敞开酸溶和偏硼酸锂碱熔ICP-MS法测定多金属矿中的稀土元素及铌钽锆铪

用电感耦合等离子体质谱法(ICP-MS)测定地质样品中的稀土及难熔元素,混合酸敞开酸溶法和碱熔融法是两种主要的溶样方法。但地质样品组分复杂,元素之间存在相互共生的现象,对于特殊元素、特殊样品用传统酸溶法会造成部分元素消解不完全,使测定结果不准确;而碱熔法的操作过程繁琐,且溶液盐度高,易产生基体干扰和堵塞仪器进样系统。本文改进了传统四酸和五酸体系,采用氢氟酸-硝酸-硫酸敞开酸溶体系,用国家一级标准物质制作标准曲线测定15种稀土元素,方法准确度(ΔlgC)为0.001～0.027。同时改进了偏硼酸锂碱熔法,样品用偏硼酸锂碱熔提取,加入氢氧化钠调节溶液至碱性条件,所测元素与偏硼酸锂共沉淀后过滤分离熔剂,再用硝酸复溶测定15种稀土元素及铌钽锆铪。两种溶样方法的测定值与认定值的相对误差为1.09%～9.30%。将混合酸敞开酸溶法测定稀土元素、偏硼酸锂碱熔法测定铌钽锆铪的结果与其他实验室密闭酸溶法相比,两组数据的相对偏差为0.13%～15.32%。本实验表明,混合酸敞开酸溶法适用于测定地质样品中的稀土元素,偏硼酸锂碱熔法不仅适用于测定地质样品中的稀土元素及铌钽锆铪,也适用于测定如古老高压变质岩石及铝含量高的样品中的铌钽锆铪。     

羌塘中部白措花岗岩岩石地球化学特征、锆石U Pb年龄和Hf同位素组成及其构造意义

本文对羌塘中部白措花岗岩的研究表明,岩体是由花岗闪长岩和二长花岗岩同时侵位的复合岩基,锆石U Pb年龄分别为213. 8±1. 3 Ma、210. 0±1. 1 Ma和208. 1±1. 4 Ma。白措花岗岩为硅过饱和的准铝质—弱过铝质岩石,Eu负异常明显,富集大离子亲石元素,亏损高场强元素,显示典型的壳源特征。εHft)为负值,主要集中于-10～-15,对应的Hf同位素二阶段模式年龄峰值为1. 78 Ga,显示源区为古元古代古老地壳;同时,花岗岩中含有大量闪长质暗色包体,表明有壳幔岩浆混合作用,推测为同时期玄武质岩浆的底侵作用,在地壳深部诱发富硅质基底岩石重熔,快速喷发形成玄武岩—流纹岩双峰式组合,而花岗岩则是由玄武质岩浆在地壳充分熔融后,岩浆沿羌塘中部已有的构造破碎带侵入形成,并且在熔融过程中有镁铁质岩浆注入少量结晶的长英质岩浆中形成暗色包体。因此,花岗岩与双峰式火山岩是同一裂陷动力机制的产物。花岗岩的侵入预示了晚三叠世羌塘盆地构造岩浆活动的结束,之上开始了羌塘侏罗纪海相盆地的沉积。     

准噶尔盆地南缘头屯河地区砂岩型铀矿铀源区及其成矿构造背景分析——来自碎屑锆石U-Pb年龄及Hf同位素的证据

准噶尔盆地是我国重要的多能源矿产产出盆地之一,而准噶尔盆地南缘头屯河地区也是我国砂岩型铀矿找矿的优选区段,为了厘定头屯河地区砂岩型铀矿赋矿层位沉积期的源区位置、母岩岩性及时代,本文在野外地质调查的基础上,对头屯河地区砂岩型铀矿赋矿层中的碎屑锆石进行了LA-ICP-MS U-Pb定年和Hf同位素分析,建立了碎屑锆石的U-Pb年龄及Hf模式年龄谱系。通过与周缘岩浆活动时代对比,并结合古流向数据进一步分析赋矿层位沉积期的源区位置及母岩岩性,讨论砂岩型铀矿的铀源条件。对采自侏罗系和下白垩统的4个砂岩样品进行碎屑锆石年龄分析表明:碎屑锆石U-Pb年龄存在140～180 Ma、240～320 Ma、340～420 Ma、440～480 Ma四个主峰值年龄段,年龄较平均的分布在210～480 Ma宽泛的区间内。研究表明头屯河地区早侏罗世物源来自北天山;中侏罗世物源来自中、南天山;中侏罗晚期开始转变为以北天山为主;早白垩世物源大部分来自中、北天山,少量来自博格达山地区。砂岩型铀矿化层铀源主要来自南侧天山地区的古生代中酸性火成岩,其成矿作用应该发生在盆地处于较稳定的构造环境中。     

