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The origin of crystal‐scale Zr isotopic variation remains enigmatic. Here, we report high‐precision Zr isotopic compositions of thin‐sectioned and hand‐picked zircon crystals from monzodiorites and K‐feldspar granites, which represent the mafic and felsic products of a differentiating magma. Our results reveal that zircons from both rock associations are dominated by a rim‐ward increase in the 94Zr/90Zr ratio and accompanied by ∼1‰ intracrystalline and intercrystalline variations, confirming the preferential incorporation of light Zr isotopes and thus kinetic isotopic fractionation during zircon growth. Notably, zircons enclosed by K‐feldspar in monzodiorites generally yield lower 94Zr/90Zr and higher Zr/Hf ratios than that of separated crystals, while in K‐feldspar granites, tiny zircons intergrown with apatite obtain higher 94Zr/90Zr but lower Zr/Hf ratios relative to that of sizable separates. The diversity in petrographic textures and sizes of zircon crystals, corresponding to their crystallization sequence, potentially accounts for some of the heterogeneity of Zr isotopes at the mineral scale. Plain Language Summary: Stable Zr isotopes of zircon have been proposed as a new and promising tracer for magmatic differentiation. However, how significant heterogeneity of Zr isotopes developed at the mineral scale in an evolving magma is highly debatable. Ab initio simulation calculations, experiments, and natural sampling have suggested that kinetic rather than equilibrium effect plays a dominant role in fractionating Zr isotopes during zircon crystallization, whereas how kinetic effect links with the textural contexts of zircons is not directly constrained. Here, petrographic and geochemical constraints on zircon crystals from the mafic and felsic products of a differentiating magma are provided, which reveal that earlier crystallized domains or crystals are isotopically lighter in Zr than the later ones. Besides, the δ94Zr values of zircon crystals, displaying intra‐grain and inter‐grain variations beyond ∼1‰, correlate well with Zr/Hf ratios that reflect diverse stages of magma differentiation, irrespective of the compositions of host rocks. These findings indicate that crystal‐scale elemental and stable isotopic variations (e.g., Zr isotopes in zircon) could be ascribed to the sequential crystallization of targeting minerals. Key Points: Early‐formed zircon crystals or domains are isotopically lighter in Zr than those crystallized late in both mafic and felsic rocksDiversity in textural occurrences and sizes of zircons potentially explain the Zr isotopic heterogeneity at the mineral scaleGeochemical information extracted from separated minerals does not always reflect the nature of primitive magma [ABSTRACT FROM AUTHOR]

We present detailed characterization of Tanz zircon megacrysts for the microbeam determination of U–Pb ages, Zr isotopes, Hf isotopes, O isotopes and trace element mass fractions. This batch of dark brown zircon megacrysts from Tanzania contains 269 ± 103 μg g−1 U (Th/U ∼ 0.154), and its total weight is 9.06 kg. The largest Tanz zircon megacryst in this batch weighs 366 grams. The calculated average accumulated alpha-radiation dosage is 0.54 × 1018 events per g for the Tanz zircon, which correlates with a 'well crystallized' structure. Through a large number of laser ablation ICP-MS, laser ablation MC-ICP-MS and SIMS measurements, it is found that Tanz zircon megacrysts are quite uniform in U–Pb ages, O isotopes and Zr isotopes at scales of tens of microns. The Tanz zircon has chemical abrasion isotope dilution TIMS (CA-ID-TIMS) determined mean isotopic ratio values of 0.09180 ± 0.00013 (2SD, n = 47) for 230Th corrected 206Pb/238U, 0.7473 ± 0.0014 (2SD, n = 47) for 207Pb/235U and 0.059069 ± 0.000067 (2SD, n = 47) for 230Th corrected 207Pb/206Pb. The CA-ID-TIMS method yielded a mean 230Th corrected 206Pb/238U age of 566.16 ± 0.77 Ma (2SD, n = 47). The determined mean δ18OVSMOW and δ94/90ZrSRM3169 values of the Tanz zircon megacrysts are 6.52 ± 0.28‰ (2SD, n = 29) and −0.01 ± 0.06‰ (2SD, n = 35) by gas source mass spectrometry and double spike TIMS, respectively. All of these values are in good agreement with the statistical mean values of microbeam measurements and are proposed as the best reference values for Tanz zircon megacrysts. These features make the Tanz zircon megacrysts suitable as primary U–Pb age and Zr–O isotope reference materials for microbeam analysis. However, our LA-MC-ICP-MS data suggest a relatively wide distribution of Hf isotope compositions in the Tanz zircons (0.281821 ± 0.000042, 2SD, n = 321), which makes Tanz zircons not an ideal Hf isotope reference material for microbeam analysis. We propose the Tanz zircon megacrysts as a potential reference material for the primary external calibration or monitoring of analytical validation for microbeam determination of U–Pb ages and Zr–O isotopes. [ABSTRACT FROM AUTHOR]

