A routine high-precision method for Lu-Hf isotope geochemistry and chronology

A method for chemical separation of Lu and Hf from rock, meteorite and mineral samples is described, together with a much improved mass spectrometric running technique for Hf. This allows (i) geo- and cosmochronology using the¹⁷⁶Lu¹⁷⁶Hf+ ^– decay scheme, and (ii) geochemical studies of planetary processes in the earth and moon.Chemical yields for the three-stage ion-exchange column procedure average 90% for Hf. Chemical blanks are <0.2 ng for Lu and Hf. From 1 g of Hf, a total ion current of 0.5×10^–11 Ampere can be maintained for 3–5 h, yielding 0.01–0.03% precision on the ratio¹⁷⁶Hf/¹⁷⁷Hf. Normalisation to¹⁷⁹Hf/¹⁷⁷Hf=0.7325 is used.Extensive results for the Johnson Matthey Hf standard JMC 475 are presented, and this sample is urged as an international mass spectrometric standard; suitable aliquots, prepared from a single batch of JMC 475, are available from Denver.Lu-Hf analyses of the standard rocks BCR-1 and JB-1 are given. The potential of the Lu-Hf method in isotope geochemistry is assessed.     

Separation of Hf and Lu for high-precision isotope analysis of rock samples by magnetic sector-multiple collector ICP-MS

Potential applications of the Lu-Hf isotope system have long been impeded by the analytical difficulties of obtaining data on a wide variety of geological materials. Many of these limitations will now be eliminated because Hf isotopes can be readily measured with high precision and accuracy on small and/or Hf-poor samples using the newly developed magnetic sector-multiple collector ICP-MS, also known as MC-ICP-MS or the `Plasma 54'. We present here a new method to separate and determine isotopic compositions of both Hf and Lu from various types of geological materials using MC-ICP-MS. The chemical separation of Hf and Lu has been designed to take advantage of the characteristics of this unique instrument. The separation of Hf can be achieved with a straightforward two-step ion-exchange column chemistry, which has a high efficiency (better than 85% recovery) and low blanks (typical total blanks less than 150 pg for the largest samples of 1 g bulk rock). The isolation of Lu is achieved with a single-stage ion-exchange column procedure with near 100% yields and blanks below 20 pg. Hf isotopic compositions can be routinely measured on 50 ng Hf with an internal precision better than 20 ppm in less than 15 min and with an external precision better than 40 ppm. Our value for the ¹⁷⁶Hf/¹⁷⁷Hf ratio of the JMC 475 Hf standard currently is 0.282163 ± 9 (2s). The Lu isotopic ratio is measured rapidly and precisely without isolating Lu from the bulk of Yb, and a mass fractionation correction increases the accuracy of the results compared with TIMS data. Our current reproducibility of the Lu/Hf ratio is ≈1%. Selected Lu-Hf isotope analyses of some modern and ancient geological samples validate the technique we have described here and illustrate the new opportunities for Lu-Hf isotope geochemistry that have opened up with the advent of magnetic-sector ICP mass spectrometry. Received: 12 September 1996 / Accepted: 13 January 1997     

Lu-Hf同位素体系及其岩石学应用

Lu-Hf是近几年来发展极为迅速的一门同位素定年和地球化学示踪技术。本文对这一同位素体系的发展历史、岩石学应用和存在的问题进行了全面的评述,对目前常见的样品溶解、质谱测定和激光剥蚀技术进行了全面介绍。虽然Lu-Hf同位素的发展历史可划分为TIMS、hot-SIMS、MC-ICPMS三个阶段,但MC-ICPMS仪器的出现,使Hf同位素发展速度明显加快。在介绍了Lu-Hf同位素的基本地球化学行为和基本原理之后,本文对这一同位素体系在岩石学上的应用作了全面的介绍,内容包括含石榴石和磷灰石岩石的同位素定年、早期大陆地壳形成与演化、不同端元地幔的性质及成因、岩浆作用过程的Hf同位素鉴别、区域地球动力学演化、变质作用过程中的Hf同位素变化等。最后对Lu的衰变常数、测定标准(JMC475溶液和固体锆石/斜锆石标准)的Hf同位素组成及Hf同位素的封闭温度等问题进行了讨论。     

