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.     

Metamorphic growth and recrystallization of zircons in extremely O-depleted rocks during eclogite-facies metamorphism: Evidence from U-Pb ages, trace elements, and O-Hf isotopes

A combined in situ SIMS and LA-(MC)-ICPMS study of U-Pb ages, trace elements, O and Lu-Hf isotopes was conducted for zircon from eclogite-facies metamorphic rocks in the Sulu orogen. The two microbeam techniques sampled various depths of zircon domains, revealing different element and isotope relationships between residual magmatic cores and new metamorphic rims and thus the geochemical architecture of metamorphic zircons which otherwise cannot be recognized by the single microbeam technique. This enables discrimination of metamorphic growth from different subtypes of metamorphic recrystallization. Magmatic cores with U-Pb ages of 769 ± 9 Ma have positive δ¹⁸O values of 0.1-10.1‰, high Th/U and ¹⁷⁶Lu/¹⁷⁷Hf ratios, high REE contents, and steep MREE-HREE patterns with negative Eu anomalies. They are interpreted as crystallizing from positive δ¹⁸O magmas during protolith emplacement. In contrast, newly grown domains have concordant U-Pb ages of 204 ± 4 to 252 ± 7 Ma and show negative δ¹⁸O values of −10.0‰ to −2.2‰, low Th/U and ¹⁷⁶Lu/¹⁷⁷Hf ratios, low REE contents, and flat HREE patterns with weak to no Eu anomalies. They are interpreted as growing from negative δ¹⁸O fluids that were produced by metamorphic dehydration of high-T glacial-hydrothermally altered rocks during continental subduction-zone metamorphism. Differences in δ¹⁸O between different domains within single grains vary from 0.8‰ to 12.5‰, suggesting different degrees of O isotope exchange between the positive δ¹⁸O magmatic core and the negative δ¹⁸O metamorphic fluid during the metamorphism. The magmatic zircons underwent three subtypes of metamorphic recrystallization, depending on their accessibility to negative δ¹⁸O fluids. The zircons recrystallized in solid-state maintained positive δ¹⁸O values, and REE and Lu-Hf isotopes of protolith zircon, but their U-Pb ages are lowered. The zircons recrystallized through dissolution exhibit negative δ¹⁸O values similar to the metamorphic growths, almost completely reset U-Pb ages, and partially reset REE systems. The zircons recrystallized through replacement show variably negative δ¹⁸O values, and partially reset REE, and U-Pb and Lu-Hf isotopic systems. Therefore, this study places robust constraints on the origin of metamorphic zircons in eclogite-facies rocks and provides a methodological framework for linking the different types of metamorphic zircons to petrological processes during continental collision.     

Comment on “Paleozoic ages and excess Ar in garnets from the Bixiling eclogite in Dabieshan, China: New insights from Ar/Ar dating by stepwise crushing” by Qiu and Wijbrans (2006)

Qiu and Wijbrans [Qiu H.-N. and Wijbrans J. R. (2006) Paleozoic ages and excess ⁴⁰Ar in garnets from the Bixiling eclogite in Dabieshan, China: new insights from ⁴⁰Ar/³⁹Ar dating by stepwise crushing. Geochim. Cosmochim. Acta70, 2354-2370] present three Ar-Ar age spectra for fluid inclusions in garnet from eclogite at Bixiling in the Dabie orogen, east-central China. These Paleozoic ages of 427 ± 20 to 444 ± 10 Ma are interpreted to represent the first formation of Dabie ultrahigh-pressure (UHP) eclogite and thus require subduction of Yangtze crust to have started much earlier than previously accepted. However, no petrographic evidence, such as mineral inclusions in the garnet relating to the particular metamorphic conditions, is presented to substantiate the proposed UHP metamorphic event. Because garnet growth is not uniquely responsible for UHP eclogite-facies metamorphism, a distinction between UHP and high-pressure (HP) metamorphic events must be made in the interpretation of geochronological results. Available data from mineral Sm-Nd and zircon U-Pb dating of eclogites from the same area have firmly established that the UHP eclogite-facies metamorphism took place at Triassic. Neither the age of UHP metamorphism nor the timing of continental collision is reliably constrained by their presented data; the fluid inclusions in garnet must contain inherited ⁴⁰Ar from UHP eclogite precursor, without considerable resetting of the Ar-Ar isotopic system during Triassic UHP metamorphism. Therefore, their data are either meaningless, or at best viewed as the age of garnet growth by low-T/HP blueschist/eclogite-facies metamorphism of the UHP eclogite precursor during arc-continent collision in the early Paleozoic. Furthermore, it is critical for metamorphic geochronology to substantiate the timing of UHP metamorphic event by means of zircon U-Pb in situ dating on coesite-bearing domains of metamorphically grown zircon.     