• ∼1.4 Ga juvenile magmatism occurs in most microcontinents in the southern CAOB. • The microcontinents show distinct evolution compared to nearby cratons at ∼1.4 Ga. • Mesoproterozoic magmatism records geodynamic transition along the margin of Nuna. The southern Central Asian Orogenic Belt contains numerous microcontinents including the Kazakhstan-Yili block, Central Tianshan Arc and Junggar block in the west, the Erguna, Xing'an, Songliao and Jiamusi-Khanka blocks in the east, bridging by the Tuva-Mongolia block, Beishan Orogenic Belt and Alax block in the central region. New geochemical and geochronological data from the microcontinental blocks within the southern Beishan Orogenic Belt provide new insight into the Precambrian crustal evolution of this region. Five granitoids from the Jiujing region yielded igneous zircon 206Pb/238U ages of 1450–1401 Ma, and zircon xenocrysts from late Paleozoic plutons in the Jiujing, Qiaowan, and Shibandun regions have 206Pb/238U ages that also cluster at ∼1.4 Ga. Those data suggest that crust of this age is widespread beneath the southern Beishan Orogenic Belt. The ∼1.4 Ga zircons display depleted Hf isotopic signatures (ε Hf(t) = 2.0–11.1) and show relatively young two-stage Hf model ages (1.9–1.4 Ga), indicating rapid reworking of juvenile mantle-derived materials. Integrating these results with similar geochronological data from the Kyrgyz North Tianshan, Yili block, Central Tianshan Arc, northern Alxa block and Xilinhot block, we propose that the CAOB incorporates an extensive assemblage of Mesoproterozoic (1450–1360 Ma) magmatism that can be traced over ca. 3000-km long a west-east trending belt. These Mesoproterozoic granitoids display distinct geochemical signatures (e.g., Ga/Al*10,000 ranging from 1.46 to 3.88 and Zr + Nb + Ce + Y varying largely from 101 to 1066 ppm) and show a temporal progression from orogenic to anorogenic over a relatively short period. This suggests a tectonic setting that likely evolved from compressional to extensional environments during 1450–1360 Ma, perhaps resulting from slab roll back. We suggest that the 1450–1360 Ma magmatism along the southern CAOB corresponds with a transition from a compressional to extensional environment on the margin of the Nuna supercontinent. [ABSTRACT FROM AUTHOR]

In this study, the Pb/U fractionation between zircon and uraninite during femtosecond Laser Ablation Inductively Coupled Plasma Mass Spectrometry (fs-LA-ICP-MS) analysis was studied in detail. The results show significant Pb/U fractionation between zircon and uraninite during fs-LA-ICP-MS analysis that when calibrated against the zircon standard M257, the obtained U-Pb age of the Chinese national uraninite standard GBW04420 is 17% older than the recommended value. Thus, the accurate in-situ U-Pb dating of uraninite by LA-ICP-MS requires matrix-matched external standards for calibration. Uraninite in thin sections of two U-mineralized leucogranite from the Gaudeanmus in Namibia was analyzed by a fs-LA-ICP-MS equipped with a Signal Smooth Device (SSD), using laser spot and frequency of 10 µm and 1 Hz, respectively. When calibrated using GBW04420 as the external standard, two samples give weighted mean Pb/U ages of 504±3 Ma (2 σ, n=21) and 503±3 Ma (2 σ, n=22), and only one of two samples yields a concordia U-Pb age of 507±1 Ma (2 σ, n=21). These results are consistent with ID-TIMS U-Pb ages of 509±1 and 508±12 Ma and are also indistinguishable from zircon U-Pb upper intercept ages of 506±33 Ma (2 σ, n=29) and 501±51 Ma (2 σ, n=29). The present study shows that in-situ U-Pb dating of uraninite can deliver more reliable formation ages of the deposit than dating coeval high-U zircon because the latter commonly suffer significant Pb loss after formation. Our results confirm that GBW04420 is an ideal matrix matching standard for in-situ U-Pb dating of uraninite. [ABSTRACT FROM AUTHOR]

