In situ U-Pb dating of titanite by LA-ICPMS

Titanite is an ideal mineral for U-Pb isotopic dating because of its relatively high U,Th and Pb contents.Here,we developed a technique for U-Pb dating of titanite using the 193 nm ArF laser-ablation system and Agilent 7500a Q-ICP-MS.Standards of titanite (BLR-1 and OLT-1) and zircon (91500 and GJ-1) were dated using single spot and line raster scan analytical methods.To check the matrix effect,titanite (BLR-1) and zircon (91500) standards were analyzed as the external standards.The weighted mean 206 Pb/238 U ages of OLT-1 titanite are 1015±5 Ma (2,n=24) and 1017±6 Ma (2,n=24) by single spot and line raster scan analyses,respectively,using BLR-1 titanite as the external standard.These ages are consistent with its reference age of about 1014 Ma.However,using 91500 zircon as the external standard,the weighted mean 206 Pb/238 U ages are 917±4 Ma (2,n=24) and 927±5 Ma (2,n=24) for BLR-1 titanite,and 891±4 Ma (2,n=24) and 901±5 Ma (2,n=24) for OLT-1 titanite by single spot and line raster scan analyses,respectively.It is evident that these ages are ～12% younger than their reference values.Our results reveal that significant matrix effect does exist between different kinds of minerals during LA-ICPMS U-Pb age determination,whereas it is insignificant between same minerals.Therefore,same mineral must be used as the external standard for fractionation corrections during in situ LA-ICPMS U-Pb age analysis.In addition,we determined U-Pb ages for titanites from the Early Cretaceous Fangshan pluton,which indicates a rapid cooling history of this pluton.     

Simultaneous in-situ determination of U-Pb age and trace elements in zircon by LA-ICP-MS in 20 μm spot size

Simultaneous in-situ determination of U-Pb ages and 20 trace elements of three international zircon standards （91500, GJ1 and TEMORA 1） and one laboratory zircon standard （SK10-2） separated from Cenozoic fine-grained gabbro was carried out on quadrupole ICP-MS equipped with 193 nm excimer laser in 20 μm spot size. The weighted mean ^206Pb/^238U ages of 91500, GJ1 and TEMORA 1 are 1064.4±4.8 Ma （2σ）, 603.2±2.4 Ma （2σ） and 418.2±2.4 Ma （2σ）, respectively. The relative standard deviations （RSDs） of ^206Pb/^238U ages （2σ） are less than 2.2% for single measurements and 0.6% for weighted means. The obtained weighted mean ^206Pb/^238U ages of three standard zircons agree with the recommended values within 2σrerror. The weighted mean ^206Pb/^238U age of SK10-2 is 31.42=0.25 Ma （2σ） and the RSDs of ^206Pb/^238U ages （2σ） are between 2.4% and 5.7% for single measurements and less than 0.8% for weighted mean. The obtained weighted mean ^206Pb/^238U age is in good agreement with the age obtained by Yuan （2004）. Trace element concentrations of NIST612 and NIST614 obtained under the same LA-ICP-MS operating conditions agree with the recommended values within analytical error. The results indicate that it is possible to measure U-Pb age and trace elements simultaneously by LA-ICP-MS in a small spot size of 20μm.     

Garnet Sm-Nd and U-Pb systems: A case study of a granulite from the European Variscan belt

This study presents zircon and garnet ages of a mafic granulite from the high-grade Variscan basement of the Black Forest, Germany and discuss isotope closure temperature of garnet Sm-Nd and U-Pb systems. Zircon grains yield 207Pb/206Pb ages between ～340 and ～414 Ma by the U-Pb and evaporation methods. In contract, garnet dating gives Sm-Nd and Pb-Pb isochron ages of (398±3) Ma and (411±14) Ma, respectively, which are older than most of zircon ages. These data imply that most of zircons lost radiogenic Pb, probably due to metamictization or recrystallisation during the granulite-facies metamorphism (～800℃) at ～340 Ma. Garnet Sm-Nd and U-Pb systems preserve chronological information of pro-grade metamorphism, probably profiting from a fluid-absence metamorphic environment. These results demonstrate that garnet mineral can be a better candidate than zircon mineral to date high-grade metamorphism by the U-Pb and Sm-Nd methods in some cases.     

