Empirical calibration of oxygen isotope fractionation in zircon

New empirical calibrations for the fractionation of oxygen isotopes among zircon, almandine-rich garnet, titanite, and quartz are combined with experimental values for quartz-grossular. The resulting A-coefficients (‰K²) are:

	Zrc	Alm	Grs	Ttn
Qtz	2.64	2.71	3.03	3.66
Zrc		0.07	0.39	1.02
Alm			0.32	0.95
Grs				0.63

Full-size table

     

Experimental calibration of oxygen isotope fractionation between quartz and zircon

We report the results of an experimental calibration of oxygen isotope fractionation between quartz and zircon. Data were collected from 700 to 1000 °C, 10–20 kbar, and in some experiments the oxygen fugacity was buffered at the fayalite–magnetite–quartz equilibrium. Oxygen isotope fractionation shows no clear dependence on oxygen fugacity or pressure. Unexpectedly, some high-temperature data (900–1000 °C) show evidence for disequilibrium oxygen isotope partitioning. This is based in part on ion microprobe data from these samples that indicate some high-temperature quartz grains may be isotopically zoned. Excluding data that probably represent non-equilibrium conditions, our preferred calibration for oxygen isotope fractionation between quartz and zircon can be described by:

This relationship can be used to calculate fractionation factors between zircon and other minerals. In addition, results have been used to calculate WR/melt–zircon fractionations during magma differentiation. Modeling demonstrates that silicic magmas show relatively small changes in δ¹⁸O values during differentiation, though late-stage mafic residuals capable of zircon saturation contain elevated δ¹⁸O values. However, residuals also have larger predicted melt–zircon fractionations meaning zircons will not record enriched δ¹⁸O values generally attributed to a granitic protolith. These results agree with data from natural samples if the zircon fractionation factor presented here or from natural studies is applied.     

锆石Hf同位素：MC-ICP-MS和LA-MC-ICP-MS分析结果的比较

采用单柱离子色谱法高效提取锆石中的Hf元素,用MC—ICP—MS测定锆石Hf同位素组成。三个锆石样品及其平行样的分析结果显示,同一样品的Hf同位素组成在误差范围内高度一致,表明用单柱离子交换色谱法能够有效分离锆石的Hf元素,可以保证Hf同位素分析结果的再现。对比MC—ICP—MS和LA—MC—ICP—MS分析结果发现,同一样品锆石的Hf同位素在误差范围内一致,具有很好的可对比性。但对颗粒较小的锆石,缩小激光束斑使之不超出锆石颗粒的范围,能够获得更好的结果。     

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.     

Metasomatic zones in metamorphic rocks

Prediction of a unique sequence of metasomatic zones that would develop by intergranular diffusion with local equilibrium is possible only for relatively simple systems, unless extensive thermochemical and kinetic information is available. The complexity of the problem for a given example will depend on what portion of the set of chemical components required to describe the example are ‘diffusing components’, that is, components that move relative to ‘inert markers’. Diffusing components are commonly K-components (Thompson, 1970) for the various local equilibria of a sequence of metasomatic zones, since diffusion tends to impose a monotonie variation of the chemical potentials of these components across the zones. The number of diffusing components may vary from zone to zone in a particular example, as may the number of diffusing components that are K-components. Calculation of the rate of growth of a specific sequence of zones is relatively straightforward only for cases where the zones are primarily due to the variation of the chemical potential of one independent diffusing component. Calculation of the material transfer involved in the growth of a sequence of zones, assuming a single sharp initial contact is meaningful only if ‘inert markers’ or a discontinuity in the otherwise-constant ratio of two components indicate the present location of the initial contact. Examination of some natural calc-silicate diffusion zones suggests that a diffusion-imposed gradient in the chemical potential of calcium is largely responsible for the observed zonation. Metasomatic zones developed at the boundaries of ultramafic bodies, however, are produced by diffusion-imposed chemical potential gradients of several components, notably silica and magnesia, the number varying from zone to zone.     