Deep-water canyon systems can provide important sandstone reservoirs for deep-water oil and gas exploration in the South China Sea; however, the sedimentary provenance of the Central Canyon in the Qiongdongnan Basin remains controversial. In this work, detrital zircon grains from three drilling sandstones in the Upper Miocene Huangliu Formation in the western part of the Central Canyon were analysed by LA-ICP-MS for U-Pb ages, in order to constrain their provenance. One hundred and ninety-one zircon grains yield concordant U-Pb ages ranging from 28.6 to 3285 Ma. Most of them show oscillatory or linear zoning in CL-images and high Th/U ratios (>0.1), suggesting that they are magmatic zircons. Three major age clusters at about 30 Ma ( N=6), 220-270 Ma ( N=29), and 420-440 Ma ( N=13), and five minor age clusters at 70-110 Ma ( N=7), 150-170 Ma ( N=4), 800-850 Ma ( N=11), 1800-2000 Ma ( N=16), and 2400-2600 Ma ( N=7), can be identified in the age spectrum, which are very similar to those of the Upper Miocene sandstones and modern river sands in the Red River area, but different from those of other nearby regions (e.g., Hainan Island, the Pearl River area, and the Mekong River area) in Southeast Asia. The major age peak at about 30 Ma in our samples is consistent with the timing of tectonothermal events in the Red River Fault Zone. Therefore, we suggest that the provenance of the western part of the Central Canyon, in the Qiongdongnan Basin, was fed dominantly by the Paleo-Red River system during the Late Miocene. [ABSTRACT FROM AUTHOR]

The effect of three different cone combinations on the performance of laser ablation MC-ICP-MS (Neptune plus) for the in situ Hf isotope analysis of zircon were investigated. The signal sensitivities of Hf, Yb and Lu were improved by a factor of 1.4 and 2.5, respectively, with using the X skimmer cone + standard sampler cone and the X skimmer cone + Jet sample cone compared to the standard arrangement (H skimmer cone + standard sample cone). However, when using the high-sensitivity Jet sample cone, the instrumental mass fractionation for hafnium displayed a large non-linear component that could not be corrected using the normal mass fractionation laws. The magnitude of this non-linear mass fractionation was strongly related to the central gas flow rate. The in situ Hf isotope analysis of zircon standards 91500 and Mud Tank using the Jet cone displayed large deviations (410–470 ppm) at the optimum central gas flow rate for Hf, which seriously deteriorated the performance of the Jet cone. The addition of 4 ml min−1 nitrogen to the central gas flow in laser ablation MC-ICP-MS was found to not only increase the sensitivity of Hf by a factor of 2.1, but also suppress this non-linear mass fractionation. The determined Yb/Hf and Lu/Hf ratios at their corresponding optimum makeup gas flow rates for Hf intensity were found to be reduced by factors of 2 and 1.3 in the presence of nitrogen, respectively, which would benefit the accurate in situ determination of Hf isotopes in high-content Yb and Lu samples. Compared to the standard arrangement, the corresponding precision (2σ) of 176Hf/177Hf for single spot analysis of zircon standard 91500 was improved from 224 ppm to 50 ppm by using the newly designed X-skimmer cone and Jet sample cone in combination with the nitrogen addition technique. The determined 176Hf/177Hf ratios are in excellent agreement with published values in five reference zircon standards (91500, GJ-1, Mud Tank, Penglai and Plešovice). Our first Hf isotopic results from zircon standard M257 (0.281544 ± 0.000018; 2SD, n = 151) showed that it was fairly homogeneous in Hf isotopes. These results clearly demonstrate that the present analytical method has the potential to become an important tool for the pursuit of high-quality in situ Hf isotope data for zircons. [ABSTRACT FROM AUTHOR]

Abstract: Hydrothermally altered rocks are products of fluid–rock interactions, and typically preserve numerous quartz veins that formed as chemical precipitates from fluids that fill up cracks. Thus, quartz veins are the record of the fluid system that involved fracture flow in the direction of changing temperature or pressure. In order to decipher the fluid activity in the Sulu ultrahigh-pressure (UHP) terrane in eastern China, quartz veins together with an adjacent eclogite lens and the host gneiss were studied. In one location a deformed quartz vein is located at the boundary between the host gneiss and the eclogite lens. The amphibolite-facies overprinting of the eclogite lens decreases from the rim to the core of the lens, with fresh eclogite preserved in the core. The foliated biotite gneiss contains felsic veins and residual phengites. Zircon rims from the gneiss are characterized by melt-related signatures with steep HREE patterns, high Hf contents and negative Eu anomalies, and a pool of weighted average 206Pb/238U analyses reveal an age of 219±3Ma (2σ), which is younger than the UHP metamorphic age (236±2Ma, 2σ) recorded by zircons from the eclogite lens. This suggests that the gneiss in the Sulu UHP terrane could have suffered from partial melting due to phengite dehydration during the “hot” exhumation stage. The formation age of the quartz vein (219±2Ma, 2σ) defined by zircon rims agrees well with the partial melting time (219±3Ma, 2σ) of the host gneiss. The initial 176Hf/177Hf ratios of zircon rims from the quartz vein are obviously lower than zircons from the eclogite lens, but overlap with the coeval zircon domains from the nearby granite dikes produced by partial melting of orthogneiss. These observations suggest that the quartz vein and corresponding fluid flow could be associated with partial melting of the host gneiss. On the other hand, amphibole-bearing and HREE-rich zircon rims from the amphibolite pool an amphibolite-facies metamorphic age of 217±5Ma (2σ), overlap with the formation age of the quartz vein. This implies that retrogression of the eclogite lens could have been caused by melting-induced fluid flow. Based on the above observations, we speculate that partial melting of the gneiss in the continental subduction-related UHP belt could have induced a significant fluid flow during the exhumation stage, and thus contributed significantly to the extensive retrogression of eclogites in the Sulu UHP terrane. [Copyright &y& Elsevier]

