Precise geochronology of phoscorites and carbonatites:: The critical role of U-series disequilibrium in age interpretations

We present the results of a comparative study of several geochronometer minerals (baddeleyite, zircon, apatite, phlogopite and tetraferriphlogopite) and isotopic systems (U-Pb, Th-Pb and Rb-Sr) from phoscorites (magnetite-forsterite-apatite-calcite rocks) and carbonatites of the Kovdor ultramafic-alkaline-carbonatite massif, Kola Peninsula, Russia. Uranium, thorium and their decay products are extremely fractionated by minerals that crystallise from carbonatite and phoscorite magma. We obtain high-precision ages from different chronometers, compare their accuracy, and evaluate the role of geochronological pitfalls of initial radioactive disequilibrium, differential migration of radiogenic isotopes, and inaccurate decay constants.Apatite yielded concordant U-Th-Pb ages between 376 and 380 Ma. The accuracy of the apatite ²³⁸U-²⁰⁶Pb ages is, however, compromised by uncertainty in the amount of radiogenic ²⁰⁶Pb produced from initial excess ²³⁰Th. The ²³⁵U-²⁰⁷Pb ages are relatively imprecise due to large common Pb correction and the uncertainty in the initial Pb isotopic composition. The Th-Pb system yields a more precise age of 376.4 ± 0.6 Ma.Zircon from two carbonatite samples is characterised by moderate to low U contents, high Th contents, and very high Th/U ratios up to 9000. The ²⁰⁶Pb*/²³⁸U systems in the zircon are strongly affected by the presence of excess ²⁰⁶Pb*, produced by decay of initial ²³⁰Th. The ²⁰⁸Pb*/²³²Th ages of zircon from both carbonatite samples are uniform and yield a weighted average of 377.52 ± 0.94 Ma.Baddeleyite U-Pb analyses are 3 to 6% normally discordant and have variable ²⁰⁷Pb*/²⁰⁶Pb* apparent ages. Eleven alteration-free baddeleyite fractions from three samples with no evidence for Pb loss yield uniform ²⁰⁶Pb*/²³⁸U ages with a weighted average of 378.54±0.23 Ma (378.64 Ma after correction for initial ²³⁰Th deficiency), which we consider the best estimate for age of the phoscorite-carbonatite body of the Kovdor massif. The ²⁰⁶Pb*/²³⁸U ages of baddeleyite fractions from five other samples spread between 378.5 and 373 Ma, indicating a variable lead loss up to 1.5%. The anomalously old ²⁰⁷Pb/²³⁵U and ²⁰⁷Pb/²⁰⁶Pb ages are consistent with the presence of excess radiogenic ²⁰⁷Pb* in the baddeleyite. We interpret this as a result of preferential partitioning of ²³¹Pa to baddeleyite.Fifteen phlogopite and tetraferriphlogopite fractions from five carbonatite and phoscorite samples yielded precise Rb-Sr isochron age of 372.2 ± 1.5 Ma, which is 5 to 7 m.y. younger than our best estimate based on U-Th-Pb age values. This difference is unlikely to be a result of the disturbance or late closure of Rb-Sr system in phlogopite, but rather suggests that the accepted decay constant of ⁸⁷Rb is too high.Comparative study of multiple geochronometer minerals from the Kovdor massif has revealed an exceptional complexity of isotopic systems. Reliable ages can be understood through systematic analysis of possible sources of distortion. No single geochronometer is sufficiently reliable in these rocks. Th-Pb and Rb-Sr can be a very useful supplement to U-Pb geochronometry, but the routine use of these geochronometers together will require more precise and accurate determination of decay constants for ²³²Th and ⁸⁷Rb.     