The Hf isotopic composition of zircon reference material 91500

Ten new single zircon fragments, analyzed by solution chemistry and MC-ICP-MS, of the 91500 zircon standard show no evidence to support a recent claim based on in situ data that this reference material is heterogeneous in terms of its radiogenic Hf isotope composition and as a consequence should be abandoned as a reliable interlaboratory standard. Rather, the larger spread in ¹⁷⁶Hf/¹⁷⁷Hf among in situ data compared with solution chemistry data may reflect the uncertainties resulting from prominent isobaric interference corrections inherent to the in situ analytical protocol. The unweighted mean values of ¹⁷⁶Hf/¹⁷⁷Hf and ¹⁷⁶Lu/¹⁷⁷Hf measured for the ten zircon fragments of this study are 0.282313 ± 0.000008 (2σ) and 0.000311 ± 0.000136 (2σ), respectively. Pooling the mean ¹⁷⁶Hf/¹⁷⁷Hf of this work with those of published solution chemistry studies results in a value of 0.282308 ± 0.000006 (2σ; relative to ¹⁷⁶Hf/¹⁷⁷Hf = 0.282163 for JMC-475), which is recommended here as the currently best estimate of the Hf isotopic composition of this standard. All published studies agree on a value of ~ 0.0003 for the corresponding ¹⁷⁶Lu/¹⁷⁷Hf ratio.     

A New Digestion and Chemical Separation Technique for Rapid and Highly Reproducible Determination of Lu/Hf and Hf Isotope Ratios in Geological Materials by MC-ICP-MS

A new digestion procedure and chemical separation technique has been developed for measurement of Lu/Hf and Hf isotope ratios that does not require high‐pressure bombs or use of HF or HClO₄ acids. Samples are digested in dilute HCl or HNO₃ after flux‐fusion at 110 0 °C in the presence of lithium metaborate. High field strength elements (HFSE) and rare earth elements (REE) are separated from this solution by co‐precipitation with iron hydroxide. The dissolved precipitate (in 2 mol l^?1 HCl) is loaded directly onto a standard cation exchange column which separates remaining sample matrix from the heavy REE (Lu+Yb), and the middle‐light REE and HFSE (Hf). The middle‐light REE and individual HFSE are then separated (10.5, 9 and 6 mol l^?1 HCl) using a miniaturized column containing TEVA spec resin which provides a REE‐, Ti‐ and Zr‐free Hf cut. This chemical separation scheme can also be readily adapted for isotopic analysis of the Sm‐Nd system and/or the other HFSE (Ti, Zr). Total procedural blanks for this technique are < 10 0 pg and < 2 pg for Hf and Lu, respectively, even when digesting large (0.5 g) samples. We present data from replicate digestions of international rock reference materials which demonstrate this technique routinely reproduces Lu/Hf ratios to < 0.2% (2s) and ¹⁷⁶ Hf/¹⁷⁷ Hf isotope ratios to < 30 ppm (2s). Moreover, the technique is matrix‐independent and has been successfully applied to analysis of diverse materials including basalts, meteorites, komatiites, kimberlites and carbonatites. The relative simplicity of this technique, coupled with the ease of digestion (and sample‐spike equilibration) of large difficult‐to‐dissolve samples, and the speed (2 days) with which samples can be digested and processed through the chemical separation scheme makes it an attractive new method for preparing samples for Lu‐Hf isotopic investigation.     

U-Pb, Hf and O isotope evidence for two episodes of fluid-assisted zircon growth in marble-hosted eclogites from the Dabie orogen

