Lithium and lithium isotope profiles through the upper oceanic crust: a study of seawater-basalt exchange at ODP Sites 504B and 896A

Ocean Drilling Program (ODP) Hole 504B near the Costa Rica Rift is the deepest hole drilled in the ocean crust, penetrating a volcanic section, a transition zone and a sheeted dike complex. The distribution of Li and its isotopes through this 1.8-km section of oceanic crust reflects the varying conditions of seawater alteration with depth. The upper volcanic rocks, altered at low temperatures, are enriched in Li (5.6-27.3 ppm) and have heavier isotopic compositions (δ⁷Li=6.6-20.8‰) relative to fresh mid-ocean ridge basalt (MORB) due to uptake of seawater Li into alteration clays. The Li content and isotopic compositions of the deeper volcanic rocks are similar to MORB, reflecting restricted seawater circulation in this section. The transition zone is a region of mixing of seawater with upwelling hydrothermal fluids and sulfide mineralization. Li enrichment in this zone is accompanied by relatively light isotopic compositions (−0.8-2.1‰) which signify influence of basalt-derived Li during mineralization and alteration. Li decreases with depth to 0.6 ppm in the sheeted dike complex as a result of increasing hydrothermal extraction in the high-temperature reaction zone. Rocks in the dike complex have variable isotopic values that range from −1.7 to 7.9‰, depending on the extent of hydrothermal recrystallization and off-axis low-temperature alteration. Hydrothermally altered rocks are isotopically light because ⁶Li is preferentially retained in greenschist and amphibolite facies minerals. The δ⁷Li values of the highly altered rocks of the dike complex are complementary to those of high-temperature mid-ocean ridge vent fluids and compatible to equilibrium control by the alteration mineral assemblage. The inventory of Li in basement rocks permits a reevaluation of the role of oceanic crust in the budget of Li in the ocean. On balance, the upper 1.8 km of oceanic crusts remains a sink for oceanic Li. The observations at 504B and an estimated flux from the underlying 0.5 km of gabbro suggest that the global hydrothermal flux is at most 8×10⁹ mol/yr, compatible with geophysical thermal models. This work defines the distribution of Li and its isotopes in the upper ocean crust and provides a basis to interpret the contribution of subducted lithosphere to arc magmas and cycling of crustal material in the deep mantle.     

Chlorine-36 in groundwater of the United States: empirical data

Natural production of the radionuclide chlorine-36 (³⁶Cl) has provided a valuable tracer for groundwater studies. The nuclear industry, especially the testing of thermonuclear weapons, has also produced large amounts of ³⁶Cl that can be detected in many samples of groundwater. In order to be most useful in hydrologic studies, the natural production prior to 1952 should be distinguished from more recent artificial sources. The object of this study was to reconstruct the probable preanthropogenic levels of ³⁶Cl in groundwater in the United States. Although significant local variations exist, they are superimposed on a broad regional pattern of ³⁶Cl/Cl ratios in the United States. Owing to the influence of atmospherically transported ocean salt, natural ratios of ³⁶Cl/total Cl are lowest near the coast and increase to a maximum in the central Rocky Mountains of the United States. Electronic Publication     

Laser Ablation ICP-MS Analysis of Geological Materials Prepared as Lithium Borate Glasses

