离子探针锆石U-Pb定年的“高U效应”

高U锆石的离子探针U-Pb分析中存在随U含量升高而表现更老的现象,称之为"高U效应"。本文尝试性总结了UPb衰变过程可造成锆石晶格的损伤、后期热愈合作用造成损伤锆石的结构变化、离子探针Pb/U离子化效率差异等因素,认为"高U效应"主要源于损伤锆石处于微尺度的混晶状态(晶态Zr SiO_4、ZrO_2和无定形SiO_2),放射成因Pb容易进入无定性SiO_2,而U进入ZrO_2,造成Pb/U离子化效率差与锆石情况不同。统计发现,高U锆石不仅表现为偏老的"高U效应",还受损伤导致Pb丢失的影响,结果存在较大不确定性,不适宜离子探针精确U-Pb定年,应在测试选点过程中避免,或选用其他矿物,如独居石、磷钇矿、榍石等代替。     

含U副矿物的原位微区U-Pb定年方法

同位素地质年代学是解决地质体时、空演化及大陆动力学等地学研究的基础,而副矿物U-Pb年代学是常用的定年方法之一。含U副矿物广泛分布于各种类型的岩石中,其U[CD*2]Pb年龄可提供地质体演化过程中所发生的地质事件的时代,而传统的热电离质谱全溶年代学分析只能提供样品年龄信息的平均值。随着仪器科学和分析技术的进步,副矿物的原位微区U-Pb测年方法成为近年来U-Pb同位素地质年代学发展的主导趋势。与锆石相比,其它副矿物的U-Pb同位素体系相对比较复杂,经常含较高的普通Pb。在仔细阅读相关文献的基础上,结合近年来相关研究工作,综述副矿物原位微区U-Pb定年以及普通Pb校正方法研究的最新进展,以期推动我国副矿物原位微区U-Pb定年方法相关研究及其在地质学中的应用。     

桂东北豆乍山产铀花岗岩的铀源矿物研究

豆乍山花岗岩是桂东北重要的产铀花岗岩之一,通过精细矿物学研究,豆乍山花岗岩中绿泥石主要为铁绿泥石和辉绿泥石,而含铀副矿物的蚀变和形成温度相对较高的铁绿泥石密切相关.花岗岩中主要富铀副矿物为晶质铀矿、锆石、独居石、磷钇矿和铀钍石,其中晶质铀矿是公认铀源矿物,而其他副矿物的赋存状态及蚀变特征决定了其是否为铀源矿物.锆石多未发生蚀变,U仍保持其结构中,因此不是铀源矿物;而铁绿泥石附近的独居石和磷钇矿均发生不同程度的蚀变,蚀变作用不仅使独居石和磷钇矿结构中的U 得以释放进入热液,而且原磷钇矿包裹的铀钍石变为赋存于次生磷灰石中,其所含铀容易活化而成为铀源矿物.总之,在豆乍山产铀花岗岩含铀副矿物中,晶质铀矿、蚀变的独居石和磷钇矿、次生磷灰石中铀钍石是铀源矿物.     