A combined study of internal structure, U-Pb age, and Hf and O isotopes was carried out for metamorphic zircons from ultrahigh-pressure eclogite boudins enclosed in marbles from the Dabie orogen in China. CL imaging identifies two types of zircon that are metamorphically new growth and recrystallized domain, respectively. The metamorphic zircons have low Th and U contents with low Th/U ratios, yielding two groups of ²⁰⁶Pb/²³⁸U age at 245 ± 3 to 240 ± 2 Ma and 226 ± 4 to 223 ± 2 Ma, respectively. Anomalously high δ¹⁸O values were obtained for refractory minerals, with 9.9 to 21.4‰ for garnet and 16.9‰ for zircon. This indicates that eclogite protolith is sedimentary rocks capable of liberating aqueous fluid for zircon growth during continental subduction-zone metamorphism. Most of the zircons are characterized by very low ¹⁷⁶Lu/¹⁷⁷Hf ratios of 0.000001-0.000028, indicating their growth in association with garnet recrystallization. A few of them falling within the older age group have comparatively high ¹⁷⁶Lu/¹⁷⁷Hf ratios of 0.000192-0.000383, suggesting their growth prior to the formation of garnet in the late stage of subduction. The variations in the Lu/Hf ratios for zircons can thus be used to correlate with garnet growth during eclogite-facies metamorphism. In either case, the zircons have variable ε_Hf (t) values for individual samples, suggesting that their protolith is heterogeneous in Hf isotope composition with localized fluid availability in the bulk processes of orogenic cycle. Nevertheless, a positive correlation exists between ²⁰⁶Pb/²³⁸U ages and Lu-Hf isotope ratios for the metamorphically recrystallized zircons, suggesting that eclogite-facies metamorphism in the presence of fluid has the identical effect on zircon Lu-Hf and U-Th-Pb isotopic systems. We conclude that the zircons of the older group grew in the presence of fluid during the subduction prior to the onset of peak ultrahigh-pressure metamorphism, whereas the younger zircons grew in the presence of fluid released during the initial exhumation toward high-pressure eclogite-facies regime.     

Hafnium Isotope Characteristics of Palaeoarchaean Zircon OG1/OGC from the Owens Gully Diorite,Pilbara Craton,Western Australia

We report Hf isotope data for 3467 Ma igneous zircons from the Owens Gully Diorite of the Pilbara Craton. These zircons, designated OG1 or OGC, have simple, well‐defined U‐Pb age systematics. Measurements obtained by single crystal dissolution yield a moderate range in ¹⁷⁶Hf/¹⁷⁷Hf (mean 0.280633 ± 34) and ¹⁷⁶Lu/¹⁷⁷Hf (mean 0.00119) that translate into initial (3467 Ma) ¹⁷⁶Hf/¹⁷⁷Hf values that are equivalent within measurement uncertainty (mean 0.280554 ± 7, ε_Hf = +0.6 ± 0.2, 2s). Laser ablation analysis yielded clustered initial ¹⁷⁶Hf/¹⁷⁷Hf ratios (mean 0.280560 ± 20, 2s) indistinguishable from those obtained by solution analysis. The antiquity and moderately high ¹⁷⁶Lu/¹⁷⁷Hf of these zircons result in significant corrections for radiogenic ingrowth of ¹⁷⁶Hf (to 6 ε_Hf units). Depth profiling by concurrent Pb‐Hf isotope determination reveals trends to lower ²⁰⁷Pb/²⁰⁶Pb in several crystals, although these are not accompanied by shifts in ¹⁷⁶Hf/¹⁷⁷Hf. We conclude that zircons from the Owens Gully Diorite are homogeneous for Hf isotopes at the scale of sampling and within the uncertainty limits of the measurement techniques employed. Zircon OG1/OGC would appear to be an ideal quality monitor for laser ablation Hf isotope determination in ancient zircons, and for laser ablation techniques where Hf isotope and age information are determined concurrently or simultaneously.     

Precise and Accurate Determination of Lu and Hf Contents,and Hf Isotopic Compositions in Chinese Rock Reference Materials by MC‐ICP‐MS

In this contribution, we report Hf isotopic data and Lu and Hf mass fractions for thirteen Chinese rock reference materials (GBW07 103–105, 109–113 and 121–125, that is GSR 1–3, 7–11 and 14–18, respectively) that span a broad compositional range. Powdered samples were spiked with a ¹⁷⁶Lu‐¹⁸⁰Hf enriched tracer and completely digested using conventional HF, HNO₃ and HClO₄ acid dissolution protocols. Fluoride salts were dissolved during a final H₃BO₃ digestion, and chemical purification was performed using a single Ln resin. All measurements were carried out on a MC‐ICP‐MS. This work provides the first comprehensive report of the Lu‐Hf isotopic composition of Chinese geochemical rock reference materials, and results indicate that they are of comparable quality to the well‐characterised and widely used USGS and GSJ rock reference materials.     