Abstract: In situ U–Pb dating and trace element analysis of zircons, combined with a textural relationship investigation in thin section, is a powerful tool to constrain the ultra high-pressure stage of high-grade metamorphism. Two types of zircon grains have been identified in thin sections of a retrograde eclogite from the main hole of the Chinese Continental Scientific Drill project in the Sulu UHP terrane. Type 1 zircon grains occur as inclusions in fresh garnet and omphacite, and Type 2 zircon grains were found in symplectite around omphacite. The fresh rims of Type 1 zircons and mantles of a few Type 2 zircons exhibit remarkably lower REE, Y, Nb and Ta contents than the inherited zircon cores, suggesting coeval growth with garnet, rutile and apatite during UHP metamorphism. These may have formed in the UHP metamorphism and survived retrograde metamorphism. The weighted average 206Pb/238U age of these zircon domains (230±4Ma, 2σ) agrees well with the published age of coesite-bearing zircon separates (230±1Ma, 2σ), suggesting that the peak UHP metamorphism in the Sulu terrane may have occurred at ~230Ma. Zircon domains surrounded or cut across by symplectite could have been altered by retrograde metamorphism. Together, they provide a younger weighted average 206Pb/238U age of 209±4Ma (2σ). These retrograde zircon domains have similar REE compositions to the ~230Ma UHP zircon domains. These observations imply that the ~209Ma zircon domains could have formed by fluid activity-associated alterations in the amphibolite-facies metamorphism, which could have resulted in the complete loss of Pb but not REEs in these domains. [Copyright &y& Elsevier]

• We report high-precision Zr isotopic data of an alkaline differentiation series. • δ94Zr value increases in samples with SiO 2 > 65 wt%. • Alkaline and tholeiitic igneous series differ in Zr isotopic evolution path. • The upper continental crust is not felsic enough to have a high δ94Zr value. • The finding is essential for interpreting Zr isotopic data of samples out of context. Stable Zr isotopes have shown great potential in tracing magma differentiation. However, it remains unclear if different magmatic systems have similar Zr isotopic evolution patterns. Here we report high-precision Zr isotopic compositions of the well-defined Shidao alkaline complex (SAC), eastern China, which show small but important differences from the Hekla tholeiitic volcanic suite, Iceland. The SAC comprises monzodioritic, syenitic, and granitic intrusions with high alkali contents, representing a magmatic suite produced by various degrees of cognate magma differentiation. From mafic to felsic samples, the Zr concentrations and Zr/Hf ratios increase first and then decrease significantly at the inflection of ∼65 wt% SiO 2 , suggesting zircon saturation started at ∼65 wt% SiO 2 during magma differentiation. The δ94Zr values (permil deviation of the 94Zr/90Zr ratio from IPGP-Zr standard) remain nearly constant at ca. +0.01‰ in samples with SiO 2 < 65 wt% but then gradually increase with SiO 2 in more felsic samples (from +0.05 to +0.63‰), indicating that the Zr isotope fractionation also occurs at ∼65 wt% SiO 2. The Shidao alkaline and Hekla tholeiitic suites show zircon saturation at SiO 2 ∼ 65 wt%, but their Zr isotopic evolution paths differ. The alkaline suite increases more slowly in δ94Zr compared to the tholeiitic one, with the former reaching the same δ94Zr value at SiO 2 higher by ∼5 wt%. Our findings represent the first observation of differences in Zr isotopic evolution from different igneous systems (tholeiitic versus alkaline), which should be considered when interpreting Zr isotopic data of samples out of context, such as detrital zircons or sedimentary samples. Based on the more sluggish Zr isotopic enrichment in the alkaline series than the tholeiitic one, we re-interpret the Zr isotopic composition of the upper continental crust, which may simply be not felsic enough to be isotopically heavier. [ABSTRACT FROM AUTHOR]