Replacement of zircon with baddeleyite as a likely mechanism of the formation of zoned zircon crystals in ultrabasic rocks

Doklady Earth Sciences - The problem of the U–Pb age of zircon crystals from ultrabasic rocks is discussed in this paper. It is shown that the assumption on the xenogenic nature of zircon...     

LA-MC-ICP-MS锆石Hf同位素的分析方法及地质应用

本研究利用Thermo Finngan Neptune型多接收等离子质谱和Newwave UP213 激光剥蚀系统对两个国际锆石标准和一个实验室锆石标准进行了系统的测定.测得的TEMORA、GJ1和FM02锆石标准的176Hf/177Hf比值分别为0.282700±64(2SD,N=22),0.282008±25(2SD,N=26)和0.282967±44(2SD,N=27),该结果在误差范围内与文献报道值完全一致.采用不同的剥蚀直径对FM02锆石标准进行了对比测定,结果在误差范围内是一致的.从分析结果来看,GJ1和FM02的Hf同位素比值变化范围较小,是Hf同位素LA-MC-ICP-MS测试的理想标准锆石.文中还对四个不同地区的锆石Hf同位素进行了测定,结合前人研究,对其成因和物质来源进行了初步探讨.     

青海柴达木山岩体LA-ICP-MS锆石U-Pb定年 及Hf同位素特征

柴达木山岩体是柴北缘地区最大的岩体之一。为确定柴达木山岩体成因及其与柴北缘早古生代造山作用的关系,采用LA-ICP-MS方法对柴达木山眼球状花岗岩和花岗闪长岩中的锆石进行了U-Th-Pb同位素及Hf同位素研究。柴达木山眼球状花岗岩及花岗闪长岩206Pb/238U年龄加权平均值分别为436.9Ma±2.8Ma及440.8Ma±7.3Ma,Th/U值均大于0.2,代表了岩浆的形成年龄。眼球状花岗岩和花岗闪长岩锆石Hf同位素地球化学特征相近,45个锆石Hf同位素分析值中42个锆石176Lu/177Hf值均介于0.000735~0.002786之间,176Hf/177Hf值变化范围为0.282264~0.282439,εHf(t)变化于-8.5~-2.5之间,Hf同位素两阶段模式年龄为1.44~1.77Ga。研究表明,柴达木山岩体形成于437~446Ma,具有多期侵位特点,其原岩来自柴达木板块基底下地壳;结合柴北地区缘早古生代构造演化特点认为,柴达木山岩体为陆陆碰撞的产物。     

内蒙古色尔腾地区白彦花斜长花岗岩锆石U—Pb年龄

通过对内蒙古色尔腾地区白彦花斜长花岗岩锆石U—Pb法年龄的分析，确定该岩体的形成年龄为2400～2500Ma，结合区域地质特征厘定其形成于新太古代。     

蚌埠隆起区中生代花岗岩的岩石成因：锆石Hf同位素的证据

对蚌埠隆起区中生代不同时期的花岗岩中6个岩体的锆石LA-MC-ICP MS原位Hf同位素的研究,据此限定它们的岩浆源区和重建华北克拉通东南部的构造格架.结果表明,中生代不同时期的花岗岩中岩浆锆石的初始Hf同位素组成（εHf（t））可以分成两组：第一组的女山（130 Ma）和西庐山花岗岩（130 Ma）的εHf（t）值分别为-18.4和-16.1;第二组的曹山（110 Ma）、锥山二长花岗岩（110 Ma）和蚂蚁山花岗岩（110 Ma）以及淮光花岗闪长岩（130 Ma）的εHf（t）值分别为-22.3、-23.1和-21.1以及-28.1,这些岩浆锆石低的εHf（t）值表明它们可能来源于古老的大陆下地壳.女山和西庐山岩体中早古生代-新元古代继承锆石具有低的εHf（t）值（-2.3～-7.7）和1.52 Ga～1.79 Ga的Hf同位素两阶段模式年龄,表明它们的岩浆源区主要以扬子克拉通下地壳物质为主.曹山、锥山和蚂蚁山以及淮光岩体中岩浆锆石的Hf同位素两阶段模式年龄为1.89 Ga～2.58 Ga,结合淮光岩体中古元古代继承锆石和3400 Ma捕获锆石中低的εHf（t）值（-5.7～-6.8,-0.6、-0.9）和古老的Hf同位素两阶段模式年龄（2.44 Ga～2.80 Ga,3.7 Ga）,表明它们主要来源于华北克拉通下地壳物质的部分熔融.淮光和女山岩体中古元古代-新太古宙继承锆石中正的εHf（t）值（0.3～6.7）以及高的εHf（t）值（16.9～21.7）的存在,暗示形成这些古老继承锆石的初始物质中有幔源物质的涉入.蚌埠隆起区深部地壳中扬子克拉通基底物质的存在暗示扬子克拉通可能沿着郯庐断裂带向西或北西方向俯冲于华北克拉通之下.     