Early Archean crustal evolution of the Jack Hills Zircon source terrane inferred from Lu-Hf, Pb/Pb, and δO systematics of Jack Hills zircons

Several lines of isotopic evidence - the most direct of which is from Hadean Jack Hills zircons - suggest a very early history of crust formation on Earth that began by about 4.5 Ga. To constrain both the fate of the reservoir for this crust and the nature of crustal evolution in the sediment source region of the Jack Hills, Western Australia, during the early Archean, we report here initial ¹⁷⁶Hf/¹⁷⁷Hf ratios and δ¹⁸O systematics for <4 Ga Jack Hills zircons. In contrast to the significant number of Hadean zircons which contain highly unradiogenic ¹⁷⁶Hf/¹⁷⁷Hf requiring a near-zero Lu/Hf reservoir to have separated from the Earth’s mantle by 4.5 Ga, Jack Hills zircons younger than ca. 3.6 Ga are more radiogenic than -13ε (CHUR) at 3.4 Ga in contrast to projected values at 3.4 Ga of -20ε for the unradiogenic Hadean reservoir indicating that some later juvenile addition to the crust is required to explain the more radiogenic younger zircons. The shift in the Lu-Hf systematics together with a narrow range of mostly mantle-like δ¹⁸O values among the <3.6 Ga zircons (in contrast to the spread towards sedimentary δ¹⁸O among Hadean samples) suggests a period of transition between 3.6 and 4 Ga in which the magmatic setting of zircon formation changed and the highly unradiogenic low Lu/Hf Hadean crust ceased to be available for intracrustal reworking. Constraining the nature of this transition provides important insights into the processes of crustal reworking and recycling of the Earth’s Hadean crust as well as early Archean crustal evolution.     

人工合成锆石Lu-Hf同位素标样方法研究

研究了人工合成锆石并加入微量元素的实验方法和条件。人工合成锆石是以氧化锆和硅酸锂为原料,以钼酸锂和氧化钼为助熔剂,并加入其他元素如Hf、Lu、Yb、U、Th、Pb等元素,充分混匀后转入带盖铂金坩埚中,在高温马弗炉中连续加热生长形成锆石晶体。利用激光剥蚀系统与电感耦合等离子体质谱技术分析了合成锆石晶体中微量元素含量和Lu-Hf同位素组成,结果表明合成锆石晶体中Lu、Yb、U、Th、Pb等微量元素含量不均一,而Hf的含量和Lu-Hf同位素组成有很好的均一性。     

Trace element composition and Lu-Hf isotope systematics of zircon from plagiogneisses of the Kola superdeep well: Contribution of a Paleoarchean crust in Mesoarchean metavolcanic rocks

Zircons have been studied in three samples of Archean plagiogneisses from the Kola superdeep well (SG-3). The crystals consist of cores, magmatic shells, and metamorphic rims. The cores and shells are characterized by similar lowered concentrations of most trace elements, which is typical of zircons from plagiogranitoids, rocks of elevated basicity, and basites. At a wide range of Hf isotope characteristics, the cores and shells have similar average ¹⁷⁶Hf/¹⁷⁷Hf_i, which determines the close composition of their sources. The metamorphic rims have close ¹⁷⁶Hf/¹⁷⁷Hf_i ratio. The minimum age of the crustal contaminant of parental melts is estimated at 3.4 and 3.3 Ga for cores and 3.3–3.2 Ga for shells at almost equal proportions of mantle and crustal components in them. The contribution of Paleoarchean crust established in zircons from plagiogneisses of SG-3 using Lu-Hf isotope systematics is confirmed by the presence of 3.3and 3.4-Ga old zircons in surrounding TTG.     