云南哀牢山-红河剪切带新生代富碱侵入岩中榍石年代学和地球化学特征

榍石作为副矿物在哀牢山-红河剪切带新生代富碱侵入岩中广泛存在。原位获取榍石矿物内部微量元素、U-Pb年龄和Sm-Nd同位素的空间变化对获取矿物和岩石的成因演化信息具有重要意义。本文使用四级杆/多接收电感耦合等离子体质谱(Quadrupole/Multi-Collector Inductively Coupled Plasma Mass Spectrometry,Q/MC-ICP-MS)与激光剥蚀系统(Laser Ablation,LA)联用,对哀牢山-红河剪切带5个富碱侵入岩体(桃花岩体、宁蒗-永胜岩体、哈播岩体、铜厂岩体和十里村岩体)中榍石开展了微区原位微量元素、U-Pb年代学和Sm-Nd同位素研究。微量元素分析结果表明,三江富碱侵入岩中榍石为岩浆成因,亏损Rb、Ba、Pb、Sr等大离子亲石元素,富集Th、U、Nb、Ta、Zr、Hf等高场强元素。榍石的稀土配分图均表现为明显右倾,不具有或具有弱的Eu负异常。与云南北衙、马厂箐矽卡岩矿床中的热液榍石相比,本文榍石在稀土元素组成上,具有较高的稀土元素总量、较高的Th/U、LREE/HREE和Ce/Ce*比值,具有较低的Eu/Eu*、Nb/Ta、Zr/Hf比值。微区原位LA-Q-ICP-MS U-Pb定年结果表明,研究区富碱岩体中榍石结晶年龄在32.5～37.9Ma之间,代表了岩体形成时代,与三江地区哀牢山-红河剪切带及其附近新生代富碱岩浆活动高峰期(～35Ma)一致,属于青藏高原晚碰撞期岩浆作用的产物。榍石微区原位LA-MCICP-MS Sm-Nd同位素分析结果显示,榍石颗粒的Nd同位素组成均一,表明榍石结晶过程中寄主岩浆的Nd同位素组成没有发生明显变化。各个富碱岩体之间的榍石Nd同位素组成变化范围在-6.8～-2.1之间,与全岩的同位素特征一致,表明榍石的原位微区Sm-Nd同位素可以作为富碱侵入岩研究中有效的示踪手段之一。     

副矿物的电子探针化学定年方法原理及应用

化学定年方法是利用电子探针分析副矿物中的U、Th、Pb含量而进行定年的一种新方法。基本原理是，假设可以忽赂矿物韧始铅，封闭体系中矿物的总铅含量代表U—Th衰变形成的放射性成因铅含量，即：Pb总＝^238U(e^λ238r-1) ^235U(e^λ235r—1) ^232Th(e^λ232r—1)，该方法可利用的副矿物包括：锆石、独居石、褐帘石、碘纪矿、铀石、钍石、晶质铀矿等。本文以华南西华山岩体漂塘花岗岩中的锆石为例，对该方法进行了尝试性的研究。分析结果计算表明，两颗锆石的平均年龄分别为143．9Ma和143Ma，与前人通过同位素方法获得的年龄基本相符。结果还显示，锆石颗粒从中心到边缘的年龄呈现从老到新的趋势。     

变质岩中锆石U—Pb计时问题评述——兼论大别造山带锆石定年

锆石是U－Pb计时的首选对象，对于地质历史复杂的变质岩地区，如大别碰撞造山带的年代学研究，具有不可替代的重要性。变质岩中锆石经历了Pb的扩散丢失作用；晶格损伤导致的蜕晶化作用；增生－混合作用和重结晶作用。这些过程对锆石计时的准确性和有效性带来不同程度的影响。为了使测定的年龄有确定的地质意义，在进行锆石U－Pb定年前，必需对锆石进行成因矿物学和矿物内部结构研究，特别是阴极荧光和背散射电子成像研究，通过内部结构特征确定锆石成因过程。在化学U－Pb法定年时注意普通铅校正和^204Pb测定值对年龄的影响，尽量选择单一成因锆石。特别强调在大别造山带年代学中引入锆石微区离子探针定年技术。     

榍石LA-ICP-MS U-Pb定年中元素分馏的影响及校正研究

同位素地质年代学是探索地质体时空演化及地球动力学等问题的基础学科,应用最为广泛的当属含铀副矿物的U-Pb定年技术。榍石具有相对较低的U-Pb体系封闭温度,并广泛发育于岩浆岩、各类变质岩、热液成因岩石以及少量沉积岩中,是一种理想的中高温地质事件定年矿物。利用电感耦合等离子体质谱法(ICP-MS)测定榍石U-Pb年龄时,不可避免地要解决高普通铅以及元素分馏效应对测试的影响。本文对榍石LA-ICP-MS实验过程中的元素分馏行为进行研究,采用相同基体的标准样品与未知样品对比,发现了榍石不同颗粒之间元素分馏行为不一致的现象;同时采用不同的元素分馏校正方法,分别应用于锆石、独居石和榍石进行对比研究,认为分馏行为一致的副矿物定年可以采用"指数法"和"均值法"对数据进行校正,但是对于榍石这种分馏行为不一致的副矿物,定年时只有采用"截距法"对数据进行校正才可以获得正确的年龄。进而将此结论应用于秦岭造山带老牛山地区岩浆成因榍石样品,得到的结果与锆石年龄一致,表明"截距法"可以避免分馏行为不一致导致的校正不准确的问题。本研究成果为榍石LA-ICP-MS U-Pb定年方法的完善提供了一种思路。     