含榴花岗片麻岩 Lu-Hf 年代学初探

对西大别四道河含石榴子石花岗片麻岩进行了锆石 U-Pb 和石榴子石 Lu-Hf 年代学测试,锆石 U-Pb谐和年龄为(223±1) Ma,石榴子石-全岩 Lu-Hf 等时线年龄为(212.2±0.7) Ma.石榴子石具有极高的母子体同位素比值(176Lu/177Hf =~300).结合锆石和石榴子石的微量元素特征,该锆石 U-Pb 年龄代表的可能是超高压/高压变质时间,石榴子石 Lu-Hf 年龄代表的是石榴子石重结晶时间,可能指示了后期退变质作用流体活动     

SHRIMP U-Pb dating, trace elements and the Lu-Hf isotope system of coesite-bearing zircon from amphibolite in the SW Sulu UHP terrane, eastern China

In this study, we link mineral inclusion data, trace element analyses, U-Pb age and Hf isotope composition obtained from distinct zircon domains of complex zircon to unravel the origin and multi-stage metamorphic evolution of amphibolites from the Sulu ultrahigh-pressure (UHP) terrane, eastern China. Zircon grains separated from amphibolites from the CCSD-MH drill hole (G12) and Niushan outcrop (G13) were subdivided into two main types based on cathodoluminescence (CL) and Laser Raman spectroscopy: big dusty zircons with inherited cores and UHP metamorphic rims and small clear zircons. Weakly zoned, grey-white luminescent inherited cores preserve mineral inclusions of Cpx + Pl + Ap ± Qtz indicative of a mafic igneous protolith. Dark grey luminescent overgrowth rims contain the coesite eclogite-facies mineral inclusion assemblage Coe + Grt + Omp + Phe + Ap, and formed at T = 732-839 °C and P = 3.0-4.0 GPa. In contrast, white luminescent small clear zircons preserve mineral inclusions formed during retrograde HP quartz eclogite to LP amphibolite-facies metamorphism (T = 612-698 °C and P = 0.70-1.05 GPa). Inherited zircons from both samples yield SHRIMP ²⁰⁶Pb/²³⁸U ages of 695-520 Ma with an upper intercept age of 800 ± 31 Ma. The UHP rims yield consistent Triassic ages around 236-225 and 239-225 Ma for G12 and G13 with weighted means of 229 ± 3 and 231 ± 3 Ma, respectively. Small clear zircons from both samples give ²⁰⁶Pb/²³⁸U ages around 219-210 Ma with a weighted mean of 214 ± 3 Ma, interpreted as the age of retrograde quartz eclogite-facies metamorphism. Matrix amphibole from both samples indicate Ar-Ar ages of 209 ± 0.7 and 207 ± 0.7 Ma, respectively, probably dating late amphibolite-facies retrogression. The data suggest subduction of Neoproterozoic mafic igneous rocks to UHP conditions in Middle Triassic (∼230 Ma) times and subsequent exhumation to an early HP (∼214 Ma) and a late LP stage (∼208 Ma) over a period of ∼16 and 6 Myr, respectively. Thus, early exhumation from a mantle depth of 120-100 km to about 60 km occurred at an average rate of 0.3 cm/y, while subsequent exhumation to a middle crustal level took place at approximately 0.54 cm/y. These exhumation rates are considerably slower than those obtained for UHP rocks in the Dora Maira and Kokchetav massifs (2-3 cm/y).Based on similar P-T estimates and trace element and Hf isotope compositions, Sulu amphibolites can be identified as retrograde UHP eclogites. The εHf₍₈₀₀₎ of +8 implies a significant input from the depleted mantle to the Sulu-Dabie terrane during the middle Neoproterozoic. Overgrown rims are characterized by a distinct trace element composition with low Lu/Hf and Th/U and significantly higher ¹⁷⁶Hf/¹⁷⁷Hf ratios than inherited cores, consistent with formation during/after garnet (re-)crystallization and fractionation of the Lu-Hf system during UHP metamorphism. The combined dataset suggests homogenization of the ¹⁷⁶Hf/¹⁷⁷Hf ratio within the metamorphic mineral assemblage and during protolith formation. Observed variations are explained by mixing of material from both domains during laser ablation, e.g., due to partial recrystallization of inherited cores.     