Effects of melt fractional crystallization on Sr-Nd and Lu-Hf isotope systems: a case study of Triassic migmatite in the Sulu UHP terrane

The Weihai migmatite in the Sulu ultra-high-pressure (UHP) metamorphic terrane, eastern China, underwent partial melting in the Late Triassic during its exhumation. The primary partial melts experienced a decompressional fractional crystallization (DFC) process to produce plagioclase (Pl)-rich leucosome crystallized under eclogite to granulite facies conditions and K-feldspar (Kfs)-rich pegmatitic veins crystallized under amphibolite-facies conditions. In this study, our results demonstrate that the DFC process can cause decoupling between whole-rock Sr and Nd isotopes. The Pl-rich leucosome has ε_Nd(t) values (–10.4 to ?15.0) and initial (⁸⁷Sr/⁸⁶Sr) ratios (0.708173–0.712476) very similar to those of the melanosome, but the Kfs-rich pegmatitic veins have homogeneous ε_Nd(t) values (?14.8 to ?15.2) and significantly high initial (⁸⁷Sr/⁸⁶Sr) ratios (0.713882–0.716284). Our results also suggest that the DFC process can change zircon ¹⁷⁶Yb/¹⁷⁷Hf and ¹⁷⁶Lu/¹⁷⁷Hf isotopic ratios, with no effect on ¹⁷⁶Hf/¹⁷⁷Hf ratios or ε_Hf (t) values. Zircon ¹⁷⁶Yb/¹⁷⁷Hf and ¹⁷⁶Lu/¹⁷⁷Hf ratios increase dramatically from the Pl-rich leucosome to the Kfs-rich pegmatitic veins, but zircon ¹⁷⁶Hf/¹⁷⁷Hf ratios (Pl-rich leucosomes = 0.282330 ± 0.000017; Kfs-rich pegmatitic veins = 0.282321 ± 0.000026) and ε_Hf (t) values (Pl-rich leucosomes = ?10.9 ± 0.6; Kfs-rich pegmatitic veins = ?11.6 ± 0.8) remain almost unchanged. We propose that the isotopic decoupling between the Pl-rich leucosome and Kfs-rich pegmatitic vein might be caused by melt fractional crystallization occurring too rapidly to allow complete equilibrium between them.     

Isotope Dilution Determinations of Lu,Hf, Zr,Ta and W,and Hf Isotope Compositions of NIST SRM 610 and 612 Glass Wafers

Isotope dilution determinations of Lu, Hf, Zr, Ta and W are reported for nine test portions (five for W) of NIST SRM 610 and 612 glass wafers. Additionally, all test portions were analysed for their Hf isotope compositions. In general, high field strength elemental (HFSE) distributions in NIST SRM 610 and 612 were reproducible to ～± 1%, except for Zr (± 5%) in NIST SRM 612, and absolute reported concentrations agreed with previously published values, but with higher precision. The slightly worse reproducibility of Zr in NIST SRM 612 compared to other HFSE is interpreted to result from analytical scatter, rather than sample inhomogeneity. The analyses demonstrated elemental homogeneity for both glass wafers for samples of 1–2 mg with respect to the precision of the method, i.e., ± 1% or better. Average Hf isotope compositions for both glass wafers agreed within uncertainty and the weighted average of all determinations yielded a mean ¹⁷⁶Hf/¹⁷⁷Hf ratio of 0.282111 ± 0.000009 (95% confidence level). However, although mean values for NIST SRM 610 and 612 agreed within analytical limits, NIST SRM 610 test portions showed a tendency of systematically elevated isotope composition of ～ 0.5 _?Hf units when compared to NIST SRM 612, which may indicate a slightly more radiogenic Hf isotope composition of NIST SRM 610. The results of this study suggest that NIST SRM 610 and 612 are valuable calibrators for HFSE in situ analyses within the given uncertainties.     

