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.     

Ban-1 Zircon: A New Natural Zircon Reference Material for LA-MC-ICP-MS Zr and Hf Isotopic Determinations

New zircon reference materials for in situ zircon radiogenic Hf isotope and stable Zr isotopic determinations made by laser ablation multi-collector inductively coupled plasma-mass spectrometry (LA-MC-ICP-MS) are required due to high data productivity and consequently high reference material consumption rate. This study examines a new natural zircon for Zr isotope ratios by double spike thermal ionisation mass spectrometry (TIMS), and for Hf isotopes by bulk solution nebuliser (SN)-MC-ICP-MS with both Zr and Hf determined by LA-MC-ICP-MS. A total of five zirconium isotope measurements from drilled zircons, determined by TIMS, yield a mean δ^94/90Zr_IPGP-Zr value of -0.09 ± 0.06‰ (2s). Five and eight hafnium isotope measurements for powders from the drilled zircons and Ban-1-4 by SN-MC-ICP-MS, yield mean ¹⁷⁶Hf/¹⁷⁷Hf ratios of 0.282985 ± 0.000011 (2s) and 0.282982 ± 0.000007 (2s), respectively. The mean δ^94/90Zr_IPGP-Zr value and ¹⁷⁶Hf/¹⁷⁷Hf ratio determined by LA-MC-ICP-MS analyses are -0.06 ± 0.09‰ (2s, n = 504) and 0.282985 ± 0.000035 (2s, n = 327), respectively. The isotopic homogeneities suggest that the Ban-1 zircon is a suitable reference material for microbeam Zr and Hf isotopic measurements.     

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.     

Zircon U‐Pb age,Trace Element,and Hf Isotopic Compositions of Nordmarkite in the Lizhuang Rare Earth Element Deposit in the Western Margin of the Yangtze Block

The Mianning–Dechang(MD) rare earth element(REE) belt, located in the northern Kangdian axis(KDA) in the western margin of the Yangtze platform, is one of the most economically significant REE mineral belts in China. REE mineralization is associated with Himalayan carbonatite–alkaline complexes. The Lizhuang nordmarkite occurred in the northern part of the MD REE belt. The majority of zircons from the Lizhuang nordmarkite are characterized by pronounced positive Ce yet slightly negative Eu anomalies and high U/Yb. Moreover, all zircons have stable Hf isotopic compositions with initial ~(176) Hf/(~(177)Hf) ratios ranging from 0.282739 to 0.282808 and an average value of 0.282773. The negative Lu/Hf and positive ε_(Hf)(t) range from-0.98 to-0.94(average value of-0.96) and from-0.56 to 1.89(the majority is positive, with an average of 0.66), respectively. These characteristics indicate that the rock is derived from an enriched mantle and subducted material. LA-ICP-MS analysis of the zircons from the intrusion yields a weighted mean ~(206)Pb/(~(238)U) age of 28.57±0.61 Ma. During this period, the tectonic activity in the KDA is not plate subduction but an intraplate tectonic exhibiting fold–thrust and strike–slip behaviors in the western marginal zone of the Yangtze platform(WMYB). We suggest the possibility of an existing eastward old slab subduction under WMYB combined with a regional tectonic evolution. The Lizhuang nordmarkite may be derived from an enriched mantle beneath the western part of the Yangtze craton, which originated from the remelting of the Tethys subducting slab, because of the Himalayan strike–slip that formed a special type of REE deposit called strike–slip-type REE deposits.     

Petrogenesis of Cretaceous igneous rocks from the Duolong porphyry Cu–Au deposit,central Tibet: evidence from zircon U–Pb geochronology,petrochemistry and Sr–Nd–Pb–Hf isotope characteristics