Impact of residual zircon on Nd-Hf isotope decoupling during sediment recycling in subduction zone

The subduction factories in convergent plate margins exert crucial control on recycling terrestrial components and returning to the overlying crust. The Nd and Hf isotopic systems provide potential tracers to evaluate these processes. Here we present a case where these isotopic systems are decoupled in a suite of granites from the Chinese Altai, showing a wide range of εHf(t) values(from -4.7 to +10.8) in contrast to a limited range of εNd(t) values(from -5.8 to -1.9). The zircon xenocrysts occurring frequently in these rocks show markedly negative εHf(t) values(from -34.3 to -6.5) and positive d7 Li values(from +12.5 to +18.2). We propose a model to explain the observed relationship between residual zircon and Nde Hf isotope decoupling. We suggest that the Altai granites originated from partial melting of subducted slab components under relatively low temperature conditions which aided the residual zircon from oceanic sediments to inherit and retain a significant amount of177 Hf in the source, thereby elevating the¹⁷⁶ Hf/¹⁷⁷ Hf ratio of the melt, and decoupling from the¹⁴³ Nd/¹⁴⁴ Nd ratio during the subsequent magmatic processes. Our study illustrates a case where sediment recycling in subduction zone contributes to decoupling of Nd and Hf isotopic systems, with former providing a more reliable estimate of the source characteristics of granitic magmas.     

鄂尔多斯盆地长城系碎屑锆石SHRIMP U-Pb定年和Hf同位素研究

沉积盖层的碎屑锆石内部结构和年龄谱是了解碎屑沉积岩形成环境和物源区的重要研究对象。本文报道了鄂尔多斯盆地3口钻井中的4个长城系(变质)沉积岩样品的碎屑锆石SHRIMP U-Pb定年和Hf同位素分析结果。结果表明,主年龄峰值为～1. 8Ga,另外,在～2. 5Ga存在一个次年龄峰值,最年轻碎屑锆石年龄为～1. 6Ga,但存在大的误差。锆石的Hf同位素组成存在很大变化,εHf(t)值变化范围为-10. 5～+6. 7。结合前人研究,可得出如下结论:(1)鄂尔多斯盆地长城系底界沉积时代小于1. 7Ga,与华北克拉通东部的类似;(2)鄂尔多斯盆地长城系碎屑沉积物来自其北部古元古代孔兹岩系和/或鄂尔多斯变质基底本身;(3)鄂尔多斯盆地长城系与华北克拉通东部地区长城系形成于类似的构造环境,如大陆裂谷或坳拉槽。     

Metasomatic coronas around hornblendite xenoliths in granulite facies marble, Ivrea zone, N Italy. II: Oxygen isotope patterns