On the Lu-Hf Isotope Geochemistry of Silicate Rocks

This paper reviews the history (TIMS, hot‐SIMS, MC‐ICP‐MS), significance, geochemical behaviour and current uncertainties (λ¹⁷⁶ Lu, Hf‐Nd Bulk Silicate Earth) surrounding the Lu‐Hf isotope system, and thus marks two decades of its application to geochemical problems. An appendix further presents (a) improvements to the original chemistry protocol of Blichert‐Toft et al. (1997) for application to Mg‐rich samples and (b) a compilation of previously published and new Hf isotope determinations by MC‐ICP‐MS for a set of international rock reference materials. Prior to the advent of multiple‐collector plasma source mass spectrometry (MC‐ICP‐MS), routine analysis of the Lu‐Hf isotope system developed only slowly because of the extreme difficulty of measuring Hf isotope compositions with thermal ionisation mass spectrometry, caused by the very high first ionisation potential of Hf. However, Hf isotope compositions can be measured relatively easily using MC‐ICP‐MS and this new technique now provides reproducible measurements at high precision regardless of the matrix from which Hf is separated. Of the commonly used long‐lived radiogenic isotope systems, only the Sm‐Nd and Lu‐Hf isotope systems are unaffected by parent/daughter fractionations related to volatile nebular processes and core formation. While other systems (Rb‐Sr, U‐Th‐Pb, Re‐Os) may also be used to investigate the chemical evolution of the Earth, Moon, Mars and parent bodies of differentiated meteorites, the larger uncertainties in their bulk chemical and isotopic values limit their application to determine geochemical budgets and assess planetary mantle‐crust evolution. In the study of garnet‐bearing rocks, both for dating purposes and as an isotopic tracer for source provenance and mantle processes, the Lu‐Hf isotope system likewise is of major interest because of the high partition coefficient of Lu compared to Hf for garnet with respect to other minerals. Furthermore, the larger Lu/Hf fractionation compared to Sm/Nd during melting beneath ridges produces proportionally higher Lu/Hf in the residue and faster in‐growth of a radiogenic Hf isotopic signature (compared to Nd), which may help shed light on the dynamics of mantle melting. While the chemistry protocol and mass spectrometric technique for high‐precision Lu‐Hf isotope analysis have been resolved in satisfactory ways over the past five years, more accurate determination of the decay constant for ¹⁷⁶ Lu, at present known with a precision of only about 4%, still needs to be completed and a consensus reached on which value to use for future Lu‐Hf isotope studies. Although the current combined Lu‐Hf and Sm‐Nd Bulk Silicate Earth parameters are plagued by possible incompatibilities in chondrite selection and potential interlaboratory biases, a more accurate set of values may not be readily established owing to heterogeneities in the isotopic composition of chondrites that far exceed present analytical accuracy.     

大兴安岭南段道伦达坝黑云母花岗岩成岩时代、锆石微量元素、Lu-Hf同位素特征及地质意义

道伦达坝铜多金属矿床位于大兴安岭成矿带南段,对道伦达坝矿床黑云母花岗岩开展了锆石U-Pb测年、锆石微量元素和Lu-Hf同位素研究.锆石U-Pb LA-ICP-MS测年结果显示黑云母花岗岩形成时代为282.2±4.5~287.0±3.7 Ma.锆石Lu-Hf同位素研究结果显示黑云母花岗岩锆石均具有较高的176Hf/177Hf（平均值分别为0.282 770和0.282 769）和低的176Lu/177Hf（平均值分别为0.002 224和0.001 984）同位素组成,ε_Hf（t）值变化范围为3.05~8.58之间和2.31~7.36,二阶段模式年龄分别为730.22~1 083.46 Ma和812.42~1 134.56 Ma,暗示其来源为年轻的新生下地壳,可能遭受了古老地壳的混染.锆石微量元素研究显示,黑云母花岗岩的锆石具有低的Nb含量（< 2×10-6）和强烈的Eu异常,符合S型花岗岩特征.锆石的Ti饱和温度平均值为770℃和785℃,指示其源区经历了水近饱和情况下的部分熔融,暗示其可能形成于俯冲环境下.      