榴辉岩相峰期流体活动：来自东昆仑榴辉岩石英脉的证据

本文通过对东昆仑温泉地区榴辉岩中石英脉的锆石U-Pb定年和Lu-Hf同位素的综合研究,为榴辉岩相峰期变质阶段的流体活动提供了一定的证据。石英脉中的锆石晶型较好,具有振荡环带或弱分带,排除了从寄主榴辉岩中捕获锆石的可能性。石英脉和寄主榴辉岩中锆石U-Pb年龄的加权平均值分别为450±2Ma和451±2Ma,说明石英脉中锆石的形成年龄与榴辉岩相的峰期变质阶段一致。两种锆石Hf同位素组成的相似性说明形成石英脉的流体/熔体为内部来源,推测可能为榴辉岩中石英发生溶解以及绿辉石和石榴石分子结构中羟基的出溶作用形成。锆石较低的U、Th含量以及Th/U比值说明石英脉更可能是流体活动形成而非熔体。     

Hafnium isotope homogenization during metamorphic zircon growth in amphibolite-facies rocks: Examples from the Shackleton Range (Antarctica)

Hafnium isotope analyses of a large number of metamorphic zircon grains of two garnet-kyanite-staurolite schist samples from the Shackleton Range yielded ¹⁷⁶Hf/¹⁷⁷Hf of 0.28160 ± 0.00003 and 0.28142 ± 0.00003, respectively. The variations of these analyses are less than ±1.2 epsilon units and indicate that all metamorphic zircon grains in the two rocks formed in environments with nearly homogenous Hf isotopic composition. The metamorphic origin of the zircon grains is constrained by textures as well as by their low Th/U (<0.2), ¹⁷⁶Lu/¹⁷⁷Hf (<0.0003), and ¹⁷⁶Yb/¹⁷⁷Hf ratios (<0.009), indicating that they grew in the presence of garnet. Furthermore, the grains yield Pb-Pb ages of c. 1.7 Ga, which is the time of amphibolite-facies metamorphism. In combination with petrological results, it is suggested that the observed ¹⁷⁶Hf/¹⁷⁷Hf homogeneity was caused by a fluid- and deformation-assisted dissolution of detrital zircon grains, followed by new zircon re-precipitation that was accompanied by Hf transport on at least a hand-specimen scale. This interpretation is supported by results obtained from an additional paragneiss sample that contains zoned zircon grains with xenocrystic cores formed at 2.6-1.8 Ga and metamorphic rims with a U-Pb age of 1.7 Ga. The ¹⁷⁶Hf/¹⁷⁷Hf variation of the zircon rims is mostly at ±0.0003, which is much less than that of the magmatic cores (±0.0019). The metamorphic fluid for the dissolution-homogenization-re-precipitation process most likely resulted from prograde reactions among the minerals chlorite-muscovite-biotite-garnet-staurolite-apatite, in agreement with thin section observations and P-T pseudosection calculations.     

Extreme oxygen isotope signature of meteoric water in magmatic zircon from metagranite in the Sulu orogen, China: Implications for Neoproterozoic rift magmatism

Unusual ¹⁸O depletion, with δ¹⁸O values as negative as −10‰ to −4‰ relative to VSMOW, was reported in zircons from ultrahigh-pressure eclogite-facies metamorphic rocks in the Dabie-Sulu orogenic belt, China. But it is critical for the negative δ¹⁸O zircons to be distinguished between magmatic and metamorphic origins, because the ¹⁸O depletion can be acquired by high-T eclogite-facies metamorphism of meteoric-hydrothermally altered low δ¹⁸O rocks. While zircon O diffusion kinetics has placed a reasonable constraint on this, zircon trace element compositions can provide a straightforward distinction between the magmatic and metamorphic origins. This paper reports our finding of unusual ¹⁸O depletion in zircon from granitic gneiss in the northeastern end of the Sulu orogen. Zircon δ¹⁸O values vary from −7.8‰ to −3.1‰ along a profile of 50 m length at Zaobuzhen. They are close to extremely low δ¹⁸O values of −9.0‰ to −5.9‰ for metagranite at Qinglongshan and adjacent areas in the southwestern end of the Sulu orogen. CL imaging suggests that the low δ¹⁸O zircons at Zaobuzhen are primarily of magmatic origin, but underwent different degrees of metamorphic modification. Zircon U-Pb dating yields middle Neoproterozoic ages of 751 ± 27 to 779 ± 25 Ma for protolith crystallization and Triassic ages of 214 ± 10 to 241 ± 33 Ma for metamorphic resetting. However, no metamorphic modification occurs in zircon REE patterns that only indicate magmatic recrystallization and hydrothermal alteration, respectively. Thus, the negative δ¹⁸O zircons are interpreted as crystallizing from negative δ¹⁸O magmas due to melting of meteoric-hydrothermally altered negative δ¹⁸O rocks in an active rift setting at about 780 Ma. The variation in zircon δ¹⁸O values indicates considerable O isotope heterogeneity in its granitic protolith. Zircon Lu-Hf isotope analyses give positive ε_Hf(t) values of 1.6-4.1 and Hf model ages of 1.18-1.30 Ga. This suggests that the granitic protolith was derived from the mid-Neoproterozoic reworking of late Mesoproterozoic juvenile crust. The metagranites at Zaobuzhen and Qinglongshan, about 450 km apart, are two known occurrences of the unusually low δ¹⁸O zircons below −6‰ so far reported in the Sulu orogen. They are similar to each other in both protolith and metamorphic ages, so that they share the same nature of both Neoproterozoic protolith and Triassic metamorphism. Therefore, the locally negative δ¹⁸O zircons may register centers of low δ¹⁸O magmatism during the supercontinental rifting.     