豫西小秦岭地区秦南金矿床热液独居石U-Th-Pb定年及其地质意义

小秦岭地区是我国最重要的金矿产区之一, 目前对该区金矿床成矿作用存在两种不同的观点, 即与秦岭造山带造山作用有关的早中生代成矿和与中国东部构造体制大转折有关的晚中生代成矿.在矿床地质研究的基础上, 利用激光剥蚀ICP-MS方法对小秦岭矿集区北矿带秦南金矿床的热液独居石进行了U-Th-Pb定年, 获得了高精度的年龄数据, 为北矿带金矿床成矿时代和成矿构造背景提供了新的制约.岩相学研究表明, 所研究的独居石具有完好的晶形, 与载金矿物黄铁矿和石英的结构关系表明它们近于同时形成.13个独居石颗粒的U-Th-Pb同位素组成在206Pb/238U-207Pb/235U和206Pb/238U-208Pb/232Th图解上均位于谐和线上或其附近, 其206Pb/238U和208Pb/233Th加权平均年龄分别为120.9±0.9 Ma(MSWD=1.0)和122.6±1.9 Ma(MSWD=2.6), 在误差范围内完全一致.本次定年结果与小秦岭南矿带众多典型金矿床的Re-Os年龄和40Ar/39Ar年龄一致, 表明独居石的U-Th-Pb同位素体系自矿物形成后一直处于封闭体系, 其U-Pb和U-Th-Pb年龄可以解释为秦南金矿床的成矿时代, 从而表明秦南金矿床形成于燕山期.对已有可靠年龄数据的统计分析表明, 小秦岭地区绝大多数金矿床形成于早白垩世, 证明该区金成矿作用集中发生于晚中生代, 可能与华北克拉通岩石圈减薄作用有关.      

A LA-ICP-MS Comparison of Reference Materials Used in Cassiterite U-Pb Geochronology

Laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) is used to compare the suitability of four cassiterite (SnO₂) materials (SPG, Yankee, AY-4 and Jian-1), and three matrix-mismatched reference materials (NIST SRM 612, NIST SRM 614 and 91500 zircon) for normalisation of U-Pb and Pb-Pb isotope ratios in cassiterite. The excess variance of ages determined by LA-ICP-MS is estimated to be ±0.33% for ²⁰⁷Pb/²⁰⁶Pb vs. ²⁰⁸Pb/²⁰⁶Pb isochron ages and ± 1.8% and for U-Pb ages. Incorporation of this excess variance in cassiterite ages is necessary for realistic uncertainties. ²⁰⁷Pb-²⁰⁶Pb ages are advantageous for dating Precambrian cassiterite such as SPG compared with U-Pb ages as matrix effect on instrumental mass fractionation of Pb isotopes are generally considered to be minor. We note minor bias in ²⁰⁷Pb/²⁰⁶Pb vs. ²⁰⁸Pb/²⁰⁶Pb isochron ages (~ 0.6%) when using either the NIST SRM 614 or 91500 zircon reference materials and emphasise the requirement for uncertainty propagation of all sources of error and reference materials with comparable U and Pb mass fraction to the cassiterite. The ²³⁸U/²⁰⁶Pb isotopic ratios from normalisation to matrix-mismatched reference materials show varied results, which emphasises the need to use matrix-matched reference materials for calculating U-Pb ages. When cross-calibrated against each other, LA-ICP-MS U-Pb ages of the ca. 1535 Ma SPG, ca. 245 Ma Yankee and ca. 155 Ma Jian-1 cassiterites are all consistent with their ID-TIMS values.     

U–Pb systematics of the McClure Mountain syenite: thermochronological constraints on the age of the 40Ar/39Ar standard MMhb

Recent advances in U–Pb geochronology allow unprecedented levels of precision in the determination of geological ages. However, increased precision has also illuminated the importance of understanding subtle sources of open-system behavior such as Pb-loss, inheritance, intermediate daughter product disequilibria, and the accuracy of the model assumptions for initial Pb. Deconvolution of these effects allows a much richer understanding of the power and limitations of U–Pb geochronology and thermochronology. In this study, we report high-precision ID-TIMS U–Pb data from zircon, baddelleyite, titanite and apatite from the McClure Mountain syenite, from which the ⁴⁰Ar/³⁹Ar hornblende standard MMhb is derived. We find that excess ²⁰⁶Pb in zircon due to inclusions of high-Th minerals and elevated Th/U in titanite and apatite jeopardize the utility of the ²³⁸U–²⁰⁶Pb system in this rock. Strongly air-abraded zircons give dates that are younger than chemical-abraded zircons, which yield a statistically robust ²⁰⁷Pb/²³⁵U date of 523.98±0.12 Ma that is interpreted as the crystallization age. We explore the best method of Pb_c correction in titanite and apatite by analyzing the U–Pb isotopes of K-feldspar and using 2-D and 3-D regression methods—the latter of which yields the best results in each case. However, the calculated compositions of Pb_c for titanite, apatite and K-feldspar are different, implying that using a single Pb_c correction for multiple U–Pb thermochronometers may be inaccurate. The U–Pb thermochronological results are used to predict a closure time for Ar in hornblende of 522.98±1.00 Ma. Widely cited K–Ar and ⁴⁰Ar/³⁹Ar dates overlap with the U–Pb date, and relatively large errors make it impossible to verify whether U–Pb dates are systematically ≤1% older than K–Ar and ⁴⁰Ar/³⁹Ar dates.     

