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.     

GHR1 Zircon – A New Eocene Natural Reference Material for Microbeam U‐Pb Geochronology and Hf Isotopic Analysis of Zircon

We present multitechnique U‐Pb geochronology and Hf isotopic data from zircon separated from rapakivi biotite granite within the Eocene Golden Horn batholith in Washington, USA. A weighted mean of twenty‐five Th‐corrected ²⁰⁶Pb/²³⁸U zircon dates produced at two independent laboratories using chemical abrasion‐isotope dilution‐thermal ionisation mass spectrometry (CA‐ID‐TIMS) is 48.106 ± 0.023 Ma (2s analytical including tracer uncertainties, MSWD = 1.53) and is our recommended date for GHR1 zircon. Microbeam ²⁰⁶Pb/²³⁸U dates from laser ablation‐inductively coupled plasma‐mass spectrometry (LA‐ICP‐MS) and secondary ion mass spectrometry (SIMS) laboratories are reproducible and in agreement with the CA‐ID‐TIMS date to within < 1.5%. Solution multi‐collector ICP‐MS (MC‐ICP‐MS) measurements of Hf isotopes from chemically purified aliquots of GHR1 yield a mean ¹⁷⁶Hf/¹⁷⁷Hf of 0.283050 ± 17 (2s, n = 10), corresponding to a εHf₀ of +9.3. Hafnium isotopic measurements from two LA‐ICP‐MS laboratories are in agreement with the solution MC‐ICP‐MS value. The reproducibility of ²⁰⁶Pb/²³⁸U and ¹⁷⁶Hf/¹⁷⁷Hf ratios from GHR1 zircon across a variety of measurement techniques demonstrates their homogeneity in most grains. Additionally, the effectively limitless reserves of GHR1 material from an accessible exposure suggest that GHR1 can provide a useful reference material for U‐Pb geochronology of Cenozoic zircon and Hf isotopic measurements of zircon with radiogenic ¹⁷⁶Hf/¹⁷⁷Hf.     

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.     

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.     

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.     

Zircon SHRIMP U–Pb and in-situ Lu–Hf isotope analyses of a tuff from Western Beijing: Evidence for missing Late Paleozoic arc volcano eruptions at the northern margin of the North China block

Zircon SHRIMP U–Pb and in-situ Lu–Hf isotopic analyses via laser ablation microprobe-inductively coupled plasma mass spectrometer (LAM-ICPMS) of a tuff within the Upper Paleozoic from Western Beijing were carried out to give new constraints on volcano eruption ages and source area of the tuffs within the North China block (NCB). SHRIMP U–Pb zircon dating of the tuff yielded a ²⁰⁶Pb/²³⁸U weighted mean age of 296 ± 4 Ma (95% confidence, MSWD = 3.3), which is very similar to the emplacement age of the newly discovered Carboniferous calc-alkaline, I-type continental arc granitoid plutons in the Inner Mongolia Paleo-uplift (IMPU) on the northern margin of the NCB. In-situ Lu–Hf analysis results of most zircons from the tuff yielded initial ¹⁷⁶Hf/¹⁷⁷Hf ratios from 0.282142 to 0.282284 and ε_Hf(t) values from − 15.9 to − 10.7. These Lu–Hf isotopic compositions are very similar to those of the Late Carboniferous granitoids in the IMPU, but are very different to those of the Central Asian Orogenic Belt (CAOB). Together with the sedimentary and tectonic analyses results, we inferred that the source area of the tuffs within the NCB is the IMPU instead of the CAOB. Therefore, some arc volcanoes once existed in the IMPU on northern margin of the NCB during the Late Carboniferous, but they were entirely eroded due to strong exhumation and erosion of the IMPU during the Late Carboniferous to Early Jurassic.     

