Development of Synthetic Clinopyroxene Reference Materials for In Situ Lithium Isotope Measurement by LA-MC-ICP-MS

The isotopic composition of lithium (Li) in clinopyroxene (Cpx), determined via in situ micro-analysis, has been employed as a potential geochemical tool for studying various geological processes such as crust-mantle recycling, silicate weathering and fluid-rock interaction. To obtain precise and accurate Li isotopic compositions in Cpx by LA-MC-ICP-MS, synthetic Cpx matrix-matched reference materials (RMs) were prepared in this study. Six Cpx-matrix RMs were prepared by mixing metallic oxides with GSP-2 (granodiorite) or pure L-SVEC solution and melting them into glasses (GSP-2 + oxide; L-SVEC + oxide). Two representative synthetic glasses, CPXA01 and CPXB01, were subjected to a series of analyses to investigate the possible qualification of the RMs for in situ Li isotope measurement by LA-MC-ICP-MS, including elemental homogeneity analysis (elemental mapping analysis and spot analysis), Li isotopic homogeneity analysis and accurate Li isotopic determination. The applicability of the synthetic Cpx-matrix RMs was highlighted by comparing the δ⁷Li values of three natural Cpx calibrated against the synthetic Cpx-matrix RMs and other commonly used RMs with different matrices (NIST SRM 612, BCR-2G, GOR128-G, StHs6/80-G, KL2-G and T1-G), respectively. Additionally, CPXB01-05 RMs with the same matrix but different Li contents were prepared to explore the Li content mismatch effect, which is significant for accurate determination of in situ Li isotopic composition by LA-MC-ICP-MS. The results of the cross-calibration of Li isotopes in CPXA01 and CPXB01 suggested no obvious Li isotopic fractionation between the two types of glasses (GSP-2 + oxide; L-SVEC + oxide). Thus, the two methods of producing Cpx-matrix RMs are suitable for preparing the matrix-matched RMs for in situ microanalysis for Li isotopes.     

世界盐湖卤水型锂矿特征、分布规律与成矿动力模型

卤水锂矿在世界探明的锂矿总资源量中占比达65％,由于其易于开采,成本较低,其锂盐产品占总锂盐产品的75％左右.世界卤水锂矿主要产于现代盐湖,这些盐湖分布于世界三大高原:中国青藏高原、南美西部安第斯高原和北美西部高原,形成了三大盐湖卤水锂成矿区.中国青藏高原盐湖主要包括西藏中北部和柴达木盆地盐湖,卤水锂(LiCl)资源量为2330万t;南美西部安第斯高原盐湖,涵盖玻利维亚、智利和阿根廷盐湖,锂(Li2 O)资源量为2300万t;北美西部高原盐湖卤水锂矿(Li2 O)资源量为550万t.同时,中国华南地区在中生代晚期可能也是高原环境,高原地貌孕育了大量盐湖,并形成了一些富锂卤水矿.这些高原的形成与隆升都起因于板块俯冲及陆陆碰撞:南美安第斯高原和北美西部高原是太平洋板块向美洲板块俯冲-增生造山形成的,中国青藏高原是印度板块向欧亚板块俯冲-陆陆碰撞形成的,而中国华南古高原则可能与古太平洋板块向亚洲大陆俯冲作用有关.板块俯冲及陆陆碰撞作用,一方面形成高原地貌,挡住了来自大洋的水汽,从而导致高原内部降水减少,形成干旱气候,引发强烈蒸发作用;洋壳俯冲至上地幔之后,由于脱水和部分熔融导致其中的氯、钾、锂和溴等挥发分进入岩浆并被带到地壳浅部富集;板块俯冲-碰撞作用形成大量构造盆地,同时,岩浆活动又引起大量温热泉水活动,高温水-岩反应将地壳中大量锂等成矿物质释放出来,汇入盆地并通过蒸发浓缩形成富锂盐湖.上述构造、气候和物源等成矿要素的耦合,最终导致高原盐湖卤水富锂成矿.综合世界卤水锂矿特征与成矿作用,提出盐湖卤水锂成矿动力学模式.     