A simple, rapid and precise method is described for determining trace elements by laser ablation (LA)-ICP-MS analysis in bulk geological materials that have been prepared as lithium borate glasses following standard procedures for XRF analysis. This approach reliably achieves complete sample digestion and provides for complementary XRF and LA-ICP-MS analysis of a full suite of major and trace elements from a single sample preparation. Highly precise analysis is enabled by rastering an ArF excimer laser (λ= 193nm) across fused samples to deliver a constant sample yield to the mass spectrometer without inter-element fractionation effects during each analysis. Capabilities of the method are demonstrated by determination of twenty five trace elements (Sc, Ti, V, Ga, Rb, Sr, Y, Zr, Nb, Cs, Ba, REE, Hf, Ta, Pb, Th and U) in a diverse range of geological reference materials that includes peridotites, basalts, granites, metamorphic rocks and sediments. More than 90% of determinations are indistinguishable from published reference values at the 95% confidence level. Systematic bias greater than 5% is observed for only a handful of elements (Zr, Nb and U) and may be attributed in part to inaccurate calibration values used for the NIST SRM 612 glass in the case of Zr and Nb. Detection limits for several elements, most notably La, are compromised at ultra-trace levels by impurities in the lithium borate flux but can be corrected for by subtracting appropriate procedural blanks. Reliable Pb analysis has proved problematic due to variable degrees of contamination introduced during sample polishing prior to analysis and from Pt-crucibles previously used to fuse Pb-rich samples. Scope exists for extending the method to include internal standard element/isotope spiking, particularly where integrated XRF analysis is not available to characterise major and trace elements in the fused lithium borate glasses prior to LA-ICP-MS analysis.     

铅—试铁灵络合物吸附波及溴化十六烷基三甲基铵增敏效应的研究

在０３０ｍｏｌ／ＬＨＡｃ介质中，Ｐｂ（Ⅱ）与７＿碘＿８＿羟基喹啉＿５＿磺酸（试铁灵，Ｆｅｒｏｎ）的络合物于－０５４Ｖ（ｖｓ．ＳＣＥ）产生一尖锐的极谱波，加入溴化十六烷基三甲基铵（ＣＴＭＡＢ）显著增敏，可使极谱波增高约４倍。峰电流与Ｐｂ（Ⅱ）浓度在９６×１０－９～４８×１０－６ｍｏｌ／Ｌ呈良好的线性关系，检出限为４８×１０－９ｍｏｌ／Ｌ。用多种电化学方法研究了该极谱波的性质及电极反应机理表明，络合物组成比为ｎＰｂ（Ⅱ）∶ｎＦｅｒｏｎ＝１∶１，极谱波为吸附波，峰电流由中心离子Ｐｂ（Ⅱ）还原产生，电子转移数为２。试验了多种离子对峰电流的影响，拟定的方法用于矿样分析，结果与原结果相符。     

A Reflection on Mg, Cd, Ca, Li and Si Isotopic Measurements and Related Reference Materials

This contribution aims to report the reflections we had with the scientific community during two international workshops on reference materials for stable isotopes in Davos (2002) and Nice (2003). After evaluating the isotopic homogeneity of some existing reference materials, based on either certificates, literature data or specific inter-laboratory rounds, we confirm these as primary reference materials or propose new ones relative to which stable isotope compositions should be reported. We propose DSM-3 for Mg, NIST SRM 915a for Ca, L-SVEC for Li and NBS28 for Si. Cadmium does not yet have a well identified delta zero material, although three commercial mono-elemental Cd solutions have yielded the same isotopic composition relative to one another. In order to scale the linearity of any mass spectrometer, some secondary reference materials are also proposed: Cambridge-1 solution for Mg, the "Münster-Cd" and JEPPIM Cd solutions for Cd and the "Big Batch" silicate for Si. The team from Nancy propose to prepare a mixed spike solution for Li isotopes. Well-characterised natural samples such as ocean or continental waters, diatoms, sponges, rocks and minerals are needed to validate the entire analytical procedure, particularly to take into account the effect of sample mineralisation and of chemical manipulations for elemental separation prior to analysis.     