Characterisation of Three Sri Lankan Zircon Megacrysts as Potential Reference Materials for Microbeam U-Pb Geochronology and Hf-O-Zr Isotope Measurements

In situ U-Pb geochronology and hafnium, oxygen and zirconium isotope measurements in zircons using laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) and ion microprobe techniques can provide essential isotopic data to constrain geological evolutionary histories. Developing reliable zircon reference materials is the cornerstone for in situ zircon chronology and isotopic studies. In this study, the homogeneity of U-Pb ages and Hf-O-Zr isotope ratios in three Sri Lankan zircon megacrysts (SLZA, SLZB and SLZC) were investigated using multiple analytical methods. The obtained U, Th, Pb and Hf mass fractions of the SLZA zircon were 839 ± 56 μg g^-1 (1s), 151 ± 15 μg g^-1 (1s), 198 ± 28 μg g^-1 (1s) and 8635 ± 286 μg g^-1 (1s), respectively. The mass fractions of U, Th, Pb and Hf in the SLZB zircon were 1106 ± 106 μg g^-1 (1s), 331 ± 61 μg g^-1 (1s), 376 ± 57 μg g^-1 (1s) and 9673 ± 976 μg g^-1 (1s), respectively. The U, Th, Pb and Hf mass fractions determined in the SLZC zircon were 551 ± 35 μg g^-1 (1s), 111 ± 8 μg g^-1 (1s), 129 ± 18 μg g^-1 (1s) and 7881 ± 393 μg g^-1 (1s), respectively. The chemical abrasion isotope dilution thermal ionisation mass-spectrometry (CA-ID-TIMS) method yielded a Th-corrected weighted mean ²⁰⁶Pb/²³⁸U age of 556.94 ± 1.29 Ma (95% conf., n = 5) for the SLZA zircon, 552.90 ± 1.29 Ma (95% conf., n = 7) for the SLZB zircon and 560.83 ± 1.29 Ma (95% conf., n = 7) for the SLZC zircon. The obtained Hf isotopic compositions of the SLZA, SLZB and SLZC zircons determined with the solution MC-ICP-MS method were 0.281651 ± 0.000014 (2s, n = 10), 0.281704 ± 0.000008 (2s, n = 10) and 0.281676 ± 0.000006 (2s, n = 10), respectively. The obtained O isotopes of the SLZA and SLZB zircons measured with the laser fluorination method were 12.14 ± 0.56‰ (2s, n = 4) and 11.91 ± 0.30‰ (2s, n = 4), respectively. The Zr isotopes of the SLZA, SLZB and SLZC zircons determined with double spike TIMS analysis yielded mean δ⁹⁴/⁹⁰Zr_SRM3169 values of -0.03 ± 0.06‰ (2s, n = 10), -0.03 ± 0.04‰ (2s, n = 10) and 0.00 ± 0.07‰ (2s, n = 8), respectively. The SLZA zircon can be used as a primary reference or quality control material for microbeam U-Pb, Hf and Zr isotope measurements because of its slight heterogeneity. The U-Pb, Hf and Zr isotopic compositions of the SLZB and SLZC megacrysts were homogeneous. The O isotopic compositions in the SLZA and SLZB zircon were slightly dispersed, indicating that these two megacrysts can only serve as secondary reference materials for microbeam O isotope measurements.     

SA01 – A Proposed Zircon Reference Material for Microbeam U‐Pb Age and Hf‐O Isotopic Determination

A new natural zircon reference material SA01 is introduced for U‐Pb geochronology as well as O and Hf isotope geochemistry by microbeam techniques. The zircon megacryst is homogeneous with respect to U‐Pb, O and Hf isotopes based on a large number of measurements by laser ablation‐inductively coupled plasma‐mass spectrometry (LA‐ICP‐MS) and secondary ion mass spectrometry (SIMS). Chemical abrasion isotope dilution thermal ionisation mass spectrometry (CA‐ID‐TIMS) U‐Pb isotopic analyses produced a mean ²⁰⁶Pb/²³⁸U age of 535.08 ± 0.32 Ma (2s, n = 10). Results of SIMS and LA‐ICP‐MS analyses on individual shards are consistent with the TIMS ages within uncertainty. The δ¹⁸O value determined by laser fluorination is 6.16 ± 0.26‰ (2s, n = 14), and the mean ¹⁷⁶Hf/¹⁷⁷Hf ratio determined by solution MC‐ICP‐MS is 0.282293 ± 0.000007 (2s, n = 30), which are in good agreement with the statistical mean of microbeam analyses. The megacryst is characterised by significant localised variations in Th/U ratio (0.328–4.269) and Li isotopic ratio (?5.5 to +7.9‰); the latter makes it unsuitable as a lithium isotope reference material.     