Zircon formation during fluid circulation in eclogites (Monviso, Western Alps): implications for Zr and Hf budget in subduction zones

The zircons from an eclogite and an enclosed eclogite-facies vein from the Monviso ophiolite (Western Alps) display contrasting chemical and morphologic features and document different stages of the evolution of the ophiolite. The zircons from the eclogite show a typical magmatic zoning and are enriched in heavy rare earth elements (HREEs) over middle rare earth elements (MREEs) and have an accentuated negative Eu anomaly, which indicates that the grains co-crystallised with plagioclase. These magmatic zircons document the formation of oceanic crust at 163 ± 2 Ma. In contrast, zircons from the vein contain inclusions of garnet, omphacite, and rutile, which indicate that they crystallised under eclogite-facies conditions. The vein zircons have Th/U ratios < 0.09, lack Eu anomalies, and are only weakly enriched in HREE with respect to MREE. These features are consistent with a garnet-bearing, plagioclase-free, i.e., eclogite-facies paragenesis. Vein zircons yield an age of 45 ± 1 Ma, which is evidence for Eocene subduction-zone metamorphism of the Monviso ophiolite.In the vein, the apparent coexistence of zircon, omphacite, and garnet permits the determination of a set of trace element distribution coefficients among these minerals at high pressure. This set of partitioning can demonstrate chemical equilibrium among these phases in rocks that show less clear evidence of textural equilibrium. In addition, zircon age can now be linked to sensors of metamorphic pressure-temperature conditions. The presence of zircon and rutile in the vein is another example of high field strength element (HFSE) mobility over short distances in aqueous fluids at eclogite-facies conditions. However, the concentrations of Zr and Hf in the aqueous fluid are estimated to be at least a factor of 10 less than primitive mantle values.Mass balance calculations demonstrate that zircon hosts > 95% of the bulk Zr, 90% of Hf, and ∼25% of U in the vein. Zircon is a residual phase in subducted basalts and sediments up to temperatures of at least 800 to 900 °C. Therefore, residual zircon in subducted crust, together with rutile, control the HFSE in liberated subduction zone fluids/melts and might be partly responsible for negative Zr and Hf anomalies in subduction zone magmas.     

Rate of growth of the preserved North American continental crust: Evidence from Hf and O isotopes in Mississippi detrital zircons

Detrital zircons from the Mississippi River have been analyzed for U-Th-Pb, Lu-Hf and O isotopes to constrain the rate of growth of the preserved North American continental crust. One hundred and forty two concordant zircon U/Pb dates on grains mounted in epoxy, obtained by Excimer laser ablation ICP-MS method, resolved six major periods of zircon crystallization: 0-0.25, 0.3-0.6, 0.95-1.25, 1.3-1.5, 1.65-1.95 and 2.5-3.0 Ga. These age ranges match the ages of the recognized lithotectonic units of the North American continent in the hinterland of the Mississippi River. Ninety-six zircons mounted on tape, which show no age zonation and were within 7.5% of concordance, were selected to represent the six U/Pb age time intervals and analyzed for Lu-Hf and O isotope by laser ablation MC-ICP-MS and SHRIMP II, respectively. The δ¹⁸O values of the zircons show a small step increase in the maximum δ¹⁸O values at the Archean-Proterozoic boundary from 7.5‰ in the Archean to 9.5‰, and rarely 13‰, in the Proterozoic and Phanerozoic. However, the average value of δ¹⁸O in zircons changes little with time, showing that the increase in the maximum δ¹⁸O values between 2.5 and 2.0 Ga, which can be attributed to an increase in the sediment content of the source regions of younger granitoids, is largely balanced by an increase in zircons with anomalously low δ¹⁸O, which can be attributed to hydrothermally altered crust in the granitoid source region.εHf_i values for the zircons range from 13.1 to −26.9. Zircons derived from juvenile crust, which we define as having mantle δ¹⁸O (4.5-6.5‰) and lying within error of the Hf depleted mantle growth curve, are rare or absent in the Mississippi basin. The overwhelming majority of zircons crystallized from melted pre-existing continental crust, or mantle-derived magmas that were contaminated by continental crust. The average time difference between primitive crust formation and remelting for each of the recognized lithotectonic time intervals, which is defined as crustal incubation time in this study, is 890 ± 460 Myr. There is also a suggestion that the crustal incubation time increases with decreasing age in the Mississippi basin, which is consistent with the declining role of radioactive heat production in the lower crust with time.The average Hf model age (1.94 Ga), weighted by fraction of zircons in the river load is in reasonable agreement with the Nd model age (1.7 Ga) for the Mississippi River. However, if the zircons are weighted by the area of North America covered by the six recognized periods of zircon crystallization the average model age is 2.35 Ga, which compares favorably with an area weighted Nd model age of 2.36 Ga. Our preferred approach is to use the measured O isotope values to constrain variations in the ¹⁷⁶Lu/¹⁷⁷Hf ratio of the granitic source region from which the zircons crystallized, making the assumption that zircons with mantle-like O isotopic ratios have higher ¹⁷⁶Lu/¹⁷⁷Hf than zircons with higher O isotope values. This method gives an average Hf model age of 2.53 Ga, which is 180 Myr older than the constant ¹⁷⁶Lu/¹⁷⁷Hf calculation.The area weighted zircon Hf model ages show two distinct periods of crust formation for the North American continent, 1.6-2.2 and 2.9-3.4 Ga. At least 50% of the preserved North American continental crust was extracted from the mantle by 2.9 Ga and 90% by 1.6 Ga. Two similar periods of crustal growth are also recognized in Gondwana (Hawkesworth C. J. and Kemp A. I. S. (2006) Using hafnium and oxygen isotopes in zircons to unravel the record of crustal evolution. Chem. Geol.226, 144-162.), suggesting that these may be periods of global continental crustal growth. However, we stress that more data from other continents are required before the hypothesis of episodic global continental growth can be accepted with confidence.     