The Duolong porphyry Cu–Au deposit (5.4 Mt at 0.72% Cu, 41 t at 0.23 g/t Au) was recently discovered in the southern Qiangtang terrane, central Tibet. Here, new whole‐rock elemental and Sr–Nd–Pb isotope and zircon Hf isotopic data of syn‐ and post‐ore volcanic rocks and barren and ore‐bearing granodiorite porphyries are presented for a reconstruction of magmas associated with Cu–Au mineralization. LA–ICP–MS zircon U–Pb dating yields mean ages of 117.0 ± 2.0 and 120.9 ± 1.7 Ma for ore‐bearing granodiorite porphyry and 105.2 ± 1.3 Ma for post‐ore basaltic andesite. All the samples show high‐K calc‐alkaline compositions, with enrichment of light rare earth elements (LREE) and large ion lithophile elements (LILE: Cs and Rb) and depletion of high field strength elements (HFSE: Nb and Ti), consistent with the geochemical characteristics of arc‐type magmas. Syn‐ and post‐ore volcanic rocks show initial Sr ratios of 0.7045–0.7055, ε_Nd(t) values of −0.8 to 3.6, (²⁰⁶Pb/²⁰⁴Pb)_t ratios of 18.408–18.642, (²⁰⁷Pb/²⁰⁴Pb)_t of 15.584–15.672 and positive zircon ε_Hf(t) values of 1.3–10.5, likely suggesting they dominantly were derived from metasomatized mantle wedge and contaminated by southern Qiangtang crust. Compared to mafic volcanic rocks, barren and ore‐bearing granodiorite porphyries have relatively high initial Sr isotopic ratios (0.7054–0.7072), low ε_Nd(t) values (−1.7 to −4.0), similar Pb and enriched zircon Hf isotopic compositions [ε_Hf(t) of 1.5–9.7], possibly suggesting more contribution from southern Qiangtang crust. Duolong volcanic rocks and granodiorite porphyries likely formed in a continental arc setting during northward subduction of the Bangong–Nujiang ocean and evolved at the base of the lower crust by MASH (melting, assimilation, storage and homogenization) processes. Copyright © 2014 John Wiley & Sons, Ltd.     

Partition coefficients of Hf,Zr, and REE between zircon,apatite, and liquid

Concentration ratios of Hf, Zr, and REE between zircon, apatite, and liquid were determined for three igneous compositions: two andesites and a diorite. The concentration ratios of these elements between zircon and corresponding liquid can approximate the partition coefficient. Although the concentration ratios between apatite and andesite groundmass can be considered as partition coefficients, those for the apatite in the diorite may deviate from the partition coefficients. The HREE partition coefficients between zircon and liquid are very large (100 for Er to 500 for Lu), and the Hf partition coefficient is even larger. The REE partition coefficients between apatite and liquid are convex upward, and large (D=10–100), whereas the Hf and Zr partition coefficients are less than 1. The large differences between partition coefficients of Lu and Hf for zircon-liquid and for apatite-liquid are confirmed. These partition coefficients are useful for petrogenetic models involving zircon and apatite.     

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     

佛冈高分异I型花岗岩的成因:来自Nb-Ta-Zr-Hf等元素的制约

华南南岭地区发育有大面积的与钨锡成矿相关的侏罗纪花岗岩,然而其中有些花岗岩的成因类型却难以确定。本文以佛冈岩体为例,结合前人已发表数据,对佛冈花岗岩体中Nb、Ta、Zr和Hf等元素的迁移特征及其原理进行探讨,并对佛冈花岗岩的成因类型进行了厘定。随着分异程度增加,佛冈花岗岩Nb和Ta含量增加,Nb/Ta(3.6~15.3)和Zr/Hf(17.3~38.9)比值降低并发生分异。随着Zr含量的降低,佛冈花岗岩的Zr/Hf比值降低,这一特征表明锆石的分离结晶作用使得佛冈花岗岩的Zr/Hf比值分异。Nb/Ta比值分异可能与角闪石和黑云母的分离结晶作用有关。随着Nb/Ta比值降低,Y/Ho比值增加,这一特征表明佛冈花岗岩Nb/Ta比值的分异也和岩浆演化后期的流体有关。佛冈花岗岩不含原生的富铝矿物,为准铝质到弱过铝质岩石。随着分异程度增加,佛冈花岗岩P2O5含量降低,表明它不是S型花岗岩。随着Y/Ho比值增加和Nb/Ta和Zr/Hf比值降低,佛岗花岗岩Ga/Al和Fe OT/Mg O比值增加,从典型I型花岗岩特征演化到类似A型花岗岩的地球化学特征。因此,我们认为佛冈花岗岩不是A型花岗岩而是高分异的I型花岗岩。区域上与成矿相关的流体和花岗质岩浆的相互作用和分离结晶作用,使得华南南岭地区的花岗岩地球化学特征复杂,所以其成因类型也变的难以确定。     

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.     