西藏山南列麦始新世花岗岩独居石U-Th-Pb年龄及地质意义

西藏山南隆子县列麦地区始新世花岗岩的成岩时代和背景对喜马拉雅地区同碰撞阶段的构造演化具有重要意义。本文对隆子县列麦乡界归党村的白云母花岗岩开展独居石LA-ICP-MS U-Th-Pb测年,独居石40个测点的~(208)Pb/~(232)Th加权平均年龄为41±0.1Ma(MSWD=1.4),形成于始新世中期。结合区域上的始新世岩浆岩活动和区域变质作用,本文认为在50～45Ma印度下地壳发生中-高压变质和部分熔融;45Ma新特提斯洋洋壳板片断离,软流圈地幔上涌;45～41Ma喜马拉雅发生短暂的拉张环境导致大量的埃达克质岩浆岩侵位和麻粒岩的折返。     

Disturbance versus preservation of U–Th–Pb ages in monazite during fluid–rock interaction: textural, chemical and isotopic in situ study in microgranites (Velay Dome, France)

Monazite is extensively used to date crustal processes and is usually considered to be resistant to diffusive Pb loss. Nevertheless, fluid-assisted recrystallisation is known to be capable of resetting the monazite chronometer. This study focuses on chemical and isotopic disturbances in monazite grains from two microgranite intrusions in the French Central Massif (Charron and Montasset). Petrologic data and oxygen isotopes suggest that both intrusions have interacted with alkali-bearing hydrothermal-magmatic fluids. In the Charron intrusion, regardless of their textural location, monazite grains are sub-euhedral and cover a large domain of compositions. U–Pb chronometers yield a lower intercept age of 297 ± 4 Ma. An inherited component at 320 Ma is responsible for the scattering of the U–Th–Pb ages. The Montasset intrusion was later affected by an additional F-rich crustal fluid with crystallisation of Ca-REE-fluorocarbonates, fluorite, calcite and chloritisation. Pristine monazite is chemically homogeneous and displays ²⁰⁸Pb/²³²Th and ²⁰⁶Pb/²³⁸U concordant ages at 307 ± 2 Ma. By contrast, groundmass monazite shows dissolution-recrystallisation features associated with apatite and thorite precipitation (Th-silicate) and strong chemical reequilibration. ²⁰⁸Pb/²³²Th ages are disturbed and range between 270 and 690 Ma showing that the Th/Pb ratio is highly fractionated during the interaction with fluids. Apparent U–Pb ages are older due to common Pb incorporation yielding a lower intercept age at 312 ± 10 Ma, the age of the pristine monazite. These results show that F-rich fluids are responsible for Th mobility and incorporation of excess Pb, which thus strongly disturbed the U–Th–Pb chronometers in the monazite.     

宁芜地区玢岩铁矿Pb同位素研究

本文对宁芜地区铁矿床中磷灰石和矿石进行了Pb同位素测定。磷灰石的208Pb-232Th等时线年龄为124Ma,与辉长闪长(玢)岩和钠长石岩的形成年龄均相吻合,为成矿时代与成岩时代相近提供了佐证。岩体长石Pb同位素显示,宁芜地区中生代火成岩的原始岩浆受到了大陆壳深部3.3Ga的古老岩系的混染。矿床中矿石铅主要来自赋矿母岩浆。成矿流体具有异常高的Th/U值,表明Th相对U的明显富集,这可能反映了流体中卤素为主要的矿物质迁移载体。     