In situ U-Pb dating of xenotime by laser ablation （LA）-ICP-MS

Xenotime is an ideal mineral for U-Th-Pb isotopic dating because of its relatively high U and Th contents, but typically low concentration of common Pb. These characteristics, and the fact that it is widespread throughout various types of rocks, suggest that the U-Th-Pb dating of xenotime has broad applications. Studies of U-Pb dating on xenotime by ion microprobe (such as SHRIMP) have increased in recent years, whereas studies by laser ablation (LA)-ICP-MS are still rare. In this study, we developed a technique for U-Pb dating of xenotime using the 193 nm ArF laser-ablation system and Agilent 7500a Q-ICP-MS. To evaluate the reliability of our method, a xenotime standard, BS-1, was analyzed and calibrated against another xenotime standard, MG-1. The weighted mean 206 Pb/ 238 U ages of 510.1 ± 5.2 Ma (2 n = 21), 509.8 ± 4.3 Ma (2 n = 21) and 510.0 ± 4.6 Ma (2 n = 21) were obtained using beam diameters of 16, 24 and 32 m, respectively. These ages are identical to those determined by ID-TIMS method (weighted mean 206 Pb/ 238 U age of 508.8 ± 1.4 Ma), which supports the reliability of our LA-ICP-MS method. We also analyzed xenotimes in leucogranites from South Tibet and granites from Xihuashan in southern China, and obtained accurate and precise ages. Nevertheless, we observed systematic differences in Pb/U fractionation among xenotime, monazite and zircon. The matrix-effect resulted in either under-correction or over-correction of fractionation, and thus led to inaccurate ages. Thus, a matrix-matched material is required for U-Pb dating of xenotime by LA-ICP-MS.     

Qinghu zircon: A working reference for microbeam analysis of U-Pb age and Hf and O isotopes

Zircon is the most useful mineral for studies in U-Pb geochronology and Hf and O isotope geochemistry. Matrix effect is a major problem of the microbeam techniques such as SIMS and LA-（MC）-ICPMS. Therefore, external standardization using well-characterized natural zircon standards is fundamental for accurate microbeam measurements. While the isotopic geochro- nology and geochemistry laboratories equipped with microbeam analytical facilities have been increasingly established in China during the past decade, applications of the isotopic microanalysis are still limited due to shortage of available standards. We report here the Qinghu zircon as a potential new working reference for microbeam analysis of zircon U-Pb age and O-Hf isotopes. This zircon was separated from the Qinghu quartz monzonite from the western Nanling Range, Southeast China. It is fairly homoge- neous in U-Pb age and Hf and O isotopes in terms of large amounts of mircobeam measurements by LA-MC-ICPMS and SIMS at the scales of 20-60 ~tm. SIMS measurements yield consistent 2~6pb/238U age within analytical uncertainties with that obtained by ID-TIMS. Precise determinations of O isotopes by IRMS and Hf isotopes by solution MC-ICPMS are in good agreement with the statistical mean of microbeam measurements. We recommend U-Pb age of = 159.5 ± 0.2 Ma （2SE）, δ^18O = 5.4‰ ± 0.2%0 （2SD） and 176Hf/177Hf = 0.283002 ± 0.000004 （2SD） as the best reference values for the Qinghu zircon.     

4.1 Ga old detrital zircon in western Tibet of China

4.1 Ga old detrital zircon was found by SHRIMP U-Pb dating for quartz schist from Buring County in western Tibet, Southwest China. This is the oldest zircon U-Pb age found in China so far. The detrital zircon is a zircon of magmatic origin because its Th/ U ratios are 0.76 to 0.86. Two dates older than 4.0 Ga were measured only in one grain. U-Pb ages of 35 measured spots in 24 zircons can be subdivided into 6 groups, corresponding to at least 6 episodes of magmatic activity in the target area. The present results provide an important geochronological constraint on the geological evolution of Qinghai-Tibet Plateau.     

A combined study of SHRIMP U-Pb dating, trace element and mineral inclusions on high-pressure metamorphic overgrowth zircon in eclogite from Qinglongshan in the Sulu terrane

Methods recently advanced for discrimination on the genesis of metamorphic zircon, such as analysis of mineral inclusions and trace elements, provide us powerful means to distinguish zircon overgrowth during high-pressure metamorphism. Zircons in ultrahigh-pressure eclogite from Qinglongshan in the Sulu terrane were studied by the SHRIMP U-Pb method in combining with trace element and mineral inclusion analyses. No inherited core was identified in the analyzed zircons by means of cathodoluminescence images. The occurrence of high-pressure metamorphic mineral inclusions in zircon, such as garnet, omphacite, rutile, and the flat HREE pattern in zircon indicate that the zircon formed at high-pressure metamorphic conditions. Therefore, a weighted average U-Pb age of 227.4±3.5 Ma obtained from such a kind of zircon is interpreted to represent the timing of peak nietamorphism for the Qinglongshan eclogite.     