Petrogenesis of metatexite and diatexite migmatites determined using zircon U–Pb age,trace element and Hf isotope data,Higo metamorphic terrane,central Kyushu,Japan

Metatexite and diatexite migmatites are widely distributed within the upper amphibolite and granulite facies zones of the Higo low‐P/high‐T metamorphic terrane. Here, we report data from an outcrop in the highest grade part of the granulite facies zone, in which diatexite occurs as a 3 m thick layer between 2 m thick layers of stromatic‐structured metatexite within pelitic gneiss. The migmatites and gneiss contain the same peak mineral assemblage of biotite + plagioclase + quartz + garnet + K‐feldspar with retrograde chlorite ± muscovite and some accessory minerals of ilmenite ± rutile ± titanite + apatite + zircon + monazite ± pyrite ± zinc sulphide ± calcite. Calculated metamorphic P–T conditions are 800–900 °C and 9–12 kbar. Zircon in the diatexite forms elongate euhedral crystals with oscillatory zoning, but no core–rim structure. Zircon from the gneiss and metatexite forms euhedral–subhedral grains comprising inherited cores overgrown by thin rims. The overgrowth rims in the metatexite have lower Th/U ratios than zircon in the diatexite and yield a ²⁰⁶Pb/²³⁸U age of 116.0 ± 1.6 Ma, which is older than the 110.1 ± 0.6 Ma ²⁰⁶Pb/²³⁸U age derived from zircon in the diatexite. Zircon from the diatexite has variable REE contents with convex upward patterns and flat normalized HREE, whereas the overgrowth rims in the metatexite and gneiss have steep HREE‐enriched patterns; however, both types have similar positive Ce and negative Eu anomalies. ¹⁷⁶Hf/¹⁷⁷Hf ratios in the overgrowth rims from the metatexite are more variable and generally lower than values from zircon in the diatexite. Based on U–Pb ages, trace element and Hf isotope data, the zircon rims in the metatexite are interpreted to have crystallized from a locally derived melt, following partial dissolution of inherited protolith zircon during anatexis, whereas the zircon in the diatexite is interpreted to have crystallized from a melt that included an externally derived component. By integrating zircon and petrographic data for the migmatites and pelitic gneiss, the metatexite migmatite is interpreted to have formed by in situ partial melting in which the melt did not migrate from the source, whereas the diatexite migmatite included an externally derived juvenile component. The Cretaceous high‐temperature metamorphism of the Higo metamorphic terrane is interpreted to reflect emplacement of mantle‐derived basalts under a volcanic arc along the eastern margin of the Eurasian continent and advection of heat via hybrid silicic melts from the lower crust. Post‐peak crystallization of anatectic melts in a high‐T region at mid‐crustal depths occurred in the interval c. 116–110 Ma, as indicated by the difference in zircon ages from the metatexite and diatexite migmatites.     

Geochronology of high-pressure mafic granulite dykes in SW Sweden: tracking the P–T–t path of metamorphism using Hf isotopes in zircon and baddeleyite

Although the U–Pb zircon chronometer has been widely used for dating metamorphism in moderate‐ to high‐grade rocks, it is generally difficult to link the U–Pb age of zircon to specific metamorphic reactions. In this study, the initial Hf isotopic composition of secondary zircon is compared with the evolution of Hf isotopic composition of the bulk sample, back‐projected from the measured value through time. This approach may enhance the interpretation of radiometric ages performed on metamorphic mineral assemblages. Here, U–Pb, Sm–Nd and Lu–Hf geochronology and thermobarometry have been integrated and applied to two metamorphosed diabase dykes in the Sveconorwegian orogen, SW Sweden. The dykes are located ～5 km east of the NNE‐trending Göta Älv deformation zone in the Idefjorden terrane, and trend parallel to this zone. The Lunden dyke is recrystallized into a coronitic, granulite facies assemblage. U–Pb isotopic analyses of baddeleyite in this dyke indicate an emplacement age of c. 1300 Ma. Thermobarometric techniques applied to garnet and omphacitic clinopyroxene coronas indicate high‐pressure metamorphism at ～15 kbar and ～740 °C. The growth of polycrystalline zircon at the expense of baddeleyite occurred at 1046 ± 6 Ma. The identical Hf isotopic composition of polycrystalline zircon and baddeleyite shows that the baddeleyite‐to‐zircon transition took place before Hf equilibration among the other metamorphic minerals and, hence the c. 1046 Ma age of polycrystalline zircon sets an upper age limit of metamorphism of this sample. The Haregården dyke is recrystallized into a granoblastic transitional upper amphibolite to granulite facies assemblage. The estimated P–T conditions are ～10 kbar and ～700 °C. Analyses of small (～30 μm), clear and round zircon in this sample yield a Concordia U–Pb age of 1026 ± 4 Ma, which is indistinguishable from the Lu‐Hf and Sm‐Nd mineral isochron ages of 1027 ± 9 and 1022 ± 34 Ma, respectively. This type of secondary zircon plots at the lower end of the Lu‐Hf isochron and indicates simultaneous growth with garnet at c. 1026 Ma, a time when Hf isotopic equilibrium among minerals must have been reached.     