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.     

Growth rate of the preserved continental crust: II. Constraints from Hf and O isotopes in detrital zircons from Greater Russian Rivers

Detrital zircons from the Ob, Yenisey, Lena, Amur, Volga, Dnieper, Don and Pechora rivers have been analyzed for U-Th-Pb, O and Lu-Hf isotopes to constrain the growth rate of the preserved continental crust in Greater Russia. Four major periods of zircon crystallization, 0.1-0.55, 0.95-1.3, 1.45-2.0 and 2.5-2.9 Ga, were resolved from a compilation of 1366 zircon U/Pb ages. The Archean zircons have δ¹⁸O values lying between 4.53‰ and 7.33‰, whereas Proterozoic and Phanerozoic zircons have a larger range of δ¹⁸O values in each of the recognized U/Pb time intervals with maximum δ¹⁸O values up to 12‰. We interpret the zircons with δ¹⁸O between 4.5‰ and 6.5‰ to have been derived from a magmatic precursor that contains little or no sedimentary component. The variable δ¹⁸O values of the zircons were used to constrain the ¹⁷⁶Lu/¹⁷⁷Hf ratios of the crustal source region of the zircons, which, in turn, were used to calculate Hf model ages (T_DM^V). The crustal incubation time, the time difference between primitive crust formation (dated by T_DM^V) and crustal melting (dated by zircon U/Pb age), varies between 300 to 1000 Myr for the majority of analyzed zircon grains, but can be up to 2500 Myr. The average T_DM^V Hf model age weighted by the fraction of zircons in the river load is 2.12 Ga, which is in reasonable agreement with the area-weighted average of 2.25 Ga. The T_DM^V Hf model age crustal growth curve for zircons with mantle-like δ¹⁸O values (4.5-6.5‰), weighted by area, shows that growth of the Great Russian continental crust started at 4.2 Ga, and that there are two principal periods of crustal growth, 3.6-3.3 Ga and 0.8-0.6 Ga, which are separated by an interval of low but more or less continuous growth. An alternative interpretation, in which the average ¹⁷⁶Lu/¹⁷⁷Hf ratio (0.0115) of the continental crust is used for the Paleoproterozoic zircons from the Lena River, lowers the average T_DM^V age of these grains by about 500 Myr and delays the onset of significant crustal growth to 3.5 Ga.The two principal growth periods recognized in Greater Russia differ from those identified from the Gondwana and the Mississippi river basin, which show peaks at 1.7-1.9 and 2.9-3.1 Ga (Hawkesworth and Kemp, 2006a) and 1.6-2.2 and 2.9-3.4 Ga (Wang et al., 2009), respectively. The older 3.6-3.3 Ga or 3.5-3.3 Ga peak for Greater Russia is slightly older than the older Gondwana-Mississippi peaks, whereas the younger 0.8-0.6 Ga peak is distinctly younger than the youngest peak in either Gondwana or the Mississippi river basin. This suggests that the two major peaks of crustal growth identified in Gondwana and the Mississippi river basin may not be global periods of enhanced continental growth and that the major periods of crustal growth may differ from continent to continent.     