Genesis of zircon and its constraints on interpretation of U-Pb age

Zircon U-Pb dating is the most commonly used method for isotopic geochronology. However, it has been a difficult issue when relating zircon U-Pb ages to metamorphic conditions in complex metamorphic rocks. Much progress has been made in the past decade with respect to the genesis of zircon and its constraints on interpretation of U-Pb age. Three methods have been proposed to link zircon U-Pb age to metamorphic conditions: ( i ) internal structure; ( ii ) trace element feature; (iii) mineral inclusion composition. Magmatic zircon shows typical oscillatory zoning and/or sector zoning, whereas metamorphic zircon has internal structures such as no zoned, weakly zoned, cloudy zoned, sector zoned, planar zoned, and patched zoned ones. Zircons formed in different geological environments generally have characteristic internal structures. Magmatic zircons from different rock types have variable trace element abundances, with a general trend of increasing trace element abundances in zircons from ultramafic through mafic to granitic rocks. Zircons formed under different metamorphic conditions have different trace element characteristics that can be used to relate their formation to metamorphic conditions. It is an effective way to relate zircon growth to certain P-T conditions by studying the trace element partitioning between coexisting metamorphic zircon and garnet in high-grade metamorphic rocks containing both zircon and garnet. Primary mineral inclusions in zircon can also provide unambiguous constraints on its formation conditions. Therefore, interpretation of zircon U-Pb ages can be constrained by its internal structure, trace element composition, mineral inclusion and so on.     

U-Pb zircon dating constraints on formation time of Qilian high-grade metamorphic rock and its tectonic implications

In order to constrain the formation time of high-grade metamorphic rocks in the Qilian Mountains, U-Pb zircon dating was carried out by using LA-ICPMS technique for a paragneiss of the Hualong Group in the Qilian Mountains basement series and a weakly foliated granite that intruds into the Hualong Group. Zircons from the paragneiss consist dominantly of detrital magma zircons with round or sub-round shape. They have 207Pb/206Pb ages mostly ranging from 880 to 900 Ma, with a weighted mean age of 891 ±9 Ma, which is interpreted as the magma crystallization age of its igneous provenance and can be taken as a lower age limit for the Hualong Group. Magma crystallization age for the weak-foliated granite is 875±8 Ma, which can be taken as an upper age limit for the Hualong Group. Accordingly, the formation time of the Hualong Group is constrained at sometime between 875 and 891 Ma. A few zir- cons from both paragneiss and weak-foliated granite display old inherited ages of 1000 to 1700 Ma and young metamorphic ages of Early Paleozoic. The zircon age distribution pattern confirms that the Qilian Mountains and the northern margin of Qaidam Basin had a united basement, with geotectonic affinity to the Yangtze Block. The results also reveal that sediments of the Hualong Group formed by rapid accumulation due to rapid crustal uplift-erosion. This process may result from intensive Neoproterozoic orogenesis due to assembly of the suppercontinent Rodinia.     

Formation and evolution of Precambrian continental crust in South China

The occurrence of zircons with U-Pb ages of ~3.8 Ga and Hf model ages of ~4.0 Ga in South China suggests the existence of the Hadean crustal remnants in South China. Furthermore, a detrital zircon with a U-Pb age as old as 4.1 Ga has been found in Tibet. This is the oldest zircon so far reported in China. These results imply that continental crust was more widespread than previously thought in the late Hadean, but its majority was efficiently reworked into Archean continental crust. On the basis of available zircon U-Pb age and Hf isotope data, it appears that the growth of continental crust in South China started since the early Archean, but a stable cratonic block through reworking did not occur until the Paleoproterozoic. Thus the operation of some form of plate tectonics may occur in China conti- nents since Eoarchean. The initial destruction of the South China craton was caused by intensive magmatic activity in association with the assembly and breakup of the supercontinent Rodinia during the Neoproterozoic. However, most of the Archean and Paleoproterozoic crustal materials in South China do not occur as surface rocks, but exist as sporadic crustal remnants. Nevertheless, the occur- rence of Neoproterozoic magmatism is still a signature to distinguish South China from North China.     