高精度Lu—Hf同位素测定的新技术与新方法

综述了Ｌｕ－Ｈｆ同位素体系的基本地质地球化学特征,对比了Ｌｕ－Ｈｆ同位素现有的分析方法,并介绍了包括化学流程在内的应用多接收器双耦合等离子体质谱仪（ＭＣ－ＩＣＰ－ＭＳ）进行高精度和高准确度,Ｌｕ－Ｈｆ同位素分析的原理和测试过程,列举了部分最新地质应用成果。     

Characteristics of Rare Earth Elements,Zr, and Hf in Ore‐Bearing Porphyries from the Western Awulale Metallogenic Belt,Northwestern China and their Application in Determining Metal Fertility of Granitic Magma

The western Awulale metallogenic belt in northwestern China hosts a number of small‐ to medium‐sized porphyry Cu deposits that are associated with albite porphyry. The common presence of plagioclase (albite) as phenocrysts and the absence of hydrous minerals (amphibole and biotite) indicate that the water content of albite porphyry is low. Trace‐element compositions of whole rocks and zircon grains from these ore‐bearing porphyries were measured. Zircon grains from albite porphyries exhibit Ce⁴⁺/Ce³⁺ ratios ranging from 7.75 to 95.1, which indicate that these porphyries have a low oxygen fugacity. Trace element compositions of ore‐bearing porphyries exhibit (La/Yb)_N ratios ranging from 1.09 to 11.1 and Eu/Eu^* ratios ranging from 0.10 to 0.66. These ore‐bearing porphyries have Zr values ranging from 171 to 707 ppm and Hf values ranging from 8.30 to 18.9 ppm. Combining these porphyries with other ore‐bearing porphyries that formed in the Central Asian Orogenic Belt (CAOB) and the Pacific Rim metallogenic belt, we found that the (La/Yb)_N and Eu/Eu^* ratios of ore‐bearing porphyries in western Awulale are low, while the Zr and Hf values are high. Specifically, REEs can be used to evaluate the degree of differentiation and degree of partial melting, and Zr and Hf can be used to evaluate the redox conditions and water content of magmatic rocks. Our findings indicate that ore‐bearing porphyries in western Awulale have a lower oxygen fugacity, degree of differentiation, and water content than do others in the CAOB and the Pacific Rim metallogenic belt. Compared to those of ore‐bearing porphyries with lower zircon Ce⁴⁺/Ce³⁺ ratios, the (La/Yb)_N ratios of ore‐bearing porphyries in our study are low, and the Zr and Hf values are high. This finding indicates that, under reducing conditions, the degree of evolution and water content may have an important influence on the metal abundance in magmas. There is also a clear relationship between (La/Yb)_N, Eu/Eu^*, Zr, Hf, and the size of the deposits. Large‐ (>4 Mt Cu) and intermediate (1.5–4 Mt Cu)‐sized porphyry Cu deposits are associated with granitic intrusions that have higher (La/Yb)_N and Eu/Eu^* ratios and lower Zr and Hf values. This finding indicates that, in addition to oxygen fugacity, the degree of evolution and water content are controlling parameters for metal abundance in magmas, especially in low oxygen fugacity porphyry Cu deposits. Such a conclusion may be useful in the exploration for other concealed porphyry Cu deposits.     

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.     

In Situ Analyses of Trace Elements,U–Pb and Lu–Hf Isotopes in Zircons from the Tongshankou Granodiorite Porphyry in Southeast Hubei Province,Middle-Lower Yangtze River Metallogenic Belt,China

The Tongshankou Cu-Mo deposit, located in southeast Hubei province, is a typical skarn–porphyry type ore deposit closely related to the Tongshankou granodiorite porphyry, characterized by a high Sr/Y ratio.Detailed in situ analyses of the trace elements and U–Pb and Lu–Hf isotopes in zircons from the Tongshankou granodiorite porphyry were performed.Scarcely any inherited zircons were observed, and the analyzed zircons yielded highly concordant results with a weighted mean 206Pb/238 U age of 143.5 ± 0.45 Ma(n=20, mean square weighted deviation was 0.75), which was interpreted to represent the crystallization age of the Tongshankou granodiorite porphyry.The chondrite-normalized rare-earth element pattern was characterized by a slope that steeply rises from the light-group rare-earth elements(LREE) to the heavy-group rare-earth elements(HREE) with a positive Ce-anomaly and inconspicuous Eu-anomaly, which was coincident with the pattern of the zircons from the Chuquicamata West porphyry, Chile.The analyzed zircons also had relatively low 176Hf/177 Hf ratios of 0.282526–0.282604.Assuming t=143 Ma, the corresponding calculated initial Hf isotope compositions(εHf(t)) ranged from-5.6 to-2.9.The results of the in situ analysis of trace elements and U–Pb and Lu–Hf isotopes in zircons from the Tongshankou granodiorite porphyry suggest that a deep-seated process involving a thickened-crust/enriched-mantle interaction may play an important role in the generation of high Sr/Y-ratio magma and potentially in the generation of porphyry Cu-Mo systems.     