锡石LA-ICP-MSU-Pb定年在稀有金属矿床研究中的应用

<正>原生锡矿床具多种类型,如矽卡岩型、云英岩型、石英脉型、斑岩型、花岗岩型、伟晶岩型和喷流沉积型。如何厘定与锡矿有关的花岗岩的结晶时间,目前已经有了较成熟的原位单矿物U-Pb同位素定年方法,用于定年的副矿物通常包括锆石、独居石、榍石、铌钽矿、磷钇矿等。然而,用来厘定锡矿成矿年龄的测     

电子探针Th-U-Pb微区测年方法及其在铀矿地质研究中的应用前景

电子探针Th-U-Pb微区测年方法是新近发展起来的一项测年技术.该技术以放射性核素的衰变理论为基础,在一定条件下通过电子探针测量矿物中的Th、U、Pb含量,经过数据处理,最终计算出矿物的年龄.由于该项技术具有省时、费用低、不破坏样品等优点,现已广泛地应用于独居石、锆石的年龄研究中.在晶质铀矿年龄研究中的应用仅有零星报道,但由于该技术的高空间分辨率,将对不同产出状态的微小晶质铀矿颗粒的定年研究大有裨益.     

新疆拜城波孜果尔碱性岩中副矿物的特征

在野外地质调查的基础上,结合室内显微镜观察及电子探针分析测试,对新疆拜城波孜果尔碱性岩中的副矿物的矿物学特征和化学成分进行了研究.发现这些副矿物常以共生组合的形式产在碱性岩中,主要分布在石英二长闪长岩和石英二长岩中.烧绿石中U、Th和REE替代Ca、Na.独居石富含LREE,Th和LREE相互替代;根据独居石中w(La+ Ce) ＞40％和La/Nd比值在1.6～4.5,推断独居石为热液成因.磷钇矿中富含REE,且以HREE为主;w(Th)＞w(U).锆石中Zr/Hf比值在60％以上,符合碱性岩特征;其Th/U比值为0.6,属于岩浆锆石.星叶石中w(Rb2O)、w(Cs2O)较高.萤石中Y、Ce替代Ca.锆石中的钍石w(U)明显高于磁铁矿中钍石w(U).在石英二长岩中,烧绿石的w(CaO)、w(TiO2)、w(ZrO2)、w(U3O8),磷钇矿的w(Y2O3),星叶石的w(TiO2),萤石的w(Ca),氟碳铈镧矿的w(CaO)较丰富;而在石英二长闪长岩中,烧绿石的w(Ce2O3),磷钇矿的REE含量,星叶石的w(Nb2O5)、w(Rb2O),萤石w(Ce)、w(Y)和氟碳铈镧矿的w(La2O3)较高.     

LA-MC-ICP-MS独居石微区原位U-Pb同位素年龄测定

独居石富含U、Th, 同时具有较低的初始普通Pb含量, 是U-Pb和Th-Pb同位素定年的理想对象。由于普遍存在于多种岩石中, 独居石的U-Th-Pb定年具有广阔的应用前景。本文报道利用193 nm ArF准分子激光剥蚀系统和NEPUNE多接收器电感耦合等离子体质谱仪, 对独居石进行微区原位U-Pb同位素年龄测定的新方法。运用这一新方法对独居石样品AL01、BL02和CL03进行微区原位U-Pb同位素年龄测定, 获得AL01和BL02号样品的206Pb/238U年龄加权平均值分别为(288.3±1.1) Ma (n=19)和(446.8±2.3) Ma (n=41); CL03号样品的U-Pb等时线年龄为(396.8±8.8) Ma (n=55), 取得了令人满意的结果。     

