。这种择位的结果就产生一种晶畴结构,其中具有两种通过交切(100)的反射而彼此联系的配位位置。有序——无序转变也产生双晶(a′)结构,这种结构具有单斜对称,空间群 B_2_,a=13.01,b=10.41,C=10.07(?),β≈90°。     

高效分离Li及其同位素的MC-ICP-MS精确测定

为了高效地从地质/环境样品中分离纯化Li元素并进行Li同位素测定,经反复实验和改良发现:采用8 m L容积(树脂体积)离子交换柱,选取AG 50W-X12阳离子交换树脂,以0.5 mol/L HNO3为淋洗液,过柱一次,并收集20~48 m L区间的淋洗液,即可一步实现Li的完全纯化分离。对于高盐样品,建议过柱两次确保Na/Li1,以达到上机测试的要求。由多种单元素标准混合的工作溶液(IEECAS-Li)经此流程分离后,采用Neptune Plus MC-ICP-MS测量得到的δ7Li值为8.31‰±0.12‰,与未混合的标准值(8.33‰±0.20‰)在误差范围内一致。采用此流程,获得的岩石标准物质AGV-2、BHVO-2和海水标准物质NASS-6的δ7Li值(2 s.d.,n=5)也与推荐值一致,分别为6.83‰±0.75‰、4.32‰±0.33‰和31.10‰±0.60‰。由此,我们建立了一套高效分离纯化Li及其同位素的MC-ICP-MS测试程序。将该程序用到Li含量在15 ng/g~90μg/g之间的实际样品中,δ7Li的长期内精度均好于0.30‰,且重现性高,表明该方法的分析精度和准确度都达到了国际标准水平。尤为重要的是,本方法可用于精确测量含痕量Li的环境样品的Li同位素组成。     

俯冲带Li同位素地球化学: 回顾与展望

板块俯冲伴随着多种复杂的地质过程,例如流体释放、流体岩石相互作用、可能的部分熔融、元素迁移及同位素分馏等。在俯冲带壳/幔循环过程中,Li同位素(6Li和7Li)高达16%的相对质量差异使其成为研究俯冲带各种地质过程的良好示踪剂。总结了近年来有关俯冲带Li同位素的研究进展,并按照相对时间序列系统地介绍了Li同位素在俯冲各个阶段的地球化学行为,包括俯冲初始物质的Li同位素组成特征,俯冲过程中Li随流体释放及与上覆地幔楔相互作用中Li同位素的行为,富Li流体与残余板片Li的去向,最终俯冲相关产物的Li同位素组成特征以及对全球Li循环的地学意义的综合介绍。随着Li同位素测试精度的提高和各种地球化学储库Li同位素数据库的不断完善,Li同位素体系可以为俯冲过程研究提供更多信息,成为一种可靠的示踪剂。     

Li—F花岗岩液态分离的微量元素地球化学标志

华南和世界其他国家典型Ｌｉ－Ｆ花岗岩１９５个微量元素分析结果的研究表明,随Ｌｉ－Ｆ花岗岩自下而上不同岩相变化：Ｚｒ／Ｈｆ－Ｆ、Ｎｂ／Ｔａ－Ｆ等有负相关变化;同样,随Ｆ增加,Ｔａ（Ｎｂ）、Ｓｎ、Ｗ、Ａｌ升高和Ｎｂ／Ｔａ（Ｚｒ／Ｈｆ）降低;在Ｋ／Ｒｂ－Ｒｂ图中黄英岩成分点位于相关斜线左下方;在Ｋ－Ｌｉ图中有低Ｌｉ、Ｋ的异常变化;在Ｒｂ／Ｓｒ－Ｐ２Ｏ５图中相关的二￣三个数量级异常变化等,均是Ｌｉ－Ｆ花岗     

Li—F花岗岩液态分离的同位素地球化学标志

Li-F花岗岩液态分离包括不混溶为主和气液分馏为主两种液态分离作用。Li-F花岗岩不混溶为主液态分离的同位素标志是：在复式Li-F花岗岩体中，随由早至晚阶段Li-F花岗岩侵入变化，岩石中δ^18O、ISr有先降低后突然升高的变化趋势；在典型Li-F花岗岩体中，由下部岩相成分相当翁岗岩（纳长花岗岩）向上至顶部岩相成分相当香花岭岩（云英岩、似伟晶岩）的全岩和石英δ^18O突然升高。Li-F花岗岩气液分馏为主液态分离的同位素标志是：典型Li-F花岗岩体的中、深部岩相向上至浅部岩相，岩石有δ^18O降低和δD升高的变化趋势。     

Li—F花岗岩液态分离和稀土地球化学标志

华南和其他国家典型Ｌｉ－Ｆ花岗岩的１１８个稀土分析研究表明,随Ｌｉ－Ｆ花岗岩由早至晚阶段或自下而上不同岩相演化,稀土模式曲线有三种变化类型;（１）降低变化。（２）升高变化;（３）突然变化等类型。（４）称为正向演化类型,是结晶分异结果;（２０称为反向演化类型,代表气液分馏为主的液态分离;（３）称为演变突变类型,是不混为主的液态分离形成。     

REE Geochemical Indicatrices of Li—F Granite Liquid Segregation

The results of 118 REE analyses of Li-F granites from South China and other countries indicate that there are three variation types of REE pattern curves with different evolution trends from early to late stages of Li-F granite complex of from lower to upper petrofacies of the Li-F granite body;(1) the decreasing,(2) the increasing,and (3) the saltatory variation types.The first variation type is called the positive evolution type,attributed to crystallization differentiation.The second is called the reversion evolution type.which represents liquid segreation dominated by vapor-liquid distillation.The third is called the saltatory variation type,which is formed from liquid segregation dominated by immiscibilty,Therefore,the indicatices of liquid segregation dominated by immiscibility are the saltatory variation type of REE pattern evolution and the separation of the main evolution trend lines either from the sub-evolution trend lines or from the composition points of Li-F granites in the diagrams of REE-(La-Yb)N and La/Sm-La,The indicatrices of liquid segregation dominated by vapor-liquid fractional distillation are the reverstion evolution type of REE pattern curves and the main evolution trend lines of Li-F granites directing to the upper right-hand on the REE-La/Yb)N and La/Sm-La diagrams.