地质样品的一次阴离子色谱法Hf分离及其MC-ICP-MS分析

本文建立了适合MC-ICP-MS测试地质样品中Hf同位素的一次阴离子交换化学分离方法。使用常规的阴离子交换树脂就可以完成Hf与干扰元素和基体元素的分离,避免了当前广泛采用的多次离子交换柱的麻烦,也无需使用特效树脂,HF处理样品后,也不必使用HClO_4赶尽HF。Hf的回收率大于90%,过程空白约为50pg。岩石标样的重复分析表明,该方法简单、快速、经济、有效,尤其适合年轻地质样品Hf同位素组成分析。     

Methodology and Application of Hafnium Isotopes in Ilmenite and Rutile by MC‐ICP‐MS

The high abundances of the high field‐strength elements in ilmenite and rutile make these minerals particularly suitable for hafnium isotopic investigations. We present a technique for separating Hf by ion exchange chemistry from high‐TiO₂ (> 40% m/m) minerals to achieve precise Hf isotopic composition analyses by MC (multiple collector)‐ICP‐MS. Following digestion and conversion to chlorides, the first elution column is used to separate iron and the rare earth elements, the second column is designed to separate most of the titanium from Hf, an evaporation step using HClO₄ is then performed to remove any trace of HF in preparation for the third column, which is needed to eliminate any remaining trace of titanium. The modified chemistry helped to improve the yields from < 10 to > 78% as well as the analytical precision of the processed samples (e.g., sample 2033‐A1, ¹⁷⁶Hf/¹⁷⁷Hf = 0.282251 ± 25 before vs. 0.282225 ± 6 after). The technique was tested on a case study in which the Hf isotopic ratios of ilmenite and rutile (analysed prior to the chemistry improvement) were determined and permitted to evaluate that the origin of rutile‐bearing ilmenite deposits is from the same or similar magma than their, respectively, associated Proterozoic anorthosite massifs (Saint‐Urbain and Lac Allard) of the Grenville Province in Québec, Canada.     

峨眉山二滩高钛玄武岩Zr/Hf分异的指示意义

对峨眉山二滩高钛玄武岩高场强元素的研究表明,Zr/Hf比值出现了明显分异,可分为高Zr/Hf组和低Zr/Hf组两组玄武岩。Zr/Hf比值的分异与岩浆结晶分异作用无关,而是由部分熔融和地幔源区的不同所导致,暗示高Zr/Hf组和低Zr/Hf组玄武岩分别具有不同的部分熔融条件和不同的地幔物质组分。     

锆石Hf同位素组成的LAM-MC-ICPMS精确测定

在配备了NewWaveMerchantekLUV213型紫外激光探针进样系统的Isoprobe型MC—ICPMS上进行了溶液和锆石单矿物的Hf同位素比值测定，并对^176Yb和^176Lu对^176Hf的同质异位素干扰校正进行了试验。结果表明，由于自然界Lu的丰度远远小于Yb，所以^176Hf的同质异位素干扰主要来自^176Yb。当Yb／Hf较低时，可以通过同质异位素干扰校正直接难确测定出^176Hf／^177Hf比值；当Yb／Hf比值较高时，则需要进行同质异位素干扰校正和外部校正来获得难确的^176Hf／^177Hf比值。因此，用LAM—MC-ICPMS可以难确、快速地测定锆石的Hf同位素组成。     

Determination of the Neoproterozoic Shicaogou Syn-collisional Granite in the Eastern Qinling Mountains and Its Geological Implications