喜马拉雅东段库曲岩体锂、铍和铌钽稀有金属矿物研究及指示意义

稀有金属矿物记录了花岗伟晶岩成岩成矿的重要信息。喜马拉雅是全球著名的淡色花岗岩带,库曲岩体位于喜马拉雅东段的特提斯喜马拉雅岩系中。本文调查了库曲岩体的二云母花岗岩、白云母花岗岩、电气石花岗岩和花岗伟晶岩,其中,花岗伟晶岩涉及花岗岩的伟晶岩相和独立伟晶岩脉。库曲岩体产出的稀有金属矿物包括锂辉石、锂绿泥石、绿柱石、铌铁矿-钽铁矿、钇铀钽烧绿石和细晶石,它们主要赋存于似文象伟晶岩、石英-钠长石-白云母伟晶岩、块体长石-钠质细晶岩、块体长石-电气石钠质细晶岩、锂辉石-块体长石-细晶岩、白云母花岗岩的伟晶岩相以及电气石花岗岩内。显微镜观察、电子探针和LA-ICP-MS测试结果显示锂辉石具有四种产状,包括粗粒锂辉石自形-半自形晶、细粒锂辉石-石英镶嵌晶、中细粒锂辉石-钾长石-钠长石-云母镶嵌晶以及发育锂绿泥石的粗粒锂辉石,揭示了其形成时复杂的熔流体动荡结晶环境。绿柱石背散射电子图像（BSE）下呈均一结构和不均一结构（蚀变边、不规则分带和补丁分带）,元素替代机制包括通道-八面体替代、通道-四面体替代以及通道中碱金属阳离子间的置换。铌铁矿族矿物包括原生、蚀变边和不规则分带结构,部分被钇铀钽烧绿石和细晶石交代。与原生铌铁矿相比,蚀变边和不规则分带铌铁矿族矿物总体上富钽贫锰,显示了结晶分异、过冷却引起的过饱和以及流体作用。根据稀有金属矿物揭示的成因信息,独立伟晶岩脉（似文象伟晶岩）、白云母花岗岩的伟晶岩相和电气石花岗岩在岩浆分异程度、经历的演化过程、以及流体活动方面存在差异,很可能是不同期次岩浆活动的产物。库曲岩体绿柱石的Rb和Zn含量、以及铌铁矿族矿物的Sc₂O₃、SiO₂和PbO含量,与已有指示标志存在相关性,作为潜在指示标志仍需开展更多的研究工作。综合含锂辉石伟晶岩的产出、岩浆分异演化程度、多期花岗质岩浆活动、复杂的流体作用以及所属锂丰度高值区等因素,库曲岩体是喜马拉雅东段找锂的有利地段。     

以PAC为原料合成锂吸附剂的工艺研究

研究了聚合氯化铝（PAC）为原料合成锂吸附剂的基本工艺路线,并探究了加料方式、反应物配比、反应温度、反应时间和加料速度等对所合成吸附剂吸附量的影响,研究结果表明配比是影响吸附剂吸附量的最主要因素,得到了最佳合成条件,在此条件下所合成吸附剂对锂离子的吸附容量为6.1mg/g。推断吸附剂的主要成分为晶态或非晶态的LiCl·2Al(OH)3·nH2O,同时含有Al(OH)3、(CaO)3Al2O3·6H2O及 LiCl·H2O等成分。从吸附结果来看,结晶度较差的片状LiCl·2Al(OH)3·nH2O和非晶态的Al(OH)3为主成分的吸附剂吸附性能最好。     

新疆大红柳滩伟晶岩型锂矿深部结构与区域成矿模型解释

为揭示花岗岩- 伟晶岩型锂等稀有金属矿成矿系统的深部结构,对西昆仑造山带大红柳滩伟晶岩型锂矿集区开展了大地电磁测深法(MT)探测。通过MT三维反演电阻率模型,探测到两个0~20 km深度范围的高阻体,反映了出露于地表的大红柳滩复式花岗岩基和半隐伏的大红柳滩东花岗岩基;20~80 km深度范围内发现的大范围高导异常,则反映了深达上地幔的地壳重熔形成的大规模长英质岩浆储库。可见,成矿母岩大红柳滩花岗岩基是有根的,而且是规模巨大深达上地幔的岩浆储库,它们为超大型大红柳滩伟晶岩型锂矿的形成提供了物源和热源。与松潘- 甘孜甲基卡超大型伟晶岩型锂矿集区对比,尽管川西甲基卡地区地表出露的花岗岩有限,但MT三维反演电阻率模型显示,其也存在深达上地幔的大范围高导异常,同样反映了大规模长英质岩浆储库的存在,只是剥蚀深度浅,上侵的花岗岩未被剥蚀出来而已。从而,深剥蚀的大红柳滩地区表现为大面积花岗岩出露的“热隆”特征,而浅剥蚀的甲基卡地区则表现为花岗岩围岩“片麻岩穹隆”热变质构造特征。西昆仑- 松潘- 甘孜伟晶岩型锂等稀有金属巨型成矿带两端的晚三叠世超大型矿床是大规模地壳重熔长英质岩浆作用中心的产物,由于锂等稀有金属的喜水性,H2O的饱和度是造就伟晶岩型锂超常富集的关键,并在长英质岩浆储库、上侵花岗岩和伟晶岩不同分异演化阶段,锂的“预富集”为大规模伟晶岩型锂矿成矿奠定了重要基础。     