Experimental petrology constraints on the recycling of mafic cumulate: a focus on Cr-spinel from the Rum Eastern Layered Intrusion,Scotland

The ¹⁷⁶Lu–¹⁷⁶Hf and ¹⁴⁷Sm–¹⁴³Nd decay systems are routinely used to determine garnet (Grt)–whole-rock (WR) ages; however, the ¹⁷⁶Lu–¹⁷⁶Hf age of garnet is typically older than the ¹⁴⁷Sm–¹⁴³Nd age determined from the same aliquots. Here we present experimental data for Lu³⁺ and Hf⁴⁺ diffusion in garnet as functions of temperature, pressure and oxygen fugacity and show that the diffusivity of Hf⁴⁺ in almandine/spessartine garnet is significantly slower than that of Lu³⁺. The diffusive closure temperature (T _C) of Hf⁴⁺ is significantly higher than that of Nd³⁺, and although this property is partly responsible for the observed ¹⁷⁶Lu–¹⁷⁶Hf and ¹⁴⁷Sm–¹⁴³Nd Grt–WR age discrepancies, the difference between the T _C-s of Lu³⁺ and Hf⁴⁺ could lead to apparent Grt–WR ¹⁷⁶Lu–¹⁷⁶Hf ages that are skewed from the age of Hf⁴⁺ closure in garnet. In addition, the slow diffusivity of Hf⁴⁺ indicates that the bulk of metamorphic garnets retain a substantial fraction of prograde radiogenic ¹⁷⁶Hf throughout peak metamorphic conditions, a phenomenon that further complicates the interpretation of ¹⁷⁶Lu–¹⁷⁶Hf garnet ages and invalidates the use of analytical T _C expressions. We argue that the diffusion of trivalent rare earth elements in garnet becomes much faster when their concentration level falls below a few hundred ppm, as in the experiments of Tirone et al. (Geochim Cosmochim Acta 69: 2385–2398, 2005), and further argue that this low-concentration mechanism is appropriate for modeling the susceptibility of ¹⁴⁷Sm–¹⁴³Nd garnet ages to diffusive resetting.     

Hafnium isotope results from mid-ocean ridges and Kerguelen

¹⁷⁶Hf/¹⁷⁷Hf ratios are presented for oceanic volcanics representing both extremes of the range of mantle HfNdSr isotopic variation. Hf from critical mid-ocean ridgebasalts shows that ¹⁷⁶Hf/¹⁷⁷Hf does indeed have a greater variability than ¹⁴³Nd/¹⁴⁴Nd and ⁸⁷Sr/⁸⁶Sr in the depleted mantle. This extra variation is essentially of a random nature, and can perhaps be understood in terms of known Rb/SrSm/NdLu/Hf fractionation relationships. At the other extreme of mantle isotopic composition, ¹⁷⁶Hf/¹⁷⁷Hf ratios for igneous rocks from the Indian Ocean island of Kerguelen show a closely similar variation to published ¹⁴³Nd/¹⁴⁴Nd ratios for the same samples. Comparison of HfNdSr c relationships for Tristan da Cunha, Kerguelen and Samoa reveals divergences in the mantle array for ocean island magma sources, and perhaps suggests that these irregularities are largely the result of an extra component of ⁸⁷Sr/⁸⁶Sr variation.     

Metamorphic growth and recrystallization of zircon: Distinction by simultaneous in-situ analyses of trace elements,U–Th–Pb and Lu–Hf isotopes in zircons from eclogite-facies rocks in the Sulu orogen