The Shicaogou granite has been identified as a magnesian (Fe-number=0.71-0.76), calcic to calc-alkalic (MALI=3.84-5.76) and peraluminous (ASI=1.06-1.13) granite of the syn-collisional S-type, with high SiO2(>71%), A12O3 (>13%) and Na2O+K2O (6.28%-7.33%, equal for NaO2 and K2O). Trace element and REE analyses show that the granite is rich in LILE such as of Rb, Sr, Ba and Th, and poor in HFSE like Yb, Y, Zr and Hf. Its Rb/Sr ratio is greater than 1; the contents of Nb and Ta, and the ratio of Nb/Ta as well as the REE geochemical features (e.g. REE abundance, visible fractionation of LREE and HREE and medium to pronounced negative Eu anomalies) are all similar to those of crust-origin, continent-continent syn-collisional granite. Moreover, the granite exhibits almost the same pattern as that of the typical continent-continent syn-collisional granite on the spider diagram and all samples fall within the syn-collisional granite field.The cathodoluminescence (CL) investigations have revealed that the zircon f     

Crustal reworking and orogenic styles inferred from zircon Hf isotopes:Proterozoic examples from the North Atlantic region

Zircon Hf evolutionary patterns are powerful tools to investiage magma petrogenesis and crustal evolution. The ~(176)Hf/~(177)Hf isotopic signature of a rock is particularly informative and can be used to derive an estimation of the time when mantle extraction and diagnose closed system reworking where successive samples through time define an Hf evolution array dependant on the source Lu/Hf ratio. However, many magmatic events require new mantle addition as the thermal impetus for melting pre-existing crust. In this situation, rather than simply reflecting reworking, the isotopic signature indicates mixing with contributions from both reworked crust and new radiogenic input. Different geodynamic settings have different propensities for either reworking or addition of new mantle-derived magma. Hence, Hf-time trends carry within them a record, albeit cryptic, of the evolving geodynamic environment as different tectonic configurations recycle and add new crust at different rates, magnitudes, and from different sources. As an example of the difference in apparent Hf evolution slopes, we present Hf-time compilations from three geographically distinct Meso-to Neoproterozoic orogenic belts in the North Atlantic Region whose geodynamic configurations remain a subject of debate. We use the εHf/Ma trajectory to assist in understanding their evolution. The εHf/Ma trajectory of the Sveconorwegian Orogen corresponds to a ~(176)Lu/~(177) Hf ratio of 0.012, which implies a process driven primarily by reworking of preexisting crust that is balanced with input from the depleted mantle resulting in a relatively shallowεHf/Ma slope. The Valhalla Orogen reveals a similar comparatively shallow εHf/Ma path. In stark contrast to these patterns is the steep εHf/Ma trajectory of the Grenville Orogen that requires a mixing process involving a greater contribution of old crust of at least ～ 1.8 Ga age. The degree of reworking required to produce the εHf/Ma trend of the Grenville Orogen is consistent with a continent-continent collisional orogeny whereas both Sveconorwegian and Valhalla orogens appear more consistent with accretionary margins.     

Metamorphic garnet pyroxenite from the 540-600 m main borehole of the Chinese Continental Scientific Drilling (CCSD) project

Compared to other mafic and ultramafic rocks from the CCSD main borehole as well as from the outcrops, rocks from the 540-600 m section is extraordinary in terms of its geophysical as well as geochemical properties. It consists of > 70% hematite-ilmenite garnet pyroxenite (HI-GPX) and < 30% intercalated rutile garnet pyroxenite (R-GPX). Whole-rock geochemical data show that HI-GPXs have: (1) relatively high V with an average of 606 ppm, but lower Nb and Ta; (2) highest TFeO, Fe₂O₃/FeO ratio, and highly variable but strong positive Eu anomalies with Eu/Eu? up to 2.9; (3) anomalously high V/Sc ratios ranging from 8.39 to 43.23, average 15.03; and (4) high amounts of hematite-ilmenite solid solutions with a very fine intergrowth structure down to nanometer scale. V/Sc ratios in the CCSD garnet pyroxenites are correlated negatively with MgO, but positively with Fe₂O₃/FeO ratios. Both suites of pyroxenites have similar rare earth elements and high field strength elements geochemistry. These features demonstrate that these pyroxenites were formed from metamorphism of high-Fe and/or -Ti gabbroic cumulates. This can account not only for low high field strength elements (HFSE) and rare earth elements (REE) but also low Nb/Ta and Zr/Hf ratios in these rocks. Seemingly negative correlation between Nb/Ta and Zr/Hf in the CCSD metabasites, not significantly affected by UHP metamorphism, is also consistent with the silicate differentiation trend in a basaltic magma chamber.