Mud Tank Zircon: Long‐Term Evaluation of a Reference Material for U‐Pb Dating,Hf‐Isotope Analysis and Trace Element Analysis

Zircon megacrysts from the Mud Tank carbonatite, Australia, are being used in many laboratories as a reference material for LA‐ICP‐MS U‐Pb dating and trace element measurement, and LA‐MC‐ICP‐MS determination of Hf isotopes. We summarise a database of > 10000 analyses of Mud Tank zircon (MTZ), collected from 2000 to 2018 during its use as a secondary reference material for simultaneous U‐Pb and trace element analysis, and for Hf‐isotope analysis. Trace element mass fractions are highest in dark red‐brown stones and lowest in colourless and gem‐quality ones. Individual unzoned grains can be chemically homogeneous, while significant variations in trace element mass fraction are associated with oscillatory zoning. Chondrite‐normalised trace element patterns are essentially parallel over large mass fraction ranges. A Concordia age of 731.0 ± 0.2 Ma (2s, n = 2272) is taken as the age of crystallisation. Some grains show lower concordant to mildly discordant ages, probably reflecting minor Pb loss associated with cooling and the Alice Springs Orogeny (450–300 Ma). Our weighted mean ¹⁷⁶Hf/¹⁷⁷Hf is 0.282523 ± 10 (2s, n = 9350); the uncertainties on this ratio reflect some heterogeneity, mainly between grains. A few analyses suggest that colourless grains have generally lower ¹⁷⁶Hf/¹⁷⁷Hf. MTZ is a useful secondary reference material for U‐Pb and Hf‐isotope analysis, but individual grains need to be carefully selected using CL imaging and tested for homogeneity, and ideally should be standardised by solution analysis.     

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 the¹⁷⁶Lu→¹⁷⁶Hf+β^? 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 μg 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.     

Differential subduction and exhumation of crustal slices in the Sulu HP-UHP metamorphic terrane: insights from mineral inclusions, trace elements, U-Pb and Lu-Hf isotope analyses of zircon in orthogneiss

Based on new evidence the Sulu orogen is divided from south‐east to north‐west into high‐pressure (HP) crustal slice I and ultrahigh‐pressure (UHP) crustal slices II and III. A combined set of mineral inclusions, cathodoluminescence images, U‐Pb SHRIMP dating and in situ trace element and Lu‐Hf isotope analyses was obtained on zircon from orthogneisses of the different slices. Zircon grains typically have three distinct domains that formed during crystallization of the magmatic protolith, HP or UHP metamorphism and late‐amphibolite facies retrogression, respectively: (i) oscillatory zoned cores, with low‐pressure (LP) mineral inclusions and Th/U > 0.38; (ii) high‐luminescent mantles (Th/U < 0.10), with HP mineral inclusions of Qtz + Grt + Arg + Phe + Ap for slice I zircon and Coe + Grt + Phe + Kfs + Ap for both slices II and III zircon; (iii) low‐luminescent rims, with LP mineral inclusions and Th/U < 0.08. Zircon U‐Pb SHRIMP analyses of inherited cores point to protolith ages of 785–770 Ma in all seven orthogneisses. The ages recorded for UHP metamorphism and subsequent retrogression in slice II zircon (c. 228 and c. 215 Ma, respectively) are significantly older than those of slice III zircon (c. 218 and c. 202 Ma, respectively), while slice I zircon recorded even older ages for HP metamorphism and subsequent retrogression (c. 245 and c. 231 Ma, respectively). Moreover, Ar‐Ar biotite ages from six paragneisses, interpreted as dating amphibolite facies retrogression, gradually decrease from HP slice I (c. 232 Ma) to UHP slice II (c. 215 Ma) and UHP slice III (c. 203 Ma). The combined data set suggests decreasing ages for HP or UHP metamorphism and late retrogression in the Sulu orogen from south‐east to north‐west. Thus, the HP‐UHP units are interpreted to represent three crustal slices, which underwent different subduction and exhumation histories. Slice I was detached from the continental lithosphere at ～55–65 km depth and subsequently exhumed while subduction of the underlying slice II continued to ～100–120 km depth (UHP) before detachment and exhumation. Slice III experienced a similar geodynamic evolution as slice II, however, both UHP metamorphism and subsequent exhumation took place c. 10 Myr later. Magmatic zircon cores from two types of orthogneiss in UHP slices II and III show similar mid‐Neoproterozoic crystallization ages, but have contrasting Hf isotope compositions (εHf_(～785) = ?2.7 to +2.2 and ?17.3 to ?11.1, respectively), suggesting their formation from distinct crustal units (Mesoproterozoic and Paleoproterozoic to Archean, respectively) during the breakup of Rodinia. The UHP and the retrograde zircon domains are characterized by lower Th/U and ¹⁷⁶Lu/¹⁷⁷Hf but higher ¹⁷⁶Hf/¹⁷⁷Hf(t) than the Neoproterozoic igneous cores. The similarity between UHP and retrograde domains indicates that late retrogression did not significantly modify chemical and isotopic composition of the UHP metamorphic system.     