[Display omitted] • Juvenile crust in Singhbhum Craton formed at ∼3.51, ∼3.45, 3.38–3.25, 3.15–3.05 and ∼2.80–2.75 Ga. • Reworking of older crust in the craton occurred at ∼3.46, ∼3.3, ∼3.1 and ∼2.8 Ga. • Maximum crustal thickness was attained at ∼3.3 Ga followed by a possible reduction over ∼3.1–2.8 Ga. • Paleo-Meso–Archean continental growth occurred through episodic intraplate juvenile magmatism and resultant crustal reworking. The composition of continental crust and its temporal variation, the mechanism of crust-mantle interaction, and the degree of mantle depletion during the early Archean have been widely debated. To address these issues related to the Singhbhum Craton, we present whole-rock sediment geochemistry, detrital zircon U-Pb date, trace element and Hf isotope data from four Archean clastic sedimentary successions. The rocks have high whole-rock K 2 O/Na 2 O, relatively high La and Th compared to Ni and Sc, distinct negative Eu anomaly and flat HREE patterns, and high detrital zircon U/Yb ratios. These features suggest attainment of early crustal stability with the sediments derived from a strongly weathered basement dominated by granitoids formed through shallow intracrustal melting. Detrital zircon U-Pb and Hf isotope data indicate episodic crust formation at ∼3.51, ∼3.46, 3.38–3.25, 3.15–3.05 and ∼2.80–2.75 Ga. Each major crust formation event is marked by addition of depleted mantle-derived juvenile crust and its quick reworking. Besides, episodic tapping of older crust, as indicated by a wide range (both positive and negative) of zircon εHf t values, are evident at ∼ 3.46, ∼3.3, ∼3.1 and ∼2.8 Ga. Pressure-sensitive zircon trace element ratios suggest that the crust attained the maximum thickness at ∼3.3 Ga followed by a possible reduction in thickness over ∼3.1–2.8 Ga. In the absence of strong evidence of subduction, the rock association and their temporal distribution (coeval granitoid and mafic-ultramafic magmatism) suggest that the Paleoarchean-Mesoarchean crustal growth in the Singhbhum Craton was a result of episodic, depleted mantle-derived, intraplate magmatic injection and attendant crustal reworking. [ABSTRACT FROM AUTHOR]

Abstract: Rutile and zircon in eclogites from the main hole of the Chinese Continental Scientific Drilling (CCSD-MH) were analyzed by laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) and electron microprobe (EMP). Both single spot and profile analyses of large matrix rutiles (>60μm) generally demonstrate core–rim variability of Pb, Sr, Zr and U. Pb and Sr show enrichment at the rims, while Zr and U decrease in concentration from the cores to the rims. Correspondingly, temperatures estimated by Zr-in-rutile geothermometers are higher within the cores (mainly in the range of 680–740°C) than at the rims by 10–30°C. We note that estimated temperatures within the cores of matrix rutiles correlate positively with grain diameter. This suggests that the Zr content in rutiles is not only dependent on temperature and pressure, but is also affected by fluid activity and Zr diffusion. Estimated temperatures within the cores of matrix rutiles merely represent lower limits of the peak ultra-high pressure (UHP) metamorphic temperatures. Combined with Th/U and Ce/Lu ratios, rare earth element (REE) patterns and 206Pb/238U ages, Ti-in-zircon geothermometers can be used to distinguish the thermal evolution of eclogites during the UHP metamorphism. Zircons of 745±8.0Ma (2σ, n =3) show evidence of the temperatures at which they crystallized from the original magma. Zircons of 240±7.0Ma (2σ, n =11) with flat HREE patterns suggest a definite temperature range (689±18°C (2σ, n =11)) for the prograde metamorphism. Although 226Ma is generally considered the time of the peak UHP metamorphism for the Dabie–Sulu orogen, except for a few grains with a maximum temperature of 744°C, most of the 226±2.0Ma (2σ, n =12) zircons indicate lower temperatures (average=698±12°C (2σ, n =12)). These data imply that the 226Ma zircons were probably not products of the peak UHP metamorphism, but might instead be associated with the pressure decrease in the post-peak metamorphism. The youngest zircons (<220Ma) provide evidence for temperatures (682±14°C (2σ, n =11)) associated with the retrograde metamorphism. Geothermometers that incorporate both rutile and zircon indicate that there may have been experienced a locally short-lived heating event for eclogites from the CCSD-MH. [Copyright &y& Elsevier]