U–Pb and Th–Pb dating of apatite by LA-ICPMS

Apatite is a common U- and Th-bearing accessory mineral in igneous and metamorphic rocks, and a minor but widespread detrital component in clastic sedimentary rocks. U–Pb and Th–Pb dating of apatite has potential application in sedimentary provenance studies, as it likely represents first cycle detritus compared to the polycyclic behavior of zircon. However, low U, Th and radiogenic Pb concentrations, elevated common Pb and the lack of a U–Th–Pb apatite standard remain significant challenges in dating apatite by LA-ICPMS, and consequently in developing the chronometer as a provenance tool.This study has determined U–Pb and Th–Pb ages for seven well known apatite occurrences (Durango, Emerald Lake, Kovdor, Mineville, Mud Tank, Otter Lake and Slyudyanka) by LA-ICPMS. Analytical procedures involved rastering a 10 μm spot over a 40 × 40 μm square to a depth of 10 μm using a Geolas 193 nm ArF excimer laser coupled to a Thermo ElementXR single-collector ICPMS. These raster conditions minimized laser-induced inter-element fractionation, which was corrected for using the back-calculated intercept of the time-resolved signal. A Tl–U–Bi–Np tracer solution was aspirated with the sample into the plasma to correct for instrument mass bias. External standards (Ple?ovice and 91500 zircon, NIST SRM 610 and 612 silicate glasses and STDP5 phosphate glass) along with Kovdor apatite were analyzed to monitor U–Pb, Th–Pb, U–Th and Pb–Pb ratiosCommon Pb correction employed the ²⁰⁷Pb method, and also a ²⁰⁸Pb correction method for samples with low Th/U. The ²⁰⁷Pb and ²⁰⁸Pb corrections employed either the initial Pb isotopic composition or the Stacey and Kramers model and propagated conservative uncertainties in the initial Pb isotopic composition. Common Pb correction using the Stacey and Kramers (1975) model employed an initial Pb isotopic composition calculated from either the estimated U–Pb age of the sample or an iterative approach. The age difference between these two methods is typically less than 2%, suggesting that the iterative approach works well for samples where there are no constraints on the initial Pb composition, such as a detrital sample. No ²⁰⁴Pb correction was undertaken because of low ²⁰⁴Pb counts on single collector instruments and ²⁰⁴Pb interference by ²⁰⁴Hg in the argon gas supply.Age calculations employed between 11 and 33 analyses per sample and used a weighted average of the common Pb-corrected ages, a Tera–Wasserburg Concordia intercept age and a Tera–Wasserburg Concordia intercept age anchored through common Pb. The samples in general yield ages consistent (at the 2σ level) with independent estimates of the U–Pb apatite age, which demonstrates the suitability of the analytical protocol employed. Weighted mean age uncertainties are as low as 1–2% for U- and/or Th-rich Palaeozoic–Neoproterozoic samples; the uncertainty on the youngest sample, the Cenozoic (31.44 Ma) Durango apatite, ranges from 3.7–7.6% according to the common Pb correction method employed. The accurate and relatively precise common Pb-corrected ages demonstrate the U–Pb and Th–Pb apatite chronometers are suitable as sedimentary provenance tools. The Kovdor carbonatite apatite is recommended as a potential U–Pb and Th–Pb apatite standard as it yields precise and reproducible ²⁰⁷Pb-corrected, ²³²Th–²⁰⁸Pb, and common Pb-anchored Tera–Wasserburg Concordia intercept ages.     

三峡地区二叠系牙形石的U-Th-Pb定年及古海水信息

利用激光剥蚀电感耦合等离子质谱(LA-ICP-MS)对三峡地区二叠系茅口组牙形石的U-Th-Pb同位素年龄进行测定。结果表明该地层中牙形石的208Pb/232Th放射年龄为269±44,Ma,207Pb/235U放射年龄为256±39,Ma,接近二叠系茅口组的生物地层年龄。206Pb/238U的年龄为196±6,Ma,虽然准确度较高,但与前人推测的地层年龄相比偏低。此外,作者对牙形石的稀土元素(REE)组成进行了分析,并且发现牙形石的REE组成和Ce异常与古海水氧化还原条件有一定的相关性,可以指示古海水的信息。     

Provenance ages and alteration histories of shales from the Middle Archean Buhwa greenstone belt, Zimbabwe: Nd and Pb isotopic evidence