Zircon geochemistry of two contrasting types of eclogite: Implications for the tectonic evolution of the North Qaidam UHPM belt,northern Tibet

Compared to the extensively documented ultrahigh-pressure metamorphism at North Qaidam, the pre-metamorphic history for both continental crust and oceanic crust is poorly constrained. Trace element compositions, U–Pb ages, O and Lu–Hf isotopes obtained for distinct zircon domains from eclogites metamorphosed from both continental and oceanic mafic rocks are linked to unravel the origin and multi-stage magmatic/metamorphic evolution of eclogites from the North Qaidam ultrahigh-pressure metamorphic (UHPM) belt, northern Tibet.For continental crust-derived eclogite, magmatic zircon cores from two samples with U–Pb ages of 875–856 Ma have both very high δ¹⁸O (10.6 ± 0.5‰) and mantle-like δ¹⁸O (averaging at 5.2 ± 0.7‰), high Th/U and ¹⁷⁶Lu/¹⁷⁷Hf ratios, and steep MREE-HREE distribution patterns (chondrite-normalized) with negative Eu anomalies. Combined with positive ε_Hf (t) of 3.9–14.3 and T_DM (1.2–0.8 Ga and 1.3–1.0 Ga, respectively), they are interpreted as being crystallized from either subduction-related mantle wedge or recycled material in the mantle. While the metamorphic rims from the eclogites have U–Pb ages of 436–431 Ma, varying (inherited, lower, and elevated) oxygen isotopes compared with cores, low Th/U and ¹⁷⁶Lu/¹⁷⁷Hf ratios, and flat HREE distribution patterns with no Eu anomalies. These reflect both solid-state recrystallization from the inherited zircon and precipitation from external fluids at metamorphic temperatures of 595–622 °C (T_Ti-in-zircon).For oceanic crust-derived eclogite, the magmatic cores (510 ± 19 Ma) and metamorphic rims (442.0 ± 3.7 Ma) also show distinction for Th/U and ¹⁷⁶Lu/¹⁷⁷Hf ratios, and the REE patterns and Eu anomalies. Combined with the mantle-like δ¹⁸O signature of 5.1 ± 0.3 ‰ and two groups of model age (younger T_DM close to the apparent ages and older > 700 Ma), two possible pools, juvenile and inherited, were involved in mixing of mantle-derived magma with crustal components. The relatively high δ¹⁸O of 6.6 ± 0.3‰ for metamorphic zircon rims suggests either the protolith underwent hydrothermal alteration prior to the ~ 440 Ma oceanic crust subduction, or external higher δ¹⁸O fluid activities during UHP metamorphism at ~ 440 Ma.Therefore, the North Qaidam UHPM belt witnesses multiple tectonic evolution from Late Mesoproterozoic–Neoproterozoic assembly/breakup of the Rodinia supercontinent with related magmatic emplacement, then Paleozoic oceanic subduction, and finally transition of continental subduction/collision related to UHP metamorphism.     

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.     