The processes responsible for the origin and evolution of Early Archean continental crust are not properly understood. Questions regarding the pattern of crustal growth (episodic vs. continuous) and the role of crust-mantle interaction in the temporal change of crustal composition and thickness are still being widely debated. In order to address the above issues, we present whole-rock geochemistry and detrital zircon U-Pb-Hf isotopes, and trace-element data from Mesoarchean clastic rocks of two selected greenstone belts of western Dharwar Craton. The mineralogically mature character of the sampled sandstones along with their high K 2 O/Na 2 O, Rb/Sr and CIA values, relatively enriched concentrations of La and Th over Cr and Sc, variably negative Eu-anomaly, and high U/Yb values of detrital zircons are indicative of their derivation from strongly weathered stable continental provenance dominated by low-HREE TTGs and K-rich granites of shallow crustal origin. Detrital zircon U-Pb ages indicate the maximum age of deposition for these sandstones is ∼3.1 Ga. The detrital zircon U-Pb and Lu-Hf data suggest two major crust formation events at 3.54–3.33 Ga and 3.27–3.12, mainly via juvenile crustal addition and subsequent rapid reworking. Besides, ∼3.6 Ga detrital zircons with negative εHft values suggest that the antiquity of the western Dharwar Craton can be traced back at least up to 3.8 Ga. Reworking of the older continental crust occurred during ∼ 3.25 Ga and ∼ 3.15–3.07 Ga, the last one represented by emplacement of K-rich granites. Zircon trace element ratios indicate a maximum increase in crustal thickness at ∼3.2 Ga followed by a crustal thinning at around ∼3.15 Ga. The detrital record in combination with geological setting suggests an episodic crustal growth and reworking in the western Dharwar Craton during Paleoarchean to early Mesoarchean period which was possibly related to intraplate processes. • Juvenile crust in Western Dharwar Craton formed at 3.54–3.33 Ga. • The juvenile crust reworked during 3.27–3.12 Ga. • Reworking of older crust occurred at ∼3.25 Ga, ∼3.15–3.07 Ga and ∼ 3.02 Ga. • Maximum crustal thickness attained at ∼3.2 Ga followed by thinning up to ∼3.1 Ga. • Link between crustal thickening and partial convective overturn is suggested. [ABSTRACT FROM AUTHOR]

U–Pb zircon dating for 10 rock samples collected from the Archean Jiaobei terrain of the eastern block of the North China craton (NCC) yield three groups of ages: ∼2.9 Ga, ∼2.7 Ga and ∼2.5 Ga. Thirteen rock samples studied can be classified into a low Mg# (molecular Mg/(Mg + Fe)) (Mg# = 34–52) and a high Mg# group (Mg# = 52–61), respectively. The low Mg# rocks are typical Archean TTGs with emplacement ages of ∼2.9 Ga, ∼2.7 Ga and ∼2.5 Ga whereas the high Mg# rocks are Archean sanukitoids with age of ∼2.5 Ga. Despite having different ages, all the Jiaobei TTGs have zircon δ 18 O values between 5.6‰ and 6.3‰, essentially identical to those of the ∼2.7 Ga TTGs from adjourning Taishan area and Archean TTGs from other parts of the world. Magmatic zircons from the Jiaobei sanukitoids have δ 18 O values between 6.4‰ and 7.5‰, significantly higher than the Archean TTGs. The whole-rock Nd and the zircon Hf isotopic compositions indicate that the ∼2.9 Ga and ∼2.5 Ga TTGs and ∼2.5 Ga sanukitoids represent crustal growth at ∼2.9 Ga and ∼2.5 Ga in the Jiaobei terrain. Unlike the ∼2.7 Ga TTGs in the adjourning Taishan area that are considered to reflect juvenile crust, the Jiaobei ∼2.7 Ga TTGs, however, are most likely resulted from the reworking of the pre-existing ∼3.0 Ga crust. This is in contrast to the previous suggestion that ∼2.7 Ga is the most significant crust-forming episode and ∼2.5 Ga a period of crustal reworking in the Jiaobei terrain. The high Mg# and high contents of Cr, Ni, LREE and LILE of the ∼2.5 Ga Jiaobei sanukitoids, require a metasomatized peridotitic mantle source for their origin. The significant negative Zr and Hf anomalies and the elevated δ 18 O values of the ∼2.5 Ga sanukitoids, are inconsistent with a mantle source metasomatized solely by the TTG melts. Instead, we suggest that the Jiaobei sanukitoids could have originated from a mantle wedge metasomatized by a high δ 18 O component, most likely the slab-derived fluids. The similarity of multi-element patterns and the zircon δ 18 O values between the Jiaobei and Superior Province sanukitoids may imply similar processes involved to form sanukitoids in both Jiaobei and Superior Province terrains. [ABSTRACT FROM AUTHOR]