Shales of the ca. 3.0 Ga Buhwa Greenstone Belt, Zimbabwe, were derived from a compositionally diverse provenance whose ages, determined by ion probe analyses of detrital zircons in interbedded sandstones, range from 3.8 to 3.1 Ga. Geochemical data for the shales were previously interpreted to indicate that sediments had been derived from an intensely weathered source. REE concentrations in the shales were interpreted to suggest that the provenance was compositionally mixed, with components of felsic (tonalite and alkalic granitoid) and mafic rocks. Sm/Nd and Nd isotopic compositions of these rocks can be used to model initial Nd isotopic ratios at the time of sedimentation (ε_Ndsed), as well as model crustal formation ages (T_DM). The former, at the age of sedimentation, range from +0.6 to −10.8, consistent with a range of provenance ages. The latter range from 4.46 Ga to 2.99 Ga. The oldest crustal formation ages, up to 0.7 Ga older than known detrital components, are interpreted here to indicate that the Sm-Nd system of the sediments experienced open system behavior. The implied alteration would have included an increase in Sm/Nd by about 20-25 percent, probably in the form of preferential loss of Nd with respect to Sm. The Pb isotopic compositions of whole rock samples are quite radiogenic, with a range of ²⁰⁶Pb/²⁰⁴Pb from 25.5 to 154. An array of ten samples lies scattered about a line with a ²⁰⁷Pb/²⁰⁴Pb -²⁰⁶Pb/²⁰⁴Pb slope age of about 2.73 Ga. Five individual samples were sequentially leached to further test the timing and characteristics of this U-Th-Pb alteration event. These arrays of a whole rock, three leach steps, and a residue also form linear Pb-Pb arrays (one is more scattered) with ages ranging from 2260 ± 360 Ma to 2824 ± 170 Ma, suggesting that all samples experienced a latest Archean to earliest Proterozoic enrichment in U/Pb. This age range also may be the approximate age of Sm/Nd enrichment for the shales. All samples, both whole rocks and leached samples, lie grouped on a ²⁰⁸Pb/²⁰⁴Pb - ²⁰⁶Pb/²⁰⁴Pb diagram around a line with ²³²Th/²³⁸U = 3.5 (2.9 to 3.9). Because of the lack of large differences in the Th/U of the samples through large ranges of U/Pb, we interpret this consistency in Th/U to mean that the shales of the Buhwa belt experienced Pb loss, rather than U and Th gain. Circumstances that may be responsible for Pb loss in a sedimentary basin include loss of saline fluids during basin dewatering. Such an event would likely have been related to folding associated with the thrusting and magmatic intrusion of the adjacent Limpopo Belt, suggesting that uplift, dewatering, and geochemical and isotopic alteration can be genetically related.     

数据不协调时独居石EPMA CHIME定年计算方法的改进

Th-U-Pb系统数据不协调是独居石电子探针化学定年(EPMA CHIME Dating)中一种很常见的问题。独居石矿物产生数据不协调的主要原因包括:1)蚀变或重结晶造成的铅丢失;2)不同年龄域在空间上的重叠或者存在于很小颗粒上的小年龄域。独居石EPMA年龄必大于U等于0时的极端情况给出的值,即当U为0时,EPMA CHIME年龄给出的是~(208)Pb/~(232)Th年龄,这是测量区域内最老年龄的下限。当Th为0时,EPMA CHIME年龄值介于~(206)Pb/~(238)U和~(207)Pb/~(235)U年龄值之间,这是EPMA法所能得到的最老年龄的上限。分析表明,当独居石EPMA数据出现不协调时,传统等时线方法计算的年龄值误差较大。本文提出了一种处理数据不协调情况下的优化算法。该算法考虑了测量误差,并根据剩余铀的总量剔出大的离散数据。利用已公开的数据进行算法对比的结果表明,本文提出的优化算法计算结果可靠。     

Community‐Derived Standards for LA‐ICP‐MS U‐(Th‐)Pb Geochronology – Uncertainty Propagation,Age Interpretation and Data Reporting

The LA‐ICP‐MS U‐(Th‐)Pb geochronology international community has defined new standards for the determination of U‐(Th‐)Pb ages. A new workflow defines the appropriate propagation of uncertainties for these data, identifying random and systematic components. Only data with uncertainties relating to random error should be used in weighted mean calculations of population ages; uncertainty components for systematic errors are propagated after this stage, preventing their erroneous reduction. Following this improved uncertainty propagation protocol, data can be compared at different uncertainty levels to better resolve age differences. New reference values for commonly used zircon, monazite and titanite reference materials are defined (based on ID‐TIMS) after removing corrections for common lead and the effects of excess ²³⁰Th. These values more accurately reflect the material sampled during the determination of calibration factors by LA‐ICP‐MS analysis. Recommendations are made to graphically represent data only with uncertainty ellipses at 2s and to submit or cite validation data with sample data when submitting data for publication. New data‐reporting standards are defined to help improve the peer‐review process. With these improvements, LA‐ICP‐MS U‐(Th‐)Pb data can be considered more robust, accurate, better documented and quantified, directly contributing to their improved scientific interpretation.     