西昆仑-喀喇昆仑造山带锂矿成矿特征与成矿规律初探

西昆仑- 喀喇昆仑造山带中生代花岗伟晶岩相当发育,主要分布于麻扎- 康西瓦缝合带以南的喀喇昆仑造山带,构成了西自木吉—塔什库尔干,东到大红柳滩长达600 km的喀喇昆仑稀有金属成矿带。通过多年的研究,本文对西昆仑- 喀喇昆仑造山带37处稀有金属矿床(点)进行了全面系统的梳理,认为喀喇昆仑- 喀喇昆仑造山带表现为“西铍东锂”的格局,稀有金属成矿年龄集中213~206 Ma。将喀喇昆仑造山带稀有金属成矿带划分为木吉- 塔什库尔干稀有金属成矿亚带、赛图拉- 大红柳滩稀有金属成矿亚带,从西向东可划定4个矿化集中区：木吉- 布伦口稀有金属集中区、塔什库尔干- 塔吐鲁沟稀有金属矿化集中区、康西瓦稀有金属矿化集中区、大红柳滩- 白龙山稀有金属矿化集中区。同时,认为西昆仑- 喀喇昆仑造山带西段下一阶段的找矿可放在西合休南锂铍找矿远景区、阿然保泰铍找矿远景区、木吉西锂铍找矿远景区。     

基墨里造山与松潘-甘孜锂矿链成因的探讨

晚三叠世—早侏罗世,基墨里大陆和泛华夏陆块与欧亚大陆的碰撞,形成了4000 km 长的基墨里造山带。位于三大陆之间、现今青藏高原北部的松潘 甘孜地体的造山属性的确定,对于探索松潘 甘孜锂矿链的成因有重要意义。松潘 甘孜地体西部和北部的早侏罗世陆相火山岩、底砾岩和煤系地层(~201 Ma)不整合在晚三叠世褶皱地层及花岗岩体之上,为晚三叠世—早侏罗世的基墨里造山时限提供了直接证据。松潘 甘孜地体中的甲基卡、可尔因、扎乌龙和白龙山 大红柳滩等稀有金属矿集区具有共同特征：赋存在由核部高分异S型花岗岩和幔部中晚三叠世浊积岩组成的片麻岩穹隆构造中、经历了巴罗 巴肯变质作用、含锂伟晶岩脉侵位在花岗岩体上部的伸展空间。通过对松潘 甘孜地体区域地质调查和对矿集区的变质、变形、岩浆和成矿作用及同位素年代学研究,提出该地体经历晚三叠世—早中侏罗世的基墨里造山过程：① 230~220 Ma：地壳缩短和加厚阶段,以盖层大规模强烈褶皱、逆冲带,盖层与基底之间向南的滑脱变形为特征,伴随深熔和巴罗式变质作用;② 220~190 Ma：地壳减压折返阶段,大量花岗岩侵位在中晚三叠世浊积岩中、形成片麻岩穹隆并伴随巴肯式变质作用。由于花岗质岩浆的高度分异及岩浆不混溶作用,导致侵位在片麻岩穹隆顶部伸展空间的伟晶岩稀有金属富集成矿。此外,伟晶岩型锂矿科学钻探(JSD)揭示了甲基卡矿集区多层次穹状花岗岩席控制含锂伟晶岩脉的成矿机制,推测大规模中下地壳基底深熔驱动岩浆上升,岩浆体沿上地壳中的构造面推叠形成岩席。