Up to 20-cm-wide metasomatic reaction bands formed coronas around hornblendite xenoliths in a marble matrix during high grade metamorphism in the Ivrea zone. The coronas are comprised of an innermost monomineralic clinopyroxene layer, a garnet-clinopyroxene layer and an outermost scapolite-clinopyroxene layer. The oxygen isotope composition of the original hornblendite core is 7‰ relative to V-SMOW and the oxygen isotope composition of the marble matrix is 19.7‰. The oxygen isotope transition across the corona is represented by a diffusion front with a step discontinuity at the inner margin of the corona. The systematics of the inter-mineral fractionations indicates preservation of the oxygen isotope compositions from high temperatures and maintenance of grain-scale oxygen isotope equilibrium during corona formation. The oxygen isotope pattern is interpreted in terms of a moving boundary diffusion problem. The growing reaction band and the reactant hornblendite and marble represent a total of five media with different transport properties and moving separation surfaces. Bulk oxygen diffusion was at least three orders of magnitude faster then expected from volume diffusion, suggesting that transport was enhanced by relatively fast diffusion along grain boundaries. Oxygen diffusivities in the individual layers correlate with the oxygen volume diffusivities in the major constituent minerals of the respective layers, suggesting mineralogical control on bulk oxygen diffusion.     

阿尔泰阿斯喀尔特Be-Nb-Mo矿床年代学、锆石Hf同位素研究及其意义

阿斯喀尔特Be-Nb-Mo矿床位于新疆阿尔泰东段可可托海伟晶岩矿集区,Be储量达大型,产出宝石并伴生Nb、Mo、Ga矿化。该矿床同时发育花岗岩型与伟晶岩型两类稀有金属矿化,晚阶段有辉钼矿、黄铁矿等硫化物发育,在阿尔泰伟晶岩省具有独特性。本文对矿区内的白云母钠长花岗岩、Be矿化白云母钠长花岗岩以及条带状伟晶岩进行锆石LA-ICP-MS U-Pb定年及Hf同位素研究,对伟晶岩中不同产状的辉钼矿进行Re-Os同位素定年。获得的锆石238U/206Pb加权平均年龄分别为219.2±2.9Ma、222.6±4.6Ma与218.2±3.9Ma,辉钼矿Re-Os加权平均年龄为218.6±1.3Ma,表明伟晶岩形成稍晚于花岗岩,花岗-伟晶岩系统的演化时间较短;锆石εHf(t)值分别为-0.72~+1.33、-0.36~+1.99与-0.45~+0.38,t DM C模式年龄分别为1169~1298Ma、1130~1279Ma与1229~1282Ma,表明花岗岩与伟晶岩具有类似的源区,以前寒武纪微陆块的壳源物质为主。花岗岩与伟晶岩形成于后造山板内演化阶段,与加厚地壳的熔融有关。根据矿化组合、源区特征并结合大地构造背景,提出阿斯喀尔特伟晶岩属于LCT型。地质、地球化学及年代学特征表明白云母钠长花岗岩为伟晶岩的成矿母岩。     

Equilibrium mercury and lead isotope fractionation caused by nuclear volume effects in crystals

Acta Geochimica - To investigate equilibrium mercury (Hg) and lead (Pb) isotope fractionation caused by the nuclear volume effect (NVE) in crystals, the electron densities at nuclei (i.e.,...     

桂东北平乐县沙子煌斑岩年代学及锆石Hf同位素特征

正在中生代,华南地区经历了印支与燕山两期构造事件,并完成了由特提斯构造域向太平洋构造域的转换,构造应力场也由总体的挤压变为拉伸体制(Jia et al., 2004)。然而华南中生代构造属性还存在着较大分歧,对华南地区中生代岩石成因及构造背景的认识也尚存争议(周新民,2003)。南岭被认为是华南中生代构造体制转换的转换区(Shu et al.,2009),桂东北地区位于南岭西段,岩浆活动频繁,     

Small-angle X-ray scattering measurement of the internal microstructure of natural zircon crystals

