Correlated δ18O and [Ti] in lunar zircons: a terrestrial perspective for magma temperatures and water content on the Moon

Zircon grains were separated from lunar regolith and rocks returned from four Apollo landing sites, and analyzed in situ by secondary ion mass spectrometry. Many regolith zircons preserve magmatic δ¹⁸O and trace element compositions and, although out of petrologic context, represent a relatively unexplored resource for study of the Moon and possibly other bodies in the solar system. The combination of oxygen isotope ratios and [Ti] provides a unique geochemical signature that identifies zircons from the Moon. The oxygen isotope ratios of lunar zircons are remarkably constant and unexpectedly higher in δ¹⁸O (5.61 ± 0.07 ‰ VSMOW) than zircons from Earth’s oceanic crust (5.20 ± 0.03 ‰) even though mare basalt whole-rock samples are nearly the same in δ¹⁸O as oceanic basalts on Earth (~5.6 ‰). Thus, the average fractionation of oxygen isotopes between primitive basalt and zircon is smaller on the Moon [Δ¹⁸O(WR-Zrc) = 0.08 ± 0.09 ‰] than on Earth (0.37 ± 0.04 ‰). The smaller fractionations on the Moon suggest higher temperatures of zircon crystallization in lunar magmas and are consistent with higher [Ti] in lunar zircons. Phase equilibria estimates also indicate high temperatures for lunar magmas, but not specifically for evolved zircon-forming melts. If the solidus temperature of a given magma is a function of its water content, then so is the crystallization temperature of any zircon forming in that melt. The systematic nature of O and Ti data for lunar zircons suggests a model based on the following observations. Many of the analyzed lunar zircons are likely from K, rare earth elements, P (KREEP)-Zr-rich magmas. Zircon does not saturate in normal mafic magmas; igneous zircons in mafic rocks are typically late and formed in the last most evolved portion of melts. Even if initial bulk water content is moderately low, the late zircon-forming melt can concentrate water locally. In general, water lowers crystallization temperatures, in which case late igneous zircon can form at significantly lower temperatures than the solidus inferred for a bulk-rock composition. Although lunar basalts could readily lose H₂ to space during eruption, lowering water fugacity; the morphology, large size, and presence in plutonic rocks suggest that many zircons crystallized at depths that retarded degassing. In this case, the crystallization temperatures of zircons are a sensitive monitor of the water content of the parental magma as well as the evolved zircon-forming melt. If the smaller Δ¹⁸O(zircon–mare basalt) values reported here are characteristic of the Moon, then that would suggest that even highly evolved zircon-forming magmas on the Moon crystallized at higher temperature than similar magmas on Earth and that magmas, though not necessarily water-free, were generally drier on the Moon.     

Oxygen isotopic composition and U-Pb discordance in zircon

We have investigated U-Pb discordance and oxygen isotopic composition of zircon using high-spatial resolution δ¹⁸O measurement by ion microprobe. δ¹⁸O in both concordant and discordant zircon grains provides an indication of the relationship between fluid interaction and discordance. Our results suggest that three characteristics of zircon are interrelated: (1) U-Pb systematics and concomitant age discordance, (2) δ¹⁸O and the water-rock interactions implied therein, and (3) zircon texture, as revealed by cathodoluminescence and BSE imaging. A key observation is that U-Pb-disturbed zircons are often also variably depleted in ¹⁸O, but the relationship between discordance and δ¹⁸O is not systematic. δ¹⁸O values of discordant zircons are generally lighter but irregular in their distribution. Textural differences between zircon grains can be correlated with both U-Pb discordance and δ¹⁸O. Discordant grains exhibit either a recrystallized, fractured, or strongly zoned CL texture, and are characteristic of ¹⁸O depletion. We interpret this to be a result of metamictization, leading to destruction of the zircon lattice and an increased susceptibility to lead loss. Conversely, grains that are concordant have less-expressed zoning and a smoother CL texture and are enriched in ¹⁸O. From this it is apparent that various stages of water-rock interaction, as evidenced by systematic variations in δ¹⁸O, leave their imprint on both the texture and U-Pb systematics of zircon.     