Complete dissolution is essential for achieving accurate analytical results for geological samples. Hydrofluoric acid is the most effective mineral acid for breaking up strong Si–O bonds to form SiF6 −2 ions in acidic solution. However, HF is rather inefficient in the open-vessel acid digestion of refractory minerals such as zircon due to its low boiling point (boiling point of 38.3% HF=112°C). In this study, a decomposition technique using the solid compound NH4F in an open vessel (Savillex Teflon vial) has been investigated for the multi-element analysis of various rock reference materials. The higher boiling point (260°C) of NH4F allows for an elevated digestion temperature in open vessels, which enables the decomposition of refractory phases. Using this method, Zr was completely recovered from the granodiorite GSP-2 reference material in 1–1.5h at 250°C, which is ~12 times faster than using conventional closed-vessel acid digestion at 190°C (high-pressure PTFE digestion bomb). There is a positive correlation between the test sample mass and the amount of NH4F required for complete recovery of Zr, Hf, Nb, Ta, and heavy rare earth elements in GSP-2, which is due to the resistance of zircon (which is a major reservoir for heavy rare earth elements) to decomposition at lower reagent to sample ratios. The recommended proportion of NH4F, relative to the amount of sample powder required for complete element recovery, is 6:1. Unlike in NH4F-assisted high-pressure acid digestion, our results clearly indicate that adding HNO3 severely inhibited the digestion capabilities of NH4F for refractory minerals such as zircon in open vessels. The most outstanding advantage of the new method is that the digestion can be performed in a conventional Savillex Teflon vial instead of a high-pressure PTFE digestion bomb. Moreover, NH4F−open-vessel acid digestion is not hampered by the formation of insoluble fluorides, which represents another important advantage of this new sample decomposition method. Similar to HF and HNO3, ultra-pure NH4F can be produced using a conventional PFA sub-boiling purification system, and it does not induce new interference species in ICP-MS analysis. Additionally, this reagent is removed by taking the sample to dryness, which is important to keep the total dissolved solid of the final solution presented to the instrument low. NH4F has many of the same safety handling requirements of HF, especially when being heated to dryness to remove the Si as SiF4, and excess reagent as HF, so safety issues are still a concern. The developed NH4F−open-vessel acid digestion method has been successfully applied to the digestion of a series of international geological reference materials. This simple, effective, and comparatively safe dissolution method shows great potential for the digestion of geological samples. [ABSTRACT FROM AUTHOR]

Abstract: A combined study of zircon U–Pb and Lu–Hf isotopes and whole rock major and trace elements and Sr–Nd isotopes has been conducted for 10 tonalitic–trondhjemitic–granodioritic (TTG) and granitic gneisses from the Kongling terrain, the only known Archean microcontinent in the Yangtze craton, South China. The results reveal a significant magmatic event at ∼2.6–2.7Ga, in addition to the previously reported ∼2.9Ga and ∼3.2–3.3Ga magmatism. The ∼2.6–2.7Ga rocks show relatively high REE (530–1074ppm), apparently negative Eu anomaly (Eu/Eu*=0.22–0.35), low #Mg (19.51–22.63) and low LaN/YbN (10.3–24.2). Besides, they have high K-feldspar proportion and relatively evaluated (K2O+Na2O)/CaO, TFeO/MgO, Zr, Nb, Ce and Y contents. Their 10,000×Ga/Al ratios range between 3.00 and 3.54. All these features suggest that the protoliths of these gneisses are A-type granites. Most of the ∼2.6–2.7Ga zircon grains have ɛ Hf(t) values >0 (up to 7.93, close to the depleted mantle value). This clearly indicates a considerably higher proportion of new crustal components in the ∼2.6–2.7Ga granitoids compared to the ∼3.2–3.3Ga and ∼2.9Ga TTGs. Our results support the conclusion of worldwide studies of igneous and detrital zircons that age peaks at 2.65–2.76Ga represent increases in the volume of juvenile continental crust. The present study also confirms the existence of the two older magmatic events in the Kongling terrain. Both whole rock ɛ Nd(t) values (−3.74 to 1.59) and the zircon ɛ Hf(t) values (−11.18 to 3.55) for the ∼2.9Ga TTG and the Hf isotopes of ∼3.2–3.3Ga igneous zircons (−7.37 to 3.12) are chondritic or subchondritic, suggesting that they were mainly generated by reworking of older rocks with a small amount of new crustal additions. [Copyright &y& Elsevier]