In situ simultaneous determination of trace elements, U-Pb and Lu-Hf isotopes in zircon and baddeleyite

This paper describes a combined method of simultaneously measuring U-Pb and Lu-Hf isotopes as well as trace elements in Phalaborwa baddeleyite and 91500, GJ-1, TEMORA-1 and SK10-2 zircons by means of Neptune MC-ICPMS and Agilent Q-ICPMS connected to a 193 nm excimer laser ablation system. Material ablated by laser was carried in different proportions into Q-ICPMS for U-Pb isotopic and trace elemental and MC-ICPMS for Lu-Hf isotopic compositions. Experiments indicate that different proportions of ablated material for the Q-ICPMS and MC-ICPMS （6：4, 5：5 and 4：6 respectively） do not show any bias for the zircon/baddeleyite U-Pb age, Lu-Hf isotope and trace elemental compositions within analytical errors. Using 40-60 μm spot size, the obtained U-Pb ages of Phalaborwa baddeleyite, 91500, GJ-1, TEMORA and SK10-2 zircons are 2065±15 （2σ, n=20）, 1063±6 （2σ, n=-19）, 613±6 （2σ, n=20）, 416±5 （2σ, n=20） and 32.6±0.5 （2σ, n=20） Ma, respectively. The ^176Hf/^177Hf ratios are 0.281231±24 （2SD, n=20）, 0.282310±35 （2SD, n=19）, 0.282028±34 （2SD, n=20）, 0.282687±34 （2SD, n=20） and 0.282752±53 （2SD, n=20）, respectively. The obtained trace elemental compositions are identical to the reference values. Therefore, this kind of technique makes it possible to simultaneously obtain the U-Pb age, Lu-Hf isotopes and trace elemental compositions of zircon and baddeleyite, which could be an important tool in solving problems in earth sciences.     

Determination of lead isotope compositions of geological samples using femtosecond laser ablation MC-ICPMS

Lead isotopic compositions of international silicate glasses, feldspar and copper-based samples are obtained using femtosecond laser ablation multiple collector inductively coupled plasma mass spectrometry (fLA-MC-ICPMS). Some international glass standards for the microanalysis are applied to evaluate the method reported here. The Pb isotopic composition of these NIST glasses (SRM 610, 612, 614), USGS (BHVO-2G, BCR-2G, BIR-1G and GSD-1G) and MPI-DING glasses (GOR132-G, KL2-G, T1-G, StHs60/80-G) agree well with recommended values in 2 s error. One of 15 copper-based metals is found to have homogenized Pb isotope data and can be used as an external calibration standard and quality control sample for chalcopyrite, ancient coins, etc., to trace the genesis of metal deposit and culture exchange among different dynasties (GBW02137, ²⁰⁸Pb/²⁰⁴Pb = 37.9661 ± 0.0005 (2 s), ²⁰⁷Pb/²⁰⁴Pb = 15.5770 ± 0.0002 (2 s), ²⁰⁶Pb/²⁰⁴Pb = 17.7462 ± 0.0002 (2 s)). We also prepared a feldspar glass to serve as the external calibration standard/QC for Pb isotope analysis using fLA-MC-ICPMS.     

吕梁地区宁家湾岩体锆石 U-Pb 年代学、地球化学特征及地质意义

对呈小规模岩株状产出的宁家湾岩体进行野外地质、岩石学、岩石地球化学、锆石U-Pb同位素年代学和Hf同位素组成研究, 目的是确定其岩石成因及地球动力学意义。两件样品的LA-ICP-MS锆石U-Pb定年结果分别为2364±6 Ma (MSWD=0.13)和2360±23 Ma (MSWD =4.0), 属古元古代岩浆活动的产物。研究结果表明, 宁家湾岩体富碱、高K和Si, 具有高FeO^T/MgO 比值和高的高场强元素(HFSE)含量, 富集Rb, Ba, Th和U等元素, 具有低的Ca和Mg含量, 明显亏损P和Ti, 具弱轻重稀土分异和强Eu负异常(δEu=0.13~0.36)的海鸥型稀土分配模式, 显示高分异I型花岗岩的特征。较高的Y/Nb值(1.2~2.8)、锆石的ε_Hf(t)均为正值(+1.6~+6.4)以及单阶段模式年龄t_DM1(Hf)和二阶段模式年龄t_DM2(Hf)分别为2449~2629 Ma和2474~2711 Ma的特点, 表明源区可能为壳幔混合。明显的Nb, P 和 Ti负异常及Ce, Nd和Zr正异常, 反映出大陆边缘弧岩浆岩的特征。结合区域地质背景, 认为宁家湾岩体很可能形成于岛弧构造环境。     