History of crustal growth and recycling at the Pacific convergent margin of South America at latitudes 29°–36° S revealed by a U–Pb and Lu–Hf isotope study of detrital zircon from late Paleozoic accretionary systems

Detrital zircon provides a powerful archive of continental growth and recycling processes. We have tested this by a combined laser ablation ICP-MS U–Pb and Lu–Hf analysis of homogeneous growth domains in detrital zircon from late Paleozoic coastal accretionary systems in central Chile and the collisional Guarguaráz Complex in W Argentina. Because detritus from a large part of W Gondwana is present here, the data delineate the crustal evolution of southern South America at its Paleopacific margin, consistent with known data in the source regions.Zircon in the Guarguaráz Complex mainly displays an U–Pb age cluster at 0.93–1.46 Ga, similar to zircon in sediments of the adjacent allochthonous Cuyania Terrane. By contrast, zircon from the coastal accretionary systems shows a mixed provenance: Age clusters at 363–722 Ma are typical for zircon grown during the Braziliano, Pampean, Famatinian and post-Famatinian orogenic episodes east of Cuyania. An age spectrum at 1.00–1.39 Ga is interpreted as a mixture of zircon from Cuyania and several sources further east. Minor age clusters between 1.46 and 3.20 Ga suggest recycling of material from cratons within W Gondwana.The youngest age cluster (294–346 Ma) in the coastal accretionary prisms reflects a so far unknown local magmatic event, also represented by rhyolite and leucogranite pebbles. It sets time marks for the accretion history: Maximum depositional ages of most accreted metasediments are Middle to Upper Carboniferous. A change of the accretion mode occurred before 308 Ma, when also a concomitant retrowedge basin formed.Initial Hf-isotope compositions reveal at least three juvenile crust-forming periods in southern South America characterised by three major periods of juvenile magma production at 2.7–3.4 Ga, 1.9–2.3 Ga and 0.8–1.5 Ga. The ¹⁷⁶Hf/¹⁷⁷Hf of Mesoproterozoic zircon from the coastal accretionary systems is consistent with extensive crustal recycling and addition of some juvenile, mantle-derived magma, while that of zircon from the Guarguaráz Complex has a largely juvenile crustal signature. Zircon with Pampean, Famatinian and Braziliano ages (< 660 Ma) originated from recycled crust of variable age, which is, however, mainly Mesoproterozoic. By contrast, the Carboniferous magmatic event shows less variable and more radiogenic ¹⁷⁶Hf/¹⁷⁷Hf, pointing to a mean early Neoproterozoic crustal residence. This zircon is unlikely to have crystallized from melts of metasediments of the accretionary systems, but probably derived from a more juvenile crust in their backstop system.     

Combining trace-element compositions, U–Pb geochronology and Hf isotopes in zircons to unravel complex calcalkaline magma chambers in the Upper Cretaceous Srednogorie zone (Bulgaria)

Precise U–Pb geochronology and Hf isotope tracing of zircon is combined with whole-rock geochemical and Sr and Nd isotope data in order to unravel processes affecting mafic to felsic calcalkaline magmas prior to and during their crystallization in crustal magma chambers along the southern border of Central Srednogorie tectonic zone in Bulgaria (SE Europe). ID-TIMS U–Pb dating of single zircons from felsic and mixed/mingled dioritic to gabbroic horizons of single plutons define crystallization ages of around 86.5–86.0, 85.0–84.5 and 82 Ma. Concordia age uncertainties are generally less than 0.3 Ma (0.35%–2σ), and as good as 0.08 Ma (0.1%), when the weighted mean ²⁰⁶Pb/²³⁸U value is used. Such precision allows the distinction of magma replenishment processes if separated by more than 0.6–1.0 Ma and when they are marked by newly saturated zircons. We interpret zircon dates from a single sample that do not overlap to reflect new zircon growth during magma recharge in a long-lived crustal chamber. Mingling/mixing of the basaltic magma with colder granitoid mush at mid- to upper-crustal levels is proposed to explain zircon saturation and fast crystallization of U- and REE-rich zircons in the hybrid gabbro.Major and trace-element distribution and Sr and Nd whole-rock isotope chemistry define island arc affinities for the studied plutons. Slab derived fluids and a sediment component are constrained as enrichment sources for the mantle wedge-derived magma, though Hf isotopes in zircon suggest crustal assimilation was also important. Inherited zircons, and their corresponding ε-Hf, from the hybrid gabbroic rocks trace the lower crust as possible source for enrichment of the mantle magma. These inherited zircons are about 440 Ma old with ε-Hf of − 7 at 82 Ma, whereas newly saturated concordant Upper Cretaceous zircons reveal mantle ε-Hf values of + 7.2 to + 10.1. The upper and middle crusts contribute in the generation of the granitoid rocks. Their zircon inheritance is Lower Palaeozoic or significantly older and crustal dominated with 82–85 Ma corrected ε-Hf values of − 28. The Cretaceous concordant zircons in the granitoids are mantle dominated with a ε-Hf values spreading from + 3.9 to + 7.     