Continuous zircon growth during long-lived granulite facies metamorphism: a microtextural,U–Pb,Lu–Hf and trace element study of Caledonian rocks from the Arctic

Microtextural, U–Pb, trace element and Lu–Hf analyses of zircons from gneisses dredged from the Chukchi Borderland indicate a long-lived, Cambrian–Ordovician, granulite facies metamorphism. These results reveal a complete prograde, peak and cooling history of zircon growth during anatexis. Early increasing temperatures caused modification and Pb-loss of Precambrian zircons by recrystallization and dissolution/re-precipitation of existing grains. Small variations in initial ¹⁷⁶Hf/¹⁷⁷Hf results (0.282325–0.282042) and flat HREE patterns of these zircons indicate that they grew by dissolution/re-precipitation in the presence of garnet. Zircons subsequently crystallized from a partial melt during peak to post-peak metamorphism from 530 to 485 Ma. A broad range of initial ¹⁷⁶Hf/¹⁷⁷Hf ratios (0.282693–0.282050) and mineral inclusions within zircons suggest that this phase of growth incorporated Zr and Hf obtained from the breakdown of Zr-enriched phases. Microtextural evidence along with trace element and isotopic data suggests that final growth of metamorphic rims on zircon occurred during slow cooling and crystallization of residual partial melts during the early Ordovician (485–470 Ma). Younger, late Ordovician–Silurian (420–450 Ma) euhedral, oscillatory-zoned, trace element-enriched zircons crystallized within leucocratic veins that intrude the gneisses. Their age corresponds to granitoids dated from this same dredge. The intrusives and veins provide evidence that the Chukchi Borderland rifted from a position near Pearya and northwest Svalbard, which represent the northern continuation of the Caledonian orogen. Evidence for earlier Cambrian metamorphism has not been reported from this region. The age of granulite facies metamorphism reported here represents the earliest phase of deformation in the Arctic Caledonides.     

Devonian to Carboniferous collision in the Greenland Caledonides: U-Pb zircon and Sm-Nd ages of high-pressure and ultrahigh-pressure metamorphism

A variety of eclogites from an east-west transect across the North-East Greenland eclogite province have been studied to establish the timing of high pressure (HP) and ultrahigh-pressure (UHP) metamorphism in this northern segment of the Laurentian margin. Garnet + omphacite ± amphibole + whole rock Sm-Nd isochrons from a quartz eclogite, a garnet + omphacite + rutile eclogite and a partially melted zoisite eclogite in the western HP belt are 401±2, 402±9 and 414±18 Ma, respectively. Corresponding sensitive high-resolution ion microprobe (SHRIMP) ²⁰⁶Pb/²³⁸U ages of metamorphic zircon in the same samples are 401±7, 414±13, and 393 ±10 Ma. Metamorphic zircon domains were identified using morphology, cathodoluminescence (CL) imaging, U, Th, Th/U and trace element contents. Zircon from the quartz eclogite and the garnet + omphacite + rutile eclogite are typical of eclogite facies zircon with rounded to subhedral shapes, patchy to homogenous CL domains, low U, and very low Th and Th/U. The partially melted eclogite contains euhedral zircons with dark, sector-zoned, higher U, Th and Th/U inherited cores. Three cores give a Paleoproterozoic ²⁰⁷Pb/²⁰⁶Pb age of 1,962±27 Ma, interpreted as the age of the leucogabbroic protolith. CL images of the bright overgrowths show faint oscillatory zoning next to homogenous areas that indicate zircon growth in the presence of a HP melt and later recrystallization. Additional evidence that zircon grew during eclogite facies conditions is the lack of a Eu anomaly in the trace element data for all the samples. These results, combined with additional less precise Sm-Nd ages and our earlier work, point to a Devonian age of HP metamorphism in the western and central portions of the eclogite province. An UHP kyanite eclogite from the eastern part of the transect contains equant metamorphic zircon with homogeneous to patchy zoning in CL and HP inclusions of garnet, omphacite and kyanite. These zircons have slightly higher U, Th and Th/U values than the HP ones, no Eu anomaly, and are thus comparable to UHP zircons in the literature. The ²⁰⁶Pb/²³⁸U age of these zircons is 360±5 Ma, much younger than the HP eclogites. The same sample gives a Sm-Nd age of 342±6 Ma. Unlike the HP eclogites, the Sm-Nd age of the UHP rock is ca. 20 Ma younger than the U-Pb zircon age and most likely records slow cooling through the closure temperature, since peak temperatures were in excess of 900°C. Widespread HP metamorphism of both the Laurentian and Baltica continental margins marks the culmination of this continent–continent collision in the Devonian. Carboniferous UHP conditions, though localized in the east, suggest a prolonged collisional history rather than a short-lived Scandian orogeny. The traditional Silurian Scandian orogeny should thus be extended through the Devonian.     