锆石U-Pb定年与微量元素分析的地质应用

 锆石U-Pb定年与微量元素同时测定的原位微区分析是目前应用最广泛的地质测年方法之一，对锆石形貌学、内部结构及地球化学特征进行深入研究，是正确理解、解释锆石原位微区分析测年结果的关键。通过锆石的阴极发光图像（CL）、背散射电子图像（BSE），结合锆石的Th/U比值及稀土配分模式曲线特征，可判别不同锆石的成因类型；通过锆石的微量元素分析，可判别锆石寄主岩石的成因类型及形成环境；利用Ti温度计可限定岩体的岩浆源区深度范围，结合锆石寄主岩石类型及寄主岩石中深源包裹体的研究，可进一步推断锆石母岩浆的起源。锆石U-Pb定年与微量元素分析相结合的地质测年方法，已成功地应用于最大沉积地层时代限定、碎屑岩物源分析以及古洋盆演化过程约束等方面，且具有强有力的发展前景。     

U-Pb zircon dating of Early Paleozoic gabbro from the Nantinghe ophiolite in the Changning-Menglian suture zone and its geological implication

The Nantinghe ophiolite is located in the northern part of the Changning-Menglian suture zone in southeast Tibet. It is composed of meta-peridotite, cumulative gabbro, meta-gabbro, plagioclase amphibolite and meta-basalt. Zircon U-Pb dating of the cumulative gabbro gives concordant ages of 473.0±3.8 Ma and 443.6±4.0 Ma respectively, indicating the early and late episodes of mafic magmatisms during the Paleo-Tethys oceanic rifting. The 16 LA-ICPMS zircon U-Pb analyses of meta-gabbro yield a weight mean age of 439±2.4Ma. The gabbro shows relatively low contents of SiO2 (46.46%-52.11%), TiO2 (0.96%-1.14%) and K2O (0.48%-0.75%). Its trace element distribution patterns are partly similar to those of the mid-ocean ridge basalts, and part is depleted in high field strength elements such as Nb, Ta, Zr, Hf and Ti. These features suggest that the mafic rocks were probably formed in a MORB-like or backarc rift basin setting. The zircon U-Pb age of gabbro is consistent with a late crystallization age of the cumulative gabbro from the Nantinghe ophiolite, suggesting that the Paleo-Tethys oceanic basin was opened during 444-439 Ma, possibly as a backarc basin. It is the first precise age which defines the formation time of the early Paleozoic ophiolite in the Changning-Menglian suture zone. These geochronological and geochemical characteristics of the Nantinghe ophiolite are consistent with those from the Guoganjianianshan and Taoxinghu of the Longmu Co-Shuanghu suture in the Qiangtang region. Thus, we suggest that the both Changning-Menglian and Longmu Co-Shuanghu sutures were probably transformed from the relic oceanic crust of the uniform Paleo-Tethys, which likely represents the original and main Paleo-Tethys oceanic basin.     

西秦岭中生代花岗岩锆石U-Pb-Lu-Hf同位素特征及地质意义

对西秦岭地区中川岩体、柏家庄岩体和教场坝花岗岩体进行LA-ICP-MS锆石U-Pb同位素年代学分析, 获得其岩浆侵位年龄分别为220±1, 216±6和222±3 Ma, 表明3个岩体均形成于中?晚三叠世。样品的全岩地球化学分析结果表明, 3个岩体具有相似的稀土及微量元素特征, 均表现为显著亏损高场强元素Nb, Ti和P等, 具有明显的右倾式球粒陨石标准化稀土元素配分模式。锆石Lu-Hf同位素分析结果表明, 3个岩体锆石测年样品的ε_Hf(t)值介于?3.31~+1.68之间, 二阶段模式年龄介于1151~1456 Ma之间。岩石成因分析表明, 这些印支期花岗岩体的母岩浆主要来源于新元古代地壳物质的部分熔融。结合岩体形成时代、岩石成因和区域岩浆作用, 认为这些岩体形成于南秦岭与华南板块沿勉略缝合带相碰撞的造山动力学背景, 可能与华南板块的俯冲板片断离有关。