华北克拉通东部古太平洋板块俯冲与回撤作用:来自辽西兴城地区晚中生代花岗质岩石的记录与启示

目前对于华北克拉通东部晚中生代花岗质岩石的成因仍存在地幔柱、加厚/拆沉下地壳部分熔融、俯冲板片脱水导致地壳熔融等不同认识。辽西兴城地区晚中生代花岗质岩石主要由二长花岗岩、石英闪长岩、花岗斑岩和石英正长岩组成,岩浆成因锆石U-Pb同位素定年结果显示岩浆活动主要发生于晚侏罗世(156Ma)、早白垩世早期(139Ma)、早白垩世中期(130～125Ma)。岩石地球化学测试分析结果显示岩石属于高钾钙碱性系列且具有富集K、Pb等大离子亲石元素而相对亏损Nb、Ta、Ti等高场强元素等活动陆缘岩浆岩特点,表明辽西地区晚中生代岩浆活动的发生与俯冲作用有关。晚侏罗世-早白垩世早期(156～139Ma)花岗质岩石地球化学特征与I型花岗岩类似,同时具有富集的Hf同位素组成(εHf(t)=-22.70～-18.66)和古老的Hf同位素二阶段模式年龄(tDM2=2387～2767Ma),其初始岩浆可能来源于古老中上地壳的部分熔融;形成于130Ma的花岗质岩石同样具有与I型花岗岩相类似的岩石地球化学特征,但其Hf同位素组成突变为亏损(εHf(t)=+3.64～+6.22、tDM1=537～969Ma),其初始岩浆起源于新元古代新生地壳物质的部分熔融并混入少量亏损地幔物质组分;形成于125Ma的花岗质岩石为碱性A型花岗岩,岩石地球化学特征与其他岩石有所不同,具有负的εHf(t)值(-17.30～-11.56)和相对古老的Hf同位素二阶段年龄(tDM2=1917～2278Ma),初始岩浆可能起源于较为古老的中下地壳部分熔融并有幔源物质的参与。华北克拉通东部形成于160～139Ma的花岗质岩石具有I型、高钾钙碱性、与埃达克质岩石类似的高Sr/Y、低Y含量特征和富集的Hf同位素组成,而形成于130～120Ma的花岗质岩石具有A型、碱性、与典型岛弧岩浆岩类似的岩石地球化学特征和相对亏损的Hf同位素组成,同时晚中生代岩浆活动具有向洋年轻化的特点,表明华北克拉通东部156～139Ma期间可能受到古太平洋板块的持续俯冲作用,而139～130Ma古太平洋俯冲板片开始回撤,130～125Ma进入古太平洋俯冲板片持续回撤导致的强烈区域伸展作用阶段。古太平洋俯冲板片脱水交代岩石圈地幔并形成幔源岩浆,幔源岩浆不断底侵作用于古老/新生地壳使其发生部分熔融为花岗质岩石提供岩浆来源。     

Petrogenesis of granitoids from the Lachlan Fold Belt,southeastern Australia: The role of disequilibrium melting