Vibrational spectroscopy of beta-eucryptite (LiAlSiO<Subscript>4</Subscript>): optical phonons and phase transition(s)

The structural behavior of -eucryptite (LiAlSiO₄) has been investigated using infrared (IR) spectroscopy over a temperature range of 20 to 900 K and FT-Raman spectroscopy at room temperature. IR reflectance measurements show that -eucryptite possesses high reflectivity in the far-IR region, as is consistent with its reported superionic conductivity along the c-axis. On heating, the Li-related IR bands near 246 and 300 cm^–1 (with A₂ symmetry) broadened and weakened dramatically, presumably as a result of Li⁺ positional disordering along the structural channels parallel to c. The disordering process appears to induce a framework distortion, as is evidenced by the broadening of some vibrations of Si(Al)–O with increasing temperature. A change in slope in the temperature dependence of the phonon frequency near 300 cm^–1 and the linewidth of the 760 cm^–1 band at 715 K indicates that Li becomes completely disordered above this temperature. In addition, the temperature dependence of the linewidth for the 760 cm^–1 band exhibits an additional change in slope at 780 K, implying the existence of an intermediate state within this temperature range. The detailed structure of this intermediate phase, however, needs further study. Our IR data provide no indication of structural changes between room temperature and 20 K.     

Li-(Mg、Zn、Ni)钒酸盐三元体系相关系和结晶化学

对Li-(Mg、Zn、Ni)钒酸盐系统在500—800℃的相图研究发现:(Mg、Zn、Ni)V_2O_6和(Mg、Zn、Ni)_2V_2O_7,二个系统中都有两个主要固溶体,一个以NiV_2O_6(或Ni_2V_2O_7)为主结构,另一个在MgV_2O_6-ZnV_2O_6间形成完全连续型,Mg_2V_2O_7-Zn_2V_2O_7间为MgZnV_2O_7结构型。(Mg、Zn、Ni)_3V_2O_8系统中,整个就是一个固溶体,而Li(Mg、Zn、Ni)VO_4系统中,端员组分相互间也形成不同的固溶体。     

祁连党河南山北坡中-基性火山岩地质特征及时代

根据地质研究、区域对比，结合首次获得的Rb-Sr等时线年龄数据，从祁连党河南山(又称乌兰达坂山）北坡原中奥陶统地层中厘定出晚震旦纪中－基性火山岩系。根据这一新成果，认为该区中基性火山岩，斜长角闪岩基底以及侵入其中的扎子沟等花岗闪长岩岩基在大地构造分区上应划归中祁连地块；晚震旦纪该区无疑有过扩张、地壳减薄的地质事件，震旦纪晚期有过挤压闭合事件。     

美国西部Owens湖地球化学记录及其古气候意义

美国加州中部Owens湖的稳定同位素、稀酸可溶相锂元素浓度及其它地球化学指标揭示本区0.155MaB.P.～62500aB.P.间的气候变化。在0.155～0.140MaB.P.,0.122～0.114MaB.P.,91000～83000aB.P.和72000～62500aB.P.期间,气候冷湿,对应于深海氧同位素(MIS)6,5d,5b和4阶段。这些期间内湖泊开放,^δ18 O和^δ13 C无协变性,Li和有机碳浓度很低。在0.140～0.122MaB.P.,0.114MaB.P.～91000aB.P.和83000～72000aB.P.期间,气候干热,对应于MIS5e,5c和5a阶段。湖泊在这些期间内封闭,^δ18 O和^δ13 C有很好的协变性,封闭湖^δ18 O的变化代表了湖水体积的变化。来自湖中自生镁硅酸盐的锂元素浓度的变化反映了盐度和温度的变化。Owens湖的记录与DevilsHole洞穴流石记录和格陵兰冰芯记录有很好的对比,进一步证实了终结期Ⅱ在海相记录中的年龄滞后。本文讨论了冰期与间冰期之间,美国西部和中国黄土地区气候模式的差异及其互动机制。     