Natural Titanite Reference Materials for In Situ U‐Pb and Sm‐Nd Isotopic Measurements by LA‐(MC)‐ICP‐MS

Titanite is a common accessory mineral that preferentially incorporates considerable amounts of U and light rare earth elements in its structure, making it a versatile mineral for in situ U‐Pb dating and Sm‐Nd isotopic measurement. Here, we present in situ U‐Pb ages and Sm‐Nd isotope measurement results for four well‐known titanite reference materials (Khan, BLR‐1, OLT1 and MKED1) and eight titanite crystals that could be considered potential reference material candidates (Ontario, YQ‐82, T3, T4, TLS‐36, NW‐IOA, Pakistan and C253), with ages ranging from ~ 20 Ma to ~ 1840 Ma. Results indicate that BLR‐1, OLT1, Ontario, MKED1 and T3 titanite have relatively homogeneous Sm‐Nd isotopes and low common Pb and thus can serve as primary reference materials for U‐Pb and Sm‐Nd microanalysis. YQ‐82 and T4 titanite can be used as secondary reference materials for in situ U‐Pb analysis because of their low common Pb. However, internal structures and mineral inclusions in YQ‐82 will require careful selection of suitable target domains. Pakistan titanite is almost concordant with an age of 21 Ma and can be used as a reference material when dating Cenozoic titanite samples.     

Columbite SN3: A New Potential Reference Material for U-Pb Dating by LA-ICP-MS

Columbite-tantalite LA-ICP-MS U-Pb dating is a fast and useful method to determine the age of rare-metal deposits and fingerprint the provenance of columbite-tantalite ore concentrates. Accurate LA-ICP-MS U-Pb dating requires matrix-matched reference materials. We analysed three columbite-tantalite samples (SN3, HND and RL2) from China using ID-TIMS and LA-ICP-MS to assess their potential as reference materials for in situ U-Pb dating. Coltan 139 and these three columbite-tantalite samples with variable compositions yielded internally consistent LA-ICP-MS U-Pb ages when using each other for calibration and the weighted mean ²⁰⁶Pb/²³⁸U ages are comparable to respective ID-TIMS ages. Composition-dependent U-Pb fractionation seems to be insignificant under the LA-ICP-MS conditions used. Sample SN3 has a low percentage of heterogeneity for ²⁰⁶Pb/²³⁸U ages (4%) with low common Pb contributions (f₂₀₆ < 1%) and shows a good potential in calibrating unknown samples as primary reference material for LA-ICP-MS analysis. Samples RL2 and HND have altered sections characterised by high LREE contents, flat LREE patterns and old ²⁰⁶Pb/²³⁸U apparent ages, and are not suited as reference materials. The low ²⁰⁷Pb/²⁰⁶Pb intercepts for samples RL2 and HND lack geological meaning but provide strong evidence that the disturbed U-Pb systematics with anomalous apparent ²⁰⁶Pb/²³⁸U ages is a secondary feature.     

广西苗儿山铀矿田张家铀矿床成矿时代:沥青铀矿微区原位测定

张家铀矿床是苗儿山铀矿田北部的代表性铀矿床之一,对其开展详细的成矿年代学研究不仅对认识区域铀成矿规律十分重要,也对探讨华南花岗岩型热液铀矿床的成矿大地构造背景及动力学机制具有重要意义.在详细的镜下观察基础上,采用电子探针U-Th-Pb化学法、LA-ICP-MS U-Pb同位素方法对脉状沥青铀矿进行了年代学研究.20个点的U-Th-Pb化学年龄为55.3~81.1 Ma,其中19个点的加权平均年龄为71.4±1.9 Ma.根据稀土元素特征的不同,将34个点的LA-ICP-MS U-Pb同位素年龄分为2组,第一组共15个点,其中13个点的206Pb/238U加权平均年龄为69.4±4.9 Ma;第二组共19个,其中16个点的206Pb/238U加权平均年龄为94.1±3.0 Ma.电子探针U-Th-Pb化学法加权平均年龄（71.4±1.9 Ma）与LA-ICP-MS U-Pb同位素法较年轻的一组206Pb/238U加权平均年龄（69.4±4.9 Ma）一致,代表张家铀矿床的成矿时代,LA-ICP-MS U-Pb同位素法较老的一组206Pb/238U加权平均年龄（94.1±3.0 Ma）可能是沥青铀矿受后期改造和/或样品剥蚀过程杂质矿物影响而地质意义不明确.晚中生代期间,古太平洋板块向欧亚大陆俯冲可能是控制华南大规模花岗岩型铀矿床形成的动力学机制,包括张家铀矿床在内的华南花岗岩型铀矿床大规模成矿作用可能受80~50 Ma古太平洋板块对亚洲东部的斜向俯冲动力体制的控制.      