Simultaneous in-situ analyses of trace elements, U–Th–Pb and Lu–Hf isotopes were carried out on distinct domains of zircons in ultrahigh-pressure (UHP) eclogite-facies metamorphic rocks from the main hole of the Chinese Continental Scientific Drilling (CCSD) in the Sulu orogen. For the first time, trace elements are directly linked to Lu–Hf isotopes in metamorphic zircons with reference to their U–Pb dates. This enables methodological integration to distinguish four types of metamorphic zircon: solid-state, replacement and dissolution recrystallizations of protolith zircons, and new growth from the aqueous fluid. Metamorphically grown zircons are characterized by concordant U–Pb ages for the metamorphism, flat HREE patterns typical of the garnet effect, low contents of REE (especially HREE), Y, Nb + Ta and Th + U, high contents of Hf, low (Lu/Gd)_N, Lu/Hf and Th/U (< 0.1) ratios, and elevated ¹⁷⁶Hf/¹⁷⁷Hf ratios relative to solid-state recrystallized zircons. This suggests the effects of both garnet and fluid on the growth of metamorphic zircons. In contrast, metamorphic recrystallization has reset the U–Th–Pb isotope system of protolith zircons to different extents, depending on the extents of fluid action during metamorphism. Solid-state recrystallized zircons exhibit the lowest degrees of resetting and thus almost inherit all geochemical features from the protolith zircons, which are characterized by discordant U–Pb ages close to or below the protolith age, steep MREE–HREE patterns typical of magmatic origin, high contents of trace elements and their ratios, and low ¹⁷⁶Hf/¹⁷⁷Hf ratios. On the other hand, dissolution recrystallized zircons show the highest degrees of reworking and thus have concordant or nearly concordant U–Pb ages for the metamorphism, steep MREE–HREE patterns, lowered contents of trace elements such as REE, Th, U, Y, Nb, Ta and Ti relative to the protolith zircons, and almost unchanged Hf isotope ratios. Replacement recrystallized zircons display intermediate degrees of reworking and thus have their many features of elements and isotopes in between. While the metamorphic growth in the presence of both garnet and fluid is characterized by both depletion of HREE with flat pattern and the low contents of trace elements, the metamorphic recrystallization in the presence of aqueous fluid is indicated by gradual decreases of MREE to HREE without the flat HREE pattern. Therefore, the simultaneous in-situ analyses of metamorphic zircons have the advantage over single-term analyses in making distinction between the new growth and the different types of recrystallization.     

Isotope Lu–Hf composition of detrital zircon from paragneisses of the Sharyzhalgai uplift: evidence for the Paleoproterozoic crustal growth

We present results of study of the trace-element and Lu–Hf isotope compositions of zircons from Paleoproterozoic high-grade metasedimentary rocks (paragneisses) of the southwestern margin of the Siberian craton (Irkut terrane of the Sharyzhalgai uplift). Metamorphic zircons are represented by rims and multifaceted crystals dated at ~ 1.85 Ga. They are depleted in either LREE or HREE as a result of subsolidus recrystallization and/or synchronous formation with REE-concentrating garnet or monazite. In contrast to the metamorphic zircons, the detrital cores are enriched in HREE and have high (Lu/Gd)_n ratios, which is typical of igneous zircon. The weak positive correlation between ¹⁷⁶Lu/¹⁷⁷Hf and ¹⁷⁶Hf/¹⁷⁷Hf in the zircon cores evidences that their Hf isotope composition evolved through radioactive decay in Hf = the closed system. Therefore, the isotope parameters of these zircons can give an insight into the provenance of metasedimentary rocks. The Paleoproterozoic detrital zircon cores from paragneisses, dated at ~ 2.3–2.4 and 2.0–1.95 Ga, are characterized by a wide range of ε_Hf values (from + 9.8 to –3.3) and model age T ^C 2.8–2.0 Ga. The provenance of these detrital zircons included both rocks with juvenile isotope Hf parameters and rocks resulted from the recycling of the Archean crust with a varying contribution of juvenile material. Zircons with high positive ε_Hf values were derived from the juvenile Paleoproterozoic crustal sources, whereas the lower ε_Hf and higher T ^C values for zircons suggest the contribution of the Archean crustal source to the formation of their magmatic precursors. Thus, at the Paleoproterozoic stage of evolution of the southwestern margin of the Siberian craton, both crustal recycling and crustal growth through the contribution of juvenile material took place. On the southwestern margin of the Siberian craton, detrital zircons with ages of ~ 2.3–2.4 and 1.95–2.0 Ga are widespread in Paleoproterozoic paragneisses of the Irkut and Angara–Kan terranes and in terrigenous rocks of the Urik–Iya graben, which argues for their common and, most likely, proximal provenances. In the time of metamorphism (1.88–1.85 Ga), the age of Paleoproterozoic detrital zircons (2.4–2.0 Ga), and their Lu–Hf isotope composition (ε_Hf values ranging from positive to negative values) the paragneisses of the southwestern margin of the Siberian craton are similar to the metasedimentary rocks of the Paleoproterozoic orogenic belts of the North China Craton. In the above two regions, the sources of detrital zircons formed by both the reworking of the Archean crust and the contribution of juvenile material, which is evidence for the crustal growth in the period 2.4–2.0 Ga.     

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).