S- and I-type granites from the Lachlan Fold Belt, southeastern Australia, have been investigated to assess the role of disequilibrium melting in their petrogenesis. Differences between the median initial εHf compositions of magmatic zircon populations and the host bulk-rock (ΔεHf^blk-zrc) range from −0.6 to +2.5 ε units, providing evidence for intra-sample (and hence inter-phase) Hf-isotopic heterogeneity. Linear variations on Harker diagrams and O and Hf isotope compositions of magmatic zircon preserved in many I- and S-type granites are inconsistent with assimilation or simple mixing hypotheses. In contrast, isotopic disequilibrium between the melt and a restite assemblage can explain the bulk-rock versus zircon differences observed in these samples.Assuming that magmatic zircon records the melt composition, differences between the bulk-rock εHf and εHf of magmatic zircon (ΔεHf^blk-zrc values) measured for I-type granites (0.4–2.5) can largely be explained by disequilibrium amphibole dehydration melting of meta-igneous protoliths that were either isotopically heterogenous at the time they were formed, or perfectly homogeneous before being aged in the crust for 0.4–1.0 billion years prior to partial melting. The Currowong Suite exhibits petrographic features and preserves geochemical and isotopic compositions that do not lend themselves to simple restite model or magma mixing explanations; however, these observations could be explained by the restite unmixing of magma batches generated from a single source rock if, as modelling has suggested, separate batches contain different melt compositions.By investigating the application of disequilibrium melting to granite genesis, this study demonstrates that isotopic heterogeneity at various sampling scales should actually be expected for the production of granites from a single source, rather than necessitating the involvement of multiple sources and mixing processes. As a result great care should be taken in the interpretation of isotope data from granitic bulk-rocks or their zircons.     

Geochemistry,detrital zircon geochronology and Hf isotope of the clastic rocks in southern Tibet: Implications for the Jurassic-Cretaceous tectonic evolution of the Lhasa terrane

In order to reconstruct tectonic evolution history of the southern margin of Asia (i.e., Lhasa terrane) before the India-Asia collision, here we present a comprehensive study on the clastic rocks in the southern Lhasa terrane with new perspectives from sedimentary geochemistry, detrital zircon geochronology and Hf isotope. Clasts from the Jurassic-Early Cretaceous sedimentary sequences (i.e., Yeba and Chumulong Formations) display high compositional maturity and experienced moderate to high degree of chemical weathering, whereas those from the late Early-Late Cretaceous sequences (Ngamring and Shexing Formations) are characterized by low compositional maturity with insignificant chemical weathering. Our results lead to a coherent scenario for the evolution history of the Lhasa terrane. During the Early-Middle Jurassic (∼192-168Ma), the Lhasa terrane was speculated to be an isolated geological block. The Yeba Formation is best understood as being deposited in a back-arc basin induced by northward subduction of the Neo-Tethys ocean with sediments coming from the interiors of the Lhasa terrane. The Middle Jurassic-Early Cretaceous Lhasa-Qiangtang collision resulted in the formation of a composite foreland basin with southward-flowing rivers carrying clastic materials from the uplifted northern Lhasa and/or Qiangtang terranes. During the late Early-Late Cretaceous (∼104-72Ma), the Gangdese magmatic arc was uplifted rapidly above the sea level, forming turbidites (Ngamring Formation) in the Xigaze forearc basin and fluvial red beds (Shexing Formation) on the retro-arc side. At the end of Late Cretaceous, the Lhasa terrane was likely to have been uplifted to high elevation forming an Andean-type margin resembling the modern South America before the India-Asia collision.     

Strategies towards robust interpretations of in situ zircon Lu-Hf isotope analyses

The combination of U-Pb and Lu-Hf compositions measured in zircon crystals is a remarkably powerful isotopic couplet that provides measures on both the timing of mineral growth and the radiogenic enrichment of the source from which the zircon grew.The U-Pb age documents the timing of zircon crystallization/recrystallization and Hf isotopes inform on the degree to which the host melt was derived from a radiogenic reservoir(e.g.depleted mantle) versus an unradiogenic reservoir(e.g.ancient continental crust),or some mixture of these sources.The ease of generating large quantities of zircon U-Pb and Lu-Hf data has been in large part facilitated by instrument advances.However,the dramatic increase in time constrained zircon Lu-Hf analyses in the Earth science community has brought to the fore the importance of careful data collection and reduction workflows,onto which robust geological interpretations may be based.In this work,we discuss the fundamentals of Lu-Hf isotopes in zircon,which then allows us to provide a robust,accessible,methodology for the assessment of data quality.Additionally,we discuss some novel techniques for:data visualization—that facilitates better transparency of data interpretation;integration of geographic information—that may reveal spatial trends where temporal trends were only apparent before;and some novel statistical evaluation tools—that may provide more rigorous interand intra-sample comparisons.     