The U, Th and Pb elemental and isotope compositions of mantle clinopyroxenes and their grain boundary contamination derived from leaching and digestion experiments

Minerals from peridotites are known to be affected by trace element contamination on their grain boundaries. In this contribution we investigate the extent and origin of exogenous contamination associated with mantle clinopyroxenes from various localities (Middle Atlas, Beni Bousera [Morocco], Pyrenean Massif, Massif Central [France]) and test the efficacy of different leaching methodologies used to remove this contamination. In doing so we present new U-Th-Pb (double-spike) isotope and trace elemental data of clinopyroxenes and their leachates from spinel-facies sub-continental lithospheric mantle (SCLM, n = 18).Sequential leaching and dissolution of one clinopyroxene separate shows that multiple and short leaching attacks with dilute HCl at moderate temperatures (e.g., 120 °C) interspersed with rigorous ultra-pure water washes do not induce elemental fractionation and are sufficient to remove grain-boundary contamination. Short attacks with very dilute mixtures of HF and HCl induced strong parent/daughter elemental fractionation and significant elemental loss prior to the clinopyroxene digestion with HF/HNO₃. Such leaching is not suitable for studies investigating parent/daughter elemental or isotope ratios of mantle clinopyroxenes. Fluoride co-precipitates that formed in the presence of moderately dilute HF, used during leaching and typical HF/HNO₃ digestions, are an important sink for all trace elements studied here and lock up at least 60% of the trace elements considered.A suite of clinopyroxene-leachate pairs from Moroccan peridotites confirm extreme grain-boundary contamination and show that up to 65% of U, 82% of Th and 91% of Pb, respectively, are of exogenous origin. Pb isotopes of all leachates considered and nearly all reconstructed unleached clinopyroxenes have highly positive Δ7/4 and ²⁰⁷Pb/²⁰⁴Pb-²⁰⁶Pb/²⁰⁴Pb systematics reminiscent of enriched mantle (particularly EM II), whereas the corresponding extensively leached clinopyroxenes have very different Pb isotope systematics (verified by replicate digestions). Furthermore, the leachates are often marked by remarkably high ²³²Th/²³⁸U (leachate ? bulk silicate Earth) in addition to ²³⁸U/²⁰⁴Pb and ²³²Th/²⁰⁴Pb that are seemingly consistent with depleted mantle (DM) and high ²³⁸U/²⁰⁴Pb (HIMU) mantle mixing. After leaching, clinopyroxenes may have highly elevated ²³⁸U/²⁰⁴Pb and ²³²Th/²⁰⁴Pb that are distinct from typical DM- and HIMU mantle, whereas corresponding leachates bear strong resemblance to anthropogenic Pb recovered from rainwater, snow and aerosols.In the light of the great potential of Pb isotope contamination associated with mantle clinopyroxene we have compiled literature data of mantle peridotites. These data seem to suggest that the SCLM is nearly devoid of HIMU signatures but ostensibly represents an important repository for enriched mantle signatures. However, the dominance of enriched mantle is not verified when ⁸⁷Sr/⁸⁶Sr and ²⁰⁸Pb/²⁰⁴Pb ratios for the same database are considered. We highlight that the scarcity of HIMU-like SCLM and the alleged dominance of EM in continental roots may be reconciled if the current Pb isotope database of SCLM contains samples that were insufficiently leached prior to digestion and thus are contaminated by anthropogenic Pb. We stress the importance of replicate digestions, adequate leaching and leachate analysis to verify the U-Th-Pb elemental and isotope systematics of any given mantle (-derived) sample.     

The thermo-tectonic history of the Song-Kul plateau, Kyrgyz Tien Shan: Constraints by apatite and titanite thermochronometry and zircon U/Pb dating

The Song-Kul Basin sits on a plateau at the Northern and Middle Kyrgyz Tien Shan junction. It is a lacustrine basin, occupied by Lake Song-Kul and predominantly developed on igneous basement. This basement was targeted for a multi-method chronological study to identify the different magmatic episodes responsible for basement formation and to constrain the timing of the development of its present-day morphology. Zircon U/Pb dating by LA-ICP-MS revealed four different magmatic episodes: a Late Cambrian (~ 500 Ma) island arc system, a Late Ordovician (~ 450 Ma) subduction related intrusion, an Early Permian (~ 290 Ma) collisional stage, and a Middle to Late Permian (~ 260 Ma) post-collisional magmatic pulse. Middle to Late Triassic (~ 200–230 Ma) titanite fission-track ages and Late Triassic – Early Jurassic (~ 180–210 Ma) apatite fission-track ages and thermal history modeling indicate the Song-Kul basement was already emplaced in the shallow crust at that time. An exhumed fossil apatite fission-track partial annealing zone is recognized in the bordering Song-Kul mountain ranges. The area experienced only minor post-Early Mesozoic denudation. The igneous basement was slowly brought to apatite (U–Th)/He retention temperatures in the Late Cretaceous–Palaeogene. Miocene to present reactivation of the Tien Shan does not manifestly affect this part of the orogen.     