Application of Laser Ablation ICP-MS to U-Th-Pb Dating of Monazite

Recent advances in laser ablation ICP-MS techniques allow accurate U-Th-Pb age dating of monazites that are as young as several tens of million years to a precision better than 2%. Accuracy of the age determinations has been improved by true real-time mass bias correction via nebulisation of a solution containing enriched ²³³U and natural Tl isotopes. The Tl-U tracer solution eliminates possible effects of variable sample matrices on the precision and accuracy of measured isotopic ratios. Mass bias corrections based on measured ²⁰⁵Tl/²³³U ratios in the tracer solution allow direct measurement of ²³⁵U in monazite. Combined with high-sensitivity laser ablation ICP-MS measurements, direct measurement of ²³⁵U particularly improves the precision of U-Pb dating of young monazites. Correction for laser-induced Pb/U and Pb/Th elemental fractionation is based on a mathematical treatment of time resolved count-rate data that is independent of laser ablation characteristics, does not require external standardisation and allows variable laser pit size or raster patterns for each measurement. The new procedures make the LA ICP-MS technique more flexible for in situ U-Th-Pb analysis.     

独居石成因特征与U-Th-Pb定年及三江特提斯构造演化研究例析

独居石U-Th-Pb定年在地质年代学研究中占有重要地位,但其成因类型的识别和年龄值的合理地质解释始终是研究的难点。论文通过对比分析岩浆、热液和沉积成因独居石的内部结构、矿物组合以及稀土和微量元素地球化学特征,厘定了不同成因类型独居石的鉴别标志;并以三江特提斯构造演化研究为例,探讨了独居石的U-Th-Pb定年及其合理地质应用。不同地质环境中形成的独居石具有不同的内部结构和矿物组合及元素组成:岩浆独居石可能存在较宽且平直的岩浆环带,常与磷钙钍石共生;相对富集重稀土,具有较高的Y、Sc、Th、U、Sm、Gd等含量和Th/U比值,较低的La、Ce含量和稀土总量,显示为Eu强烈亏损的右倾斜分布模式。而热液独居石可能存在与流体作用有关的扇形环带,常与斜钍石共生;沉积独居石形态多不规则,与自生矿物相伴生。它们具有典型的四分组稀土分布模式,稀土总量较高,相对富集轻稀土(如La、Ce),贫Y、Sc、Th、U、Sm、Gd等,Th/U比值较低。独居石U-Th-Pb定年限定了松潘-甘孜造山带204~190Ma的早期变质作用和168~158Ma的局部热干扰,约140~130Ma冈底斯浅色花岗岩的形成与地壳的缩短加厚及快速隆升作用,约33~22Ma 红河断裂带与伸展作用有关的岩体侵位和左行走滑运动年代(且北部的去顶剥蚀作用要比中部早9Ma),约8~11Myr的东喜马拉雅构造结"挤出"构造变形时限。     

Capabilities and constraints of the Pb-Pb dating of metamorphogenic minerals using the step-leaching method

Based on particular examples, this paper considers the capabilities and constraints of the step-leaching Pb-Pb dating (PbSL) of metamorphogenic minerals. It was shown that stepwise leaching allows the separation of fractions enriched in uranogenic and thorogenic Pb isotopes, which can be used for the determination of mineral ages and the time of crystallization of coexisting equilibrium and, occasionally, disequilibrium monazites. The presence of monazite in a mineral is indicated by a high Th/U ratio similar to that of monazite. The main limitation of the method is related to the presence in minerals of both disequilibrium domains of the mineral matrix and disequilibrium monazite microinclusions. By the example of minerals studied, we discussed three scenarios for the development of the U-Th-Pb isotopic systems of metamorphogenic minerals.     