A New Appraisal of Sri Lankan BB Zircon as a Reference Material for LA‐ICP‐MS U‐Pb Geochronology and Lu‐Hf Isotope Tracing

A potential zircon reference material (BB zircon) for laser ablation‐inductively coupled plasma‐mass spectrometry (LA‐ICP‐MS) U‐Pb geochronology and Hf isotope geochemistry is described. A batch of twenty zircon megacrysts (0.5–1.5 cm³) from Sri Lanka was studied. Within‐grain rare earth element (REE) compositions are largely homogeneous, albeit with some variation seen between fractured and homogeneous domains. Excluding fractured cathodoluminescence bright domains, the variation in U content for all analysed crystals ranged from 227 to 368 μg g^?1 and the average Th/U ratios were between 0.20 and 0.47. The Hf isotope composition (0.56–0.84 g/100 g Hf) is homogeneous within and between the grains – mean ¹⁷⁶Hf/¹⁷⁷Hf of 0.281674 ± 0.000018 (2s). The calculated alpha dose of 0.59 × 10¹⁸ g^?1 for a number of BB grains falls within the trend of previously studied, untreated zircon samples from Sri Lanka. Aliquots of the same crystal (analysed by ID‐TIMS in four different laboratories) gave consistent U‐Pb ages with excellent measurement reproducibility (0.1–0.4% RSD). Interlaboratory assessment (by LA‐ICP‐MS) from individual crystals returned results that are within uncertainty equivalent to the TIMS ages. Finally, we report on within‐ and between‐grain homogeneity of the oxygen isotope systematic of four BB crystals (13.16‰ VSMOW).     

桂北地区丹洲群碎屑锆石LA-ICP-MS U-Pb年龄和Hf同位素特征及其地质意义

桂北丹洲群顶部拱洞组粉砂岩的碎屑锆石的阴极发光图像和Th/U(0.2~2.4)值显示,它们均为岩浆成因的锆石。锆石~(206)Pb/~(238)Pb年龄分布在730~769Ma和771~850Ma之间,这些锆石的Hf同位素成分范围较大,ε_(Hf)(t)值和二阶段Hf模式年龄(T_(DM2))分别为-18.4~11.4和1020~2812Ma。此外,样品中还有一些年龄较老的锆石颗粒,~(207)Pb/~(206)Pb年龄为1910~3140Ma,ε_(Hf)(t)值和二阶段Hf模式年龄(T_(DM2))分别为-13.6~3.4和2740~3635Ma。结合前人的研究推测,桂北丹洲群拱洞组沉积年龄小于等于706±10Ma,物源主要由扬子板块新元古代岩浆岩组成,也有少量太古宙岩浆岩的加入。推测中国华南地区存在对应于Rodinia超大陆聚合相关的格林威尔运动的响应。根据已测锆石的ε_(Hf)(t)值和Hf二阶段模式年龄推断,研究区地壳生长主要经历3个阶段:(1)3.64~3.25Ga,初生地壳出现在3.64Ga;(2)2.98~2.37Ga;(3)2.19~1.28Ga,地壳生长的主要时期。     

大兴安岭中段索伦地区白音高老组火山岩锆石U-Pb年龄、地球化学特征及构造意义

白音高老组火山岩位于大兴安岭中段科右前旗索伦地区,主要岩性为流纹岩和流纹质晶屑凝灰岩。LA-ICP-MS锆石U-Pb同位素分析表明,3组样品的锆石U-Pb年龄分别为127±2Ma、133±2Ma和123±1Ma,即白音高老组火山岩形成于133~123Ma,为早白垩世岩浆活动的产物。岩石学和岩石地球化学特征显示,白音高老组火山岩类似于高分异的I型花岗岩,有斜长石和少量角闪石部分熔融残留。锆石的~(176)Hf/~(177)Hf值介于0.282854~0.283026之间,ε_(Hf)(t)为较高的正值,变化于+5.5~+11.5之间,Hf二阶段模式年龄(T_(DM2))为828~439Ma,表明兴安地块地壳的主体增生年代为新元古代—显生宙。通过对比东北地区(以邻区为主)同时代岩浆-构造活动,研究区内白音高老组火山岩形成于伸展构造环境,这种伸展构造环境的形成可能与古太平洋板块俯冲于欧亚大陆之下的弧后伸展环境有关。