西大别浒湾变质带洋壳和陆壳耦合俯冲的锆石U-Pb年龄记录及其动力学意义

西大别浒湾高压变质带是研究秦岭-大别-苏鲁造山带演化的关键区域.本文对该变质带熊店和学河两地的两个榴辉岩样品进行了LA-(MC)-ICPMS锆石U-Pb定年、微量元素分析及Hf同位素测定.熊店榴辉岩岩浆锆石得到的年龄为406±14Ma,具有高的εHf(t)值(εHf(t)=11.3±1.3),年轻的亏损地幔模式年龄(tDM=578±52Ma),其来源可能为亏损地幔,进而说明它们的原岩可能为古特提斯洋壳物质;学河榴辉岩岩浆锆石的年龄为703±8Ma,具有略低的εHf(t)值(εHf(t)=4.11±0.94),较老的亏损地幔模式年龄(tDM=1105±37Ma),其原岩可能为扬子克拉通新元古代裂谷岩浆作用产生的新生陆壳物质.这些结果表明浒湾地区存在原岩形成于新元古代和志留纪两个时期的榴辉岩.熊店榴辉岩中变质锆石的微量元素特征与岩浆锆石类似,可能为完全重结晶成因锆石,其206Ph/238U加权平均年龄为316±1Ma,代表了洋壳榴辉岩榴辉岩相峰期变质的最早时间.学河榴辉岩变质锆石以低Th/U、Nb/Ta比值为特征,其REE组成模式为不明显的Eu负异常,HREE呈平坦型.这些特征反映了这些锆石形成时出现了较大数量的石榴子石与金红石,而缺乏长石.根据锆石Ti温度计计算学河榴辉岩变质锆石形成的温度范围是704～741℃,与榴辉岩相变质温度一致.它们对应的206Pb/238U加权平均年龄为312±3Ma,可作为浒湾变质带榴辉岩相峰期变质年龄,这一结果表明浒湾变质带陆壳成因榴辉岩存在石炭纪榴辉岩相变质事件.空间上相近的古生代洋壳和新元古代陆壳具有相同的榴辉岩相变质年龄表明,浒湾变质带的洋壳和陆壳榴辉岩可能存在石炭纪的耦合俯冲作用.     

Timing of UHP metamorphism in the Hong’an area,western Dabie Mountains,China: evidence from zircon U–Pb age,trace element and Hf isotope composition

The Hong’an area (western Dabie Mountains) is the westernmost terrane in the Qinling-Dabie-Sulu orogen that preserves UHP eclogites. The ages of the UHP metamorphism have not been well constrained, and thus hinder our understanding of the tectonic evolution of this area. LA-ICPMS U–Pb age, trace element and Hf isotope compositions of zircons of a granitic gneiss and an eclogite from the Xinxian UHP unit in the Hong’an area were analyzed to constrain the age of the UHP metamorphism. Most zircons are unzoned or show sector zoning. They have low trace element concentrations, without significant negative Eu anomalies. These metamorphic zircons can be further subdivided into two groups according to their U–Pb ages, and trace element and Lu–Hf isotope compositions. One group with an average age of 239 ± 2 Ma show relatively high and variable HREE contents (527 ≥ Lu_N ≥ 14) and ¹⁷⁶Lu/¹⁷⁷Hf ratios (0.00008–0.000931), indicating their growth prior to a great deal of garnet growth in the late stage of continental subduction. The other group yields an average age of 227 ± 2 Ma, and shows consistent low HREE contents and ¹⁷⁶Lu/¹⁷⁷Hf ratios, suggesting their growth with concurrent garnet crystallization and/or recrystallization. These two groups of age are taken as recording the time of prograde HP to UHP and retrograde UHP–HP stages, respectively. A few cores have high Th/U ratios, high trace element contents, and a clear negative Eu anomaly. These features support a magmatic origin of these zircon cores. The upper intercept ages of 771 ± 86 and 752 ± 70 Ma for the granitic gneiss and eclogite, respectively, indicate that their protoliths probably formed as a bimodal suite in rifting zones in the northern margin of the Yangtze Block. Young Hf model ages (T _DM1) of magmatic cores indicate juvenile (mantle-derived) materials were involved in their protolith formation. Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

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.     