Titanite dates crystallization: Slow Pb diffusion during super‐solidus re‐equilibration

Titanite can be found in rocks of wide compositional range, is reactive, growing or regrowing during metamorphic and hydrothermal events, and is generally amenable to U–Pb geochronology. Experimental evidence suggest that titanite has a closure temperature for Pb ranging from 550 to 650°C, and thus titanite dates are commonly interpreted as cooling ages. However, this view has been challenged in recent years by evidence from natural titanite which suggests the closure temperature may be significantly higher (up to 800°C). Here, we investigate titanite in an enclave of migmatitic gneiss included within a granite intrusion. The titanite crystals exhibit textural features characteristic of fluid‐mediated mass transfer processes on length scales of <100 µm. These textural features are associated with variation in both Pb concentrations and distinct U–Pb isotopic compositions. Zr‐in‐titanite thermometry indicates that modification of the titanite occurred at temperatures in excess of 840°C, in the presence of a high‐T silicate melt. The Pb concentration gradients preserved in these titanite crystals are used to determine the diffusivity of Pb in titanite under high‐T conditions. We estimate diffusivities ranging from 2 × 10^?22 to 5 × 10^?25 m²/s. These results are significantly lower than experimental data predict yet are consistent with other empirical data on natural titanites, suggesting that Pb diffusivity is similar to that of Sr. Thus our data challenge the wide‐held assumption that U–Pb titanite dates only reflect cooling ages.     

Synthesis and Preliminary Characterisation of New Silicate, Phosphate and Titanite Reference Glasses

Eleven synthetic silicate and phosphate glasses were prepared to serve as reference materials for in situ microanalysis of clinopyroxenes, apatite and titanite, and other phosphate and titanite phases. Analytical results using different micro-analytical techniques showed that the glass fragments were homogeneous in major and trace elements down to the micrometre scale. Trace element determinations using inductively coupled plasma-mass spectrometry (ICP-MS), multi-collector inductively coupled plasma-mass spectrometry (MC-ICP-MS), laser-ablation inductively coupled plasma-mass spectrometry (LA-ICP-MS) and secondary ionisation mass spectrometry (SIMS) showed good agreement for most elements (Li, Be, B, Cs, Rb, Ba, Sr, Ga, Pb, U, Th, Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Er, Tm, Yb, Lu, Zr, Hf, Ta, Nb) studied and provide provisional recommended values.     

Unsupported radiogenic Pb in zircon: a cause of anomalously high Pb-Pb,U-Pb and Th-Pb ages

Ion microprobe U-Th-Pb isotopic analyses of zircons from a granodioritic orthogneiss from the Napier Complex, Mount Sones, Enderby Land, Antarctica, have identified an unambiguous example of unsupported radiogenic Pb in a 3,950 Ma-old crystal. At one 40 m spot on the crystal an unusually large heterogeneity in Pb content was found, the concentration of radiogenic Pb ranging from 5 to 50 percent higher than could have been generated in 3,950 Ma by radioactive decay of the co-existing U and Th. This relative excess of radiogenic Pb is attributed to Pb gain rather than to U and Th loss because first, the Pb content varied by more than the U or Th contents and secondly, changes in the Pb/U, Pb/Th and Pb isotopic composition correlated directly with changes in the Pb concentration. The individual ²⁰⁷Pb/²⁰⁶Pb apparent ages ranged from 4,000 Ma to 4,145 Ma, all greater than the inferred age of the crystal. A correlation between ²⁰⁷Pb/²⁰⁶Pb and Pb/U shows that the Pb excess has not resulted from recent Pb movement. The spot apparently gained radiogenic Pb about 2,500 Ma ago, at the same time as the majority of the other zircons in the rock suffered substantial Pb loss. The Pb movement occurred in response to a discrete geologic event. Reverse discordance is a phenomenon that must be considered when interpreting zircon U-Pb ages, especially ²⁰⁷Pb/²⁰⁶Pb ages of single crystals or portions of crystals. Decay constants. Ages in this paper are calculated using the decay constant convention recommended by the Subcommission on Geochronology (Steiger and Jaeger 1977).