Sodic Pyroxene and Sodic Amphibole as Potential Reference Materials for In Situ Lithium Isotope Determinations by SIMS

Two large pegmatitic crystals of sodic pyroxene (aegirine) and sodic amphibole (arfvedsonite) from the agpaitic igneous Ilímaussaq Complex, south Greenland were found to be suitable as reference materials for in situ Li isotope determinations. Lithium concentrations determined by SIMS and micro‐drilled material analysed by MC‐ICP‐MS generally agreed within analytical uncertainty. The arfvedsonite crystal was homogeneous with [Li] = 639 ± 51 μg g^?1 (2s, n = 69, MC‐ICP‐MS and SIMS results). The aegirine crystal shows strongly developed sector zoning, which is a common feature of aegirines. Using qualitative element mapping techniques (EPMA), the homogeneous core of the crystal was easily distinguished from the outermost sectors of the crystals. The core had a mean [Li] of 47.6 ± 3.6 μg g^?1 (2s, n = 33) as determined by SIMS. The seven micro‐drilled regions measured by solution MC‐ICP‐MS returned slightly lower concentrations (41–46 μg g^?1), but still overlap with the SIMS data within uncertainty. Based on MC‐ICP‐MS and SIMS analyses, the variation in δ⁷Li was about 1‰ in each of the two crystals, which is smaller than that in widely used glass reference materials, making these two samples suitable to serve as reference materials. There was, however, a significant offset between the results of MC‐ICP‐MS and SIMS. The latter deviated from the MC‐ICP‐MS results by ?6.0 ± 1.9‰ (2s) for the amphibole and by ?3.9 ± 1.9‰ (2s) for the aegirine. This indicates the presence of a significant matrix effect in SIMS determinations of Li isotopes for amphibole and pyroxene relative to the basalt glasses used for calibration. Based on the MC‐ICP‐MS results, mean δ⁷Li values of +0.7 ± 1.2‰ (2s, n = 10) for the arfvedsonite crystal and of ?3.7 ± 1.2‰ (2s, n = 7) for the core of the aegirine crystal were calculated. Adopting these values, SIMS users can correct for the specific IMF (instrumental mass fractionation) of the ion probe used. We propose that these two crystals serve as reference materials for in situ Li isotope determinations by SIMS and pieces of these two crystals are available from the first author upon request.     

桂林岩溶盆地第四纪粘土砾石层沉积与漓江袭夺

通过对桂林岩溶盆地内第四纪粘土砾石层调查研究,认为:①粘土砾石层成因不属冰川沉积或湖相沉积,而是山地河流相沉积和再沉积产物。前者时化属中更新世,后者成因复杂,已发现坡积相、洪积相,时代属晚更新世;②漓江溯源侵蚀过程中发生多次袭夺;③岩溶盆地的发育与漓江袭夺控制和影响粘土砾石层的沉积和再沉积。     

西藏扎布耶盐湖超大型B、Li矿床成矿物质来源研究

扎布耶盐湖位于西藏高原腹地,是一个现代盐湖矿床。对扎布耶地区地球化学背景的研究表明:变质岩及蚀变岩石中硼锂含量很高以及电气石脉的出现,暗示着扎布耶地区深部曾产生含硼锂高的热流体;沉积岩中除晚石炭世砂岩含硼锂稍高外,其他岩石均低于同类岩石的平均含量;火山岩中除早白垩世基性岩的硼锂含量高于基性岩平均含量外,其他均很低;该区大量发育的第四纪钙华含硼锂非常高,表明早期的热水系统曾提供过大量的成矿物质;河流及泉水中的硼锂含量是世界河水平均含量的数倍至数百倍,表明地表和近地表条件下的水-岩相互作用的产物也是成矿物质来源之一。