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。     

北苏鲁仰口地区变辉长岩中锆石U-Pb定年、微量元素和Hf同位素特征及其地质意义

北苏鲁仰口地区出露超高压的变辉长岩.锆石阴极发光图像和其内部矿物包体激光拉曼测试的联合研究结果表明,变辉长岩锆石具有弱发光效应的岩浆韵律环带的核和被改造的强发光效应的边.岩浆韵律环带的核部保存大量而复杂的矿物包体,包括普通辉石(Cpx)+斜方辉石(Opx)+斜长石(P1)+石英(Qtz)+黑云母(Bt)+钛铁矿(Ilm)+磷灰石(Ap);边部保存的矿物包体则相对较少,包括普通辉石(Cpx)+斜方辉石(Opx)+斜长石(Pl)+磷灰石(Ap).尽管岩浆韵律环带核部的稀土元素总合量比被改造的锆石边部明显偏高,但二者稀土元素配分模式具有明显的相似性,主要表现为轻稀土相对亏损,而重稀土明显富集,相应的(La/Yb)N=0.00015～0.00039,并具有明显的负Eu异常(Eu/Eu*=0.20～0.26)、相对明显的正Ce异常(Ce/Ce*=71.5～147.4)和较高的Th/U比值(1.97～2.69).上述特征表明,仰口地区变辉长岩中的锆石均为继承性的岩浆锆石,而没有新生的变质锆石.LA-(MC)-ICP-MS锆石原位U-Pb定年和Lu-Hf同位素分析结果表明,两件锆石样品Y1和Y2的年龄数据所构成的不一致线显示了十分接近的上交点和下交点年龄.其上交点年龄分别为785±15Ma(2σ)和784±12Ma(2σ),应代表原岩的形成时代,表明变辉长岩的原岩与Rodinia超大陆裂解的岩浆事件存在密切的成因关系;而下交点年龄分别为226±24Ma(2σ)和228±26Ma(2σ),与苏鲁其它类型超高压岩石中含柯石英锆石微区记录的变质年龄十分吻合,应代表变辉长岩的超高压变质时代.岩浆结晶锆石的核部具有明显偏高的176Lu/177Hf(0.00044～0.00291)和176Yh/177Hf(0.0165～0.1168)比值,而176Hf/177Hf比值变化于0.281956～0.282048之间,相应的εHf(t)=-8.5～-14.0,tDM2=2.03～2.32Ga,表明仰口地区变辉长岩的原岩起源于古元古代时期的富集地幔或发生部分熔融的下地壳残留体.被改造的岩浆结晶锆石的边部则具有明显偏低的176Lu/177Hf(0.00029～0.00060)和176Yh/177Hf(0.0112～0.0200)比值,而176Hf/177Hf(t)比值变化于0.281953～0.282002之间,相应的εHf(t)=-10.2～-11.9,tDM2=2.12～2.21Ga.与岩浆结晶锆石核部相比,被改造的岩浆锆石边部的176Lu/177Hf、176Yb/177Hf、176Hf/177Hf(t)比值和εHf(t)和tDM2值的变化范围更小,表明中-新三叠纪的超高压变质作用使岩浆结晶锆石边部的Lu-Hf同位素体系发生调整,更趋向于均一化.     

Pseudosection modelling and garnet Lu–Hf geochronology of HP amphibole schists constrain the closure of an ocean basin between the northern and southern Lhasa blocks,central Tibet

The P–T–t path of high‐P metamorphic rocks in subduction zones may reveal valuable information regarding the tectonic processes along convergent plate boundaries. Herein, we present a detailed petrological, pseudosection modelling and radiometric dating study of several amphibole schists of oceanic affinity from the Lhasa Block, Tibet. The amphibole schists experienced an overall clockwise P–T path that was marked by post‐P_max heating–decompression and subsequent isothermal decompression following the attainment of peak high‐P and low‐T conditions (~490°C and 1.6 GPa). Pseudosection modelling shows that the amphibole schists underwent water‐unsaturated conditions during prograde metamorphism, and the stability field of the assemblage extends to lower temperatures and higher pressures within the water‐unsaturated condition relative to water‐saturated model along the prograde path. The high‐P amphibole schists were highly reduced during retrograde metamorphism. Precise evaluation of the ferric iron conditions determined from the different compositions of epidote inclusions in garnet and matrix epidote is crucial for a true P–T estimate by garnet isopleth thermobarometry. Lu–Hf isotope analyses on garnet size separates from a garnet‐bearing amphibole schist yield four two‐point garnet–whole‐rock isochron ages from 228.2 ± 1.2 Ma to 224.3 ± 1.2 Ma. These Lu–Hf dates are interpreted to constrain the period of garnet growth and approximate the timing of prograde metamorphism because of the low peak metamorphic temperature of the rock and the well‐preserved Mn/Lu growth zoning in garnet. The majority of zircon U–Pb dates provide no constraints on the timing of metamorphism; however, two concordant U–Pb dates of 222.4 ± 3.9 Ma and 223.3 ± 4.2 Ma were obtained from narrow and uncommon metamorphic rims. Coexistence of zircon and sphene in the samples implies that the metamorphic zircon growth was likely assisted by retrogression of rutile to sphene during exhumation. The near coincident radiometric dates of zircon U–Pb and garnet Lu–Hf indicate rapid burial and exhumation of the amphibole schists, suggesting a closure time of c. 224–223 Ma for the fossil ocean basin between the northern and southern Lhasa blocks.