Composition and chemical microprobe dating of U-Th-Bearing minerals. Part 2. Uraninite, thorite, thorianite, coffinite, and monazite from the Urals and Siberia

To develop further chemical microprobe timing of U-Th-bearing minerals on the basis of upgraded measurement techniques and special age calculation, uraninite, thorite, thorianite, coffinite, monazite from several localities in the Urals and Siberia have been dated. The samples were taken from granitic rocks of the Pervomaisky pluton in the Central Urals; the pre-Jurassic basement of western Siberia and Yamal Peninsula; carbonatite-like dolomite from the Karabash ultramafic massif in the Southern Urals; granitic pegmatites of the Lipovsky vein field; and quartz-sulfide veins of the Pyshma-Klyuchevsky Cu-Co-Au deposit in the Central Urals. Scrutiny of the composition and chemical heterogeneity of mineral grains is a necessary stage of chemical dating aimed at the estimation of the degree of closeness of the U-Th-Pb system and unbiased screening of analytical data. The condition (Si + Ca)/(U + Th + Pb + S) ～ 1 was used as evidence for significant secondary alteration of monazite; the negative correlation between Pb and Th or U +Th in uranitite was used for the same purpose. The positive correlation between Pb and U, along with low concentrations of Ca, Si, and Fe admixtures, implies that the stoichiometric composition of thorite is close to 100%. The reliability and accuracy of the chemical dating of minerals with high contents of radioactive elements can be enhanced by using bimineralic or multimineralic isochrons, e.g., monazite-uraninite, uraninite-coffinite, etc. The results obtained have been compared with the available isotopic ages of the studied minerals; the compared data are satisfactorily consistent.     

Granular titanite from the Roter Kamm crater in Namibia: Product of regional metamorphism,not meteorite impact

Accessory minerals with so-called granular texture have risen in importance as geochronological tools for U-Pb dating of meteorite impact events. Grain-scale recrystallization, typically triggered by a combination of high-strain deformation and post-impact heating, can create a polycrystalline microstructure consisting of neoblasts that expel radiogenic Pb, which are thus ideal for isotopic dating. While granular domains in zircon and monazite from shocked rocks have been demonstrated to preserve impact ages, few U-Pb dating studies have been conducted on granular microstructures in titanite (CaTiSiO₅). Here we report the occurrence of granular-textured titanite from ～2020 Ma granite basement rock exposed in the rim of the 4–5 Ma Roter Kamm impact structure in Namibia. Orientation mapping reveals two microstructurally distinct titanite populations: one consisting of strained/deformed grains, and the other consisting of grains that comprise aggregates of strain-free neoblasts. In situ U-Pb geochronology on 37 grains shows that most grains from both titanite populations yield indistinguishable U-Pb dates of ca. 1025 Ma, consistent with the observed microstructures forming during the Mesoproterozoic Namaqua Orogeny. Only four grains preserved older age domains, recording ca. 1875 Ma Paleoproterozoic metamorphism. Two significant observations emerge: (1) none of the analyzed titanite grains yield the 2020 Ma igneous crystallization age previously established from zircon in the same sample, and (2) no age-resetting was detected that could be attributed to the 4 to 5 Ma Roter Kamm impact event. Despite the similarity of the neoblastic microstructure to minerals from other sites with an established impact provenance, the granular texture and near-complete Pb-loss in titanite from Roter Kamm granite instead records a Paleo- to Mesoproterozoic polymetamorphic history, rather than Miocene age shock-related processes. These results highlight the critical importance of grain-scale context for interpretation of U-Pb data in granular titanite, and the potential for misinterpreting inherited (pre-impact) microstructures as impact-related phenomenon in target rocks with a complex geological history.     

碎屑岩物源研究进展与展望

沉积物物源研究作为沟通沉积盆地与剥蚀区的纽带,有助于恢复源区构造背景、估计沉积物搬运路径与距离、重建古水系和恢复沉积盆地充填演化历史等,在源-汇系统分析中有着非常重要的作用。传统的方法如岩石学、沉积学、重矿物和元素地球化学等方法在物源体系分析中起着重要的作用。随着同位素测试技术的进步,越来越多的碎屑矿物同位素测年开始大量地被应用到物源分析当中。近些年碎屑锆石测年被广泛地应用到沉积盆地物源体系恢复和古水系重建中,而针对碎屑矿物如金红石、独居石和磷灰石等的同位素测年也同样发挥着巨大的作用。多种矿物组合分析以及单矿物多重定年,可以更全面地恢复物源区的构造演化史,从而更准确地恢复构造演化与盆地充填过程之间的耦合关系。同时随着碎屑锆石U/Pb数据的日益增多,越来越多的数学和统计学方法开始被引入用于定量分析不同物源区对沉积区砂体展布的影响。现今和未来的物源分析将是不断引入新的研究技术、将传统方法与新技术的结合、从单一方法到多种方法的综合、从定性分析到定量化研究、从单一学科到多学科交叉的过程,从而更好地让我们认识沉积物在地表的剥蚀搬运沉积的整个过程。     