The origin of variable-δ18O zircons in Jurassic and Cretaceous Mo-bearing granitoids in the eastern Xing–Meng Orogenic Belt,Northeast China

This study reports new zircon U–Pb ages, Lu–Hf isotope data, and oxygen isotope data for Mesozoic Mo-bearing granitoids in the eastern Xing–Meng Orogenic Belt (XMOB) of Northeast China, within the eastern Central Asian Orogenic Belt. Combining these new laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) zircon U–Pb ages with the results of previous research indicates that two stages of Mo-bearing granitoid magmatism occurred in the eastern XMOB, during the Early–Middle Jurassic (200–165 Ma) and the Early Cretaceous (ca. 111 Ma). The eastern XMOB also contains Mo-bearing granitoids with variable δ¹⁸O compositions that record variations in source oxygen isotopic compositions. Combining δ¹⁸O data with zircon U–Pb and Hf isotopic data provides evidence of the origin of these granitoids. Three types of zircon have been identified within these granitoids. Type 1 zircons formed during the Mesozoic and having high δ¹⁸O values (5.71–7.05‰) that are consistent with the compositions of magmatic zircons from the Luming, Jiapigou, and Kanchuangou areas. These zircons suggest that the Mo-bearing granitoids were derived from a source containing supracrustal materials. The type 2 zircons have extremely low and heterogeneous δ¹⁸O values (4.64–4.89‰) that are consistent with the compositions of magmatic zircons from the Jidetun and Fuanpu areas. These magmas were generated by the remelting of juvenile crustal material that was previously significantly modified by interaction with fluids. Type 3 zircons generally have mantle-like δ¹⁸O values (5.42–5.57‰), with several zircons yielding higher δ¹⁸O values, suggesting that these intrusions formed from mantle-derived magmas that assimilated and were metasomatized by crustal material. Combining these geochemical data with the geology of this region indicates that the Mo-bearing granitoids were generated as a result of subduction of the Palaeo-Pacific Plate beneath the Eurasian continent.     

Links between Mesozoic intermediate–felsic igneous rocks and lower crustal granulite xenoliths,North China Craton: O and Pb isotopic evidence

We present and compare whole-rock and zircon O and Pb isotopic compositions for the Hannuoba granulite xenoliths and Mesozoic intermediate-to-felsic igneous rocks from the Zhangjiakou region, northern margin of the North China Craton, northeast China. The xenoliths have an overall Pb isotopic range similar to rocks from the regionally exposed Neoarchaean granulite terrain. Mesozoic zircons from different types of granulite xenoliths have a narrow range of δ¹⁸O values (6.0–7.7‰) higher than normal mantle δ¹⁸O values (～5.7‰). Mesozoic intermediate–felsic igneous rocks have O and Pb isotopic compositions indistinguishable from the Hannuoba intermediate–mafic granulite xenoliths. Our new data suggest that the Mesozoic igneous rocks and granulite xenoliths are genetically linked and that both were derived from the late Neoarchaean lower crust. This argues against previous proposals that the granulite xenoliths are either products of Mesozoic basaltic underplating or formed by mixing between mantle-derived and pre-existing crustal magmas.     

Origin of the Yinshan epithermal-porphyry Cu–Au–Pb–Zn–Ag deposit,southeastern China: insights from geochemistry,Sr–Nd and zircon U–Pb–Hf–O isotopes

The Yinshan deposit is a large epithermal-porphyry polymetallic deposit, and the timing and petrogenesis of ore-hosting porphyries have been hotly debated. We present new results from geochemical, whole-rock Sr–Nd and zircon U–Pb–Hf–O isotopic investigations. Zircon U–Pb data demonstrate that the quartz porphyry, dacitic porphyry, and quartz dioritic porphyry formed at ?172.2 ± 0.4 Ma, ?171.7 ± 0.5 Ma, and ?170.9 ± 0.3 Ma, respectively. Inherited zircon cores show significant age spreads from ?730 to ?1390 Ma. Geochemically, they are high-K calc-alkaline or shoshonitic rocks with arc-like trace element patterns. They have similar whole-rock Nd and zircon Hf isotopic compositions, yet an increasing trend in ?_Nd(t) and ?_Hf(t) values typifies the suite. Older (inherited) zircons of the three porphyries display Hf compositions comparable to those of the Jiangnan Orogen basement rocks. In situ zircon oxygen isotopic analyses reveal that they have similar oxygen isotopic compositions, which are close to those of mantle zircons. Moreover, a decreasing trend of δ¹⁸O values is present. We propose that the ore-related porphyries of the Yinshan deposit were emplaced contemporaneously and derived from partial melting of Neoproterozoic arc-derived mafic (or ultra-mafic) rocks. Modelling suggests that the quartz porphyries, dacitic porphyries, and quartz dioritic porphyries experienced ?25%, ?10%, and ?10% crustal contaminations by Shuangqiaoshan rocks. Our study provides important constraints on mantle–crust interaction in the genesis of polymetallic mineralization associated with Mesozoic magmatism in southeastern China.     