Zircon crystals change their physical properties significantly over time in response to the radiation damage (metamictization) induced in the lattice by the presence of radionuclides U and Th. Crystalline zircon has extremely low diffusion rates of the radiogenic daughter product, Pb. Lead diffusion is enhanced in metamict volumes, but the observed lack of correlation between Pb loss and metamictization in natural zircons requires that other mechanisms control the incidence of Pb migration. The proposition that self-induced stress and elasticity contrasts in zoned natural crystals create fast-track Pb migration pathways, in response to time-integrated radiation damage, requires a means of detecting the microstructures within zircons at the interatomic scale at which Pb migration takes place. Small-angle X-ray scattering (SAXS) is introduced as a means of detecting candidate microstructures including subgrain boundaries, defect networks and microfractures produced by differential metamictization. It is shown that a classical X-ray source yields measurable SAXS response from contrasting metamict and crystalline domains within a crystal, and these properties are quantified for a metamict zircon megacryst. Detection of the weaker SAXS response expected from microfractures and networked defects requires the more intense X-rays of synchrotron-source radiation.     

激光探针等离子体质谱用于锆石Pb-Pb定年的分析和校正方法的进一步探讨

激光探针等离子体质谱可对锆石进行快速准确的Ｐｂ－Ｐｂ同位素定年。本文进一步探讨了该方法应用中的几个问题。对不同样品采用不同的聚焦方式可以对Ｕ／Ｐｂ分异有一定的控制作用。在一定的条件下,不连续和连续采样模式都可以得到较高精度和准确度的结果。连续采样模式还可以得到同位素计数的深度剖面。不同的测量滞留时间会影响测量结果的精度。２０ｍｓ为适合锆石２０７Ｐｂ／２０８Ｐｂ分析的最佳测量滞留时间。在对测定结果进行校正时,可以采用玻璃标样ＮＩＳＴ６１０和钻石标样两种不同的校正方法。     

4.4 billion years of crustal maturation: oxygen isotope ratios of magmatic zircon

Analysis of δ¹⁸O in igneous zircons of known age traces the evolution of intracrustal recycling and crust-mantle interaction through time. This record is especially sensitive because oxygen isotope ratios of igneous rocks are strongly affected by incorporation of supracrustal materials into melts, which commonly have δ¹⁸O values higher than in primitive mantle magmas. This study summarizes data for δ¹⁸O in zircons that have been analyzed from 1,200 dated rocks ranging over 96% of the age of Earth. Uniformly primitive to mildly evolved magmatic δ¹⁸O values are found from the first half of Earth history, but much more varied values are seen for younger magmas. The similarity of values throughout the Archean, and comparison to the composition of the “modern” mantle indicate that δ¹⁸O of primitive mantle melts have remained constant (±0.2‰) for the past 4.4 billion years. The range and variability of δ¹⁸O in all Archean zircon samples is subdued (δ¹⁸O(Zrc)=5–7.5‰) ranging from values in high temperature equilibrium with the mantle (5.3± 0.3‰) to slightly higher, more evolved compositions (6.5–7.5‰) including samples from: the Jack Hills (4.4–3.3 Ga), the Beartooth Mountains (4.0–2.9 Ga), Barberton (3.5–2.7 Ga), the Superior and Slave Provinces (3.0 to 2.7 Ga), and the Lewisian (2.7 Ga). No zircons from the Archean have been analyzed with magmatic δ¹⁸O above 7.5‰. The mildly evolved, higher Archean values (6.5–7.5‰) are interpreted to result from exchange of protoliths with surface waters at low temperature followed by melting or contamination to create mildly elevated magmas that host the zircons. During the Proterozoic, the range of δ¹⁸O(Zrc) and the highest values gradually increased in a secular change that documents maturation of the crust. After ∼1.5 Ga, high δ¹⁸O zircons (8 to >10‰) became common in many Proterozoic and Phanerozoic terranes reflecting δ¹⁸O(whole rock) values from 9 to over 12‰. The appearance of high δ¹⁸O magmas on Earth reflects nonuniformitarian changes in the composition of sediments, and rate and style of recycling of surface-derived material into magmas within the crust. Electronic Supplementary Material Supplementary material is available for this article at