Linking thermodynamic modelling,Lu–Hf geochronology and trace elements in garnet: new P–T–t paths from the Sevier hinterland

Major element, trace element and Lu–Hf geochronological data from amphibolite facies pelitic schist in the Raft River and Albion Mountains of northwest Utah and southern Idaho indicate that garnet grew during increasing pressure, interpreted to be the result of tectonic burial and crustal thickening during Sevier orogenesis. Garnet growth was interrupted by hiatuses interpreted from discontinuities in major element zonation. Pressure–temperature paths were determined from the pre‐hiatus portions of the garnet chemical zoning profiles and indicate an increase of ~2 kbar and ~50 °C in the western Raft River Mountains. Garnet Lu–Hf dates of 150 ± 1 Ma in the western Raft River Mountains and 138.7 ± 0.7 Ma and 132 ± 5 Ma in the southern Albion Mountains indicate the timing of garnet growth. Lutetium garnet zoning profiles indicate that the Lu–Hf ages are biased towards the post‐hiatus or outer pre‐hiatus segments, indicating that the determined ages likely post‐date the recorded P–T path history or date the tail end of the paths. Crustal thickening associated with Sevier orogenesis in the western Raft River Mountains thus began slightly before 150 ± 1 Ma, in the Late Jurassic. This study shows that integrating P–T paths determined from garnet growth zoning with Lu–Hf garnet geochronology and in situ garnet trace element analyses is an effective approach for interpreting and dating deformation events in orogenic belts.     

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.     

Zircon U–Pb ages, Hf and O isotopes constrain the crustal architecture of the ultrahigh-pressure Dabie orogen in China

The crustal structure of the Dabie orogen was reconstructed by a combined study of U–Pb ages, Hf and O isotope compositions of zircons from granitic gneiss from North Dabie, the largest lithotectonic unit in the orogen. The results were deciphered from metamorphic history to protolith origin with respect to continental subduction and exhumation. Zircon U–Pb dating provides consistent ages of 751 ± 7 Ma for protolith crystallization, and two group ages of 213 ± 4 to 245 ± 17 Ma and 126 ± 4 to 131 ± 36 Ma for regional metamorphism. Majority of zircon Hf isotope analyses displays negative ε_Hf(t) values of − 5.1 to − 2.9 with crust Hf model ages of 1.84 to 1.99 Ga, indicating protolith origin from reworking of middle Paleoproterozoic crust. The remaining analyses exhibit positive ε_Hf(t) values of 5.3 to 14.5 with mantle Hf model ages of 0.74 to 1.11 Ga, suggesting prompt reworking of Late Mesoproterozoic to Early Neoproterozoic juvenile crust. Zircon O isotope analyses yield δ¹⁸O values of − 3.26 to 2.79‰, indicating differential involvement of meteoric water in protolith magma by remelting of hydrothermally altered low δ¹⁸O rocks. North Dabie shares the same age of Neoproterozoic low δ¹⁸O protolith with Central Dabie experiencing the Triassic UHP metamorphism, but it was significantly reworked at Early Cretaceous in association with contemporaneous magma emplacement. The Rodinia breakup at about 750 Ma would lead to not only the reworking of juvenile crust in an active rift zone for bimodal protolith of Central Dabie, but also reworking of ancient crust in an arc-continent collision zone for the North Dabie protolith. The spatial difference in the metamorphic age (Triassic vs. Cretaceous) between the northern and southern parts of North Dabie suggests intra-crustal detachment during the continental subduction. Furthermore, the Dabie orogen would have a three-layer structure prior to the Early Cretaceous magmatism: Central Dabie in the upper, North Dabie in the middle, and the source region of Cretaceous magmas in the lower.