Abstract: Bulk element and isotopic compositions, single zircon U–Pb ages and trace element compositions of the Triassic high-Mg adakitic andesites (HMAs) from the Linxi area in the Inner Mongolia–Daxinganling orogenic belt (IMDOB) were studied to understand the area''s petrogenesis and implications for Phanerozoic crustal growth. The Linxi HMAs are characterized by typical features of high-SiO2 adakite with high Mg# and high Cr and Ni contents. Coarse clinopyroxene (cpx) phenocrysts with reverse zoning were found. These cpx phenocrysts have cores with lower Mg# and Ni contents, and higher incompatible element contents (e.g., Zr and La) compared with their mantles and rims. Bulk rock Sr–Nd isotopic compositions (87Sr/86SrI =0.70382–0.70396 and εNd(t) =3.2–4.5) fall in the range of mid-ocean ridge basalts (MORB) and modern subduction-related adakites. Single zircon U–Pb dating by LA-ICP-MS suggests an eruption at ca. 238Ma. Combined with the tectonic setting and Precambrian zircon age spectrum, these features suggest that the Linxi HMAs could be derived from the subducted Paleo-Asian oceanic slab with sediments shed from the North China Craton and hybridized by peridotite in the mantle. Trace element-age variations of zircons indicate that the oceanic crust was formed during Carboniferous–early Permian times, and then subducted during ca. 270–260Ma. Melting of the subducted oceanic slab and hybridization by peridotite could have been initiated at ca. 250Ma. It is suggested that the southern accretionary zone between the North China Craton and the Solonker suture in the IMDOB, where the Linxi HMAs are located, could have been consolidated by Carboniferous–Permian times. This implies that the Linxi HMAs could have been derived from partial melting of a fossil oceanic slab after the subduction, and subduction-related melting might have been delayed if the slab was subducted under an old, cold craton. Although we are unsure of the true extent of the fossil oceanic slab, the genesis of the Linxi HMAs is essentially a snapshot of the melting of a subducted slab lagging behind subduction, and melting of the fossil oceanic slab could have played an important role in the Phanerozoic crustal growth in the IMDOB. [Copyright &y& Elsevier]

The oxygen fugacity of a magma controlling element distribution and mobility is influenced by multiple factors including source composition and magmatic processes (e.g., assimilation and degassing). Here, whole-rock and in situ mineral analyses of the alkaline complex from the northern North China Craton are reported to investigate the influence of source composition and magmatic processes on the evolution of the melt oxidation state. The alkaline complex comprises orthoclase pyroxenites, pyroxene syenites, and syenites with similar mineral assemblages and trace element patterns. Consistent zircon and titanite U-Pb age of ~234 Ma is presented for the alkaline rocks. Their high large ion lithophile elements content, negative high field strength element anomalies, and high 87Sr/86Sr ratio suggest a metasomatized mantle origin by recycled crustal material. Magnetite and hematite inclusions were found in the early-crystallized minerals including clinopyroxene and apatite. Fluorapatites are characterized by high S (SO 3 up to 0.64 wt%) and low Mn contents, with estimated ΔFMQ higher than +3. These features together indicate a primary oxidized magma inherited from the metasomatized mantle. However, inclusion-rich fluorapatites with decreasing S and increasing Mn content from the core to the rim were found in some pyroxene syenites. Moreover, the S content of inclusion-rich fluorapatite from these pyroxene syenites is lower than that of other rock types in the complex, which may correspond to a decrease in oxygen fugacity of ~2.5 log units. These features suggest that the oxidized magma was later transformed into reduced magma. Oriented Cu-rich sulfide in inclusion-rich fluorapatite formed during the reducing event. δ65Cu of the pyroxene syenite with inclusion-rich fluorapatite (−0.06 to −0.24‰) and sulfides in fluorapatite (−0.26‰) are lighter than those of other rock types (+0.30 to +0.43‰), suggesting that the sulfides were derived from extraneous materials via magma assimilation. Variable and high 87Sr/86Sr ratios (0.7071–0.7085) in titanites and high-207Pb/206Pb rims of zoned K-feldspar in the pyroxene syenite imply that the reduced extraneous materials were derived from ancient crust. Overall, in situ mineral analyses and Cu isotopes indicate a direct link between the transformation of alkaline magma from an oxidized to a reduced state with source composition and magmatic processes, and improve our understanding of element mobility and distribution. • Oxidized alkaline magma derived from metasomatized mantle by carbonated melts. • Varied S and Mn in apatite imply the transformation of oxidized magma to reduced. • Sr–Pb–Cu isotopes suggest the redox changes induced by magma hybridization. • Redox state of alkaline magma control element mobility and mineralization. [ABSTRACT FROM AUTHOR]