U-Th-Pb and Trace Element Evaluation of Existing Titanite and Apatite LA-ICP-MS Reference Materials and Determination of 208Pb/232Th-206Pb/238U Date Discordance in Archaean Accessory Phases

The last decade has seen a marked increase in U-Th-Pb petrochronological studies focused on titanite and apatite. This has motivated the need for detailed, phase-specific method development and well-characterised reference materials with a wide variety of ages and chemical compositions. This study presents new U-Th-Pb isotope and major-, minor- and trace-element mass fraction data for ten titanite and five apatite reference materials based on integrated EPMA, LA-ICP-MS and isotope-dilution (ID) multi-collector (MC)-ICP-MS characterisation. Cross-comparison of EPMA and LA-ICP-MS data for the same titanite reference material suite demonstrates that careful selection of EPMA primary reference materials is necessary to minimise inaccuracies. We further identify a significant X-ray interference when measuring low Ce abundances in Ti-bearing phases and outline a method for its correction. New ID-MC-ICP-MS and LA-ICP-MS data suggest tri-concordance (defined as concordant ages for the ²³⁸U-²⁰⁶Pb, ²³⁵U-²⁰⁷Pb and ²³²Th-²⁰⁸Pb decay systems) of the MKED-1 titanite reference material and demonstrate the reproducibility of ²⁰⁸Pb/²³²Th measurements in some secondary titanite reference materials. Integration of ²⁰⁸Pb/²³²Th results with U-Pb geochronology provides a meaningful tool to help interpret complex U-Th-Pb isotopic age spectra. We provide example applications of ²⁰⁸Pb/²³²Th LA-ICP-MS measurements toward interpreting Archaean titanite ages from the Acasta Gneiss Complex, Northwest Territories, Canada.     

铀矿床定年研究进展评述

往往由于铀矿物(沥青铀矿)颗粒细小、易蚀变成铀的次生矿物及多期铀矿化作用相互叠加等在组成和结构上的固有特点,通常难以用挑选铀矿物(沥青铀矿)样品溶样的传统定年方法精确确定其形成年龄。随着分析技术的不断更新和发展,对铀矿床成矿年代学的研究也不断深入。但受铀矿床中铀矿物U-Pb定年方法本身的制约,以及以往对铀矿物U-Pb定年体系中铀矿物样品要求认识的不足,常常导致获得的年龄无实际地质意义或无法获得理想的等时线年龄。本文针对铀矿化定年方法的发展历程进行了系统梳理和分析,评述了铀矿物定年的五种主要方法:(1)铀矿物U-Th-totalPb化学年龄;(2)铀矿物模式年龄;(3)铀矿物传统等时线年龄;(4)铀矿物矿伴生矿物年龄;(5)原位微区铀矿物U-Pb年龄。在此基础上,深入探讨了铀矿化作用定年研究中存在的问题和对应方案,期望促进未来铀矿床成矿年代学的发展。     

Composition and chemical microprobe dating of U-Th-bearing minerals. Part I. Monazites from the Urals and Siberia

To develop chemical microprobe timing of U-Th-bearing minerals, monazite grains from several localities in the Ural and Siberia have been dated using upgraded measurement techniques and age calculation based on original software. The samples were taken from pegmatites of the Ilmeny Mountains and the Ilmeny-Vishnevy Mountains Complex in the South Urals; pegmatites from the Adui granitic pluton and its framework in the Central Urals; gneisses and granulites of the Taratash Complex in the South Urals; and felsic gneisses from the Transangara region of the Yenisei Ridge. Scrutiny of the composition, heterogeneity, and chemical substitution of U and Th ions is a necessary stage of chemical dating aimed at estimating the degree of closeness of the U-Th-Pb system and unbiased screening of analytical data. The results obtained have been compared with the known isotopic ages of the studied minerals; the compared data are satisfactorily consistent.