Oxygen isotopic and chemical compositions of cosmic spherules collected from the Antarctic ice sheet: Implications for their precursor materials

Bulk chemical compositions and oxygen isotopic compositions were analyzed for 48 stony cosmic spherules (melted micrometeorites) collected from the Antarctic ice sheet using electron- and ion-microprobes. No clear correlation was found between their isotopic compositions and textures. The oxygen isotopic compositions showed an extremely wide range from −28‰ to +93‰ in δ¹⁸O and from −21‰ to +13‰ in Δ¹⁷O. In δ¹⁸O-δ¹⁷O space, most samples (38 out of 48) plot close to the terrestrial fractionation line, but 7 samples plot along the carbonaceous chondrite anhydrous mineral (CCAM) line. Three samples plot well above the terrestrial fractionation line. One of these has a Δ¹⁷O of +13‰, the largest value ever found in solar system materials. One possible precursor for this spherule could be ¹⁶O-poor planetary material that is still unknown as a meteorite. The majority of the remaining spherules are thought to be related to carbonaceous chondrites.     

Zircon U-Pb and oxygen isotope evidence for a large-scale O depletion event in igneous rocks during the Neoproterozoic

Oxygen isotope analysis and U-Pb dating were carried out on zircons from granite, granitic gneiss and eclogite in the Dabie-Sulu orogenic belt of east-central China. The results show a wide variation in zircon δ¹⁸O values from −10.9 to 8.5‰. Most of the values are lower than normal mantle zircon and almost half have prominently negative values. The low δ¹⁸O zircons have protolith ages of 700 to 800 Ma and metamorphic ages of 205 to 250 Ma, respectively. Fluid availability within the metaigneous rocks dictates the extent of metamorphic recrystallization and overgrowth. The igneous zircons have preserved their magmatic zoning and middle Neoproterozoic U-Pb age during the Triassic metamorphism, indicating low fluid availability. Widespread low δ¹⁸O values are identified in the magmatic zircons of middle Neoproterozoic age, within an outcrop area of over 20,000 km² along the northern edge of the South China Block. The low δ¹⁸O zircons record the presence of large volumes of low δ¹⁸O igneous rocks that were derived from remelting of meteoric-hydrothermally altered rocks at some time between 700 and 800 Ma.The U-Pb ages for metaigneous protoliths and granites are correlated not only with the timing of rifting accompanying the breakup of Rodinia, but also with contemporary glacial deposits in the South China Block at paleolatitudes of 30 to 40°N. Melting of glacial ice and snow is suggested, instead of the direct involvement of meteoric water, to produce the low δ¹⁸O fluid with oxygen isotopic signatures like the cold-climate meteoric water. The rifting created conditions favorable to anatexis of meteoric-hydrothermally altered rocks. Glaciated regions supplied copious water for the water-rock interaction during magma emplacement along rifting zones. Both rifting and glaciation favored the generation of the low δ¹⁸O magmas in the region. The low δ¹⁸O zircons are thus interpreted to have crystallized from the low δ¹⁸O magmas of middle Neoproterozoic age, and onset of the generation of low δ¹⁸O magmas in the northern margin of the South China Block is estimated to occur at about 758 ± 15 Ma. The large-scale remelting of hydrothermally altered crust not only results from repetitive emplacement of mafic magmas along the rifting zones with protracted episodes of water-rock interaction, but also involves rift systems that rapidly introduce large volumes of fluid through confined pathways and traps in a short space of time in response to tectonic triggers. Occurrence of the large-scale ¹⁸O depletion during the middle Neoproterozoic may be a manifestation of the cold paleoclimate related to the snowball Earth event.     

Sub‐mantle δ18O Zircons in Malani rhyolites: Clues for a Rodinia Linkage between South China and NW India

The Malani Igneous Suite (MIS) in NW India represents one of the largest and well‐preserved Precambrian felsic igneous provinces, with minor mafic volcanics and dykes. The SIMS (Secondary Ion Mass Spectrometric) zircon U‐Pb geochronology yielded 776.8 ± 4.5 to 758.5 ± 6.9 Ma ages for rhyolites from Jodhpur region and Sindreth Basin while dacite sample from Punagarh Basin was dated to 760.5 ± 10 Ma. Zircons from rhyolitic and dacitic lavas have oxygen isotopic compositions that can be grouped into low δ¹⁸OV‐SMOW (4.12 to ‐1.11‰) and high (δ¹⁸O = 8.23‐5.12‰) categoroes, respectively. The low δ¹⁸O zircons have highly radiogenic Hf isotopic compositions (ε_Hf(t)= +13.0 to +3.6) suggesting high temperature bulk cannibalization of upper level juvenile crust as the essential process for magma generation. Older than 800 Ma xenocrystic zircons in dacite have high δ¹⁸O values whereas 795 Ma ones have mantle‐like Hf‐O isotopic compositions, reflecting a significant shift in tectono‐thermal regime in NW India during 800‐780 Ma. A synchronous transition in the South China Block and Madagascar suggests a spatially and temporally linked geodynamic system. Geochemical data in combination with the new isotopic results point towards an overall convergent plate margin setting undergoing localized lithospheric extension. The NW India and South China blocks together with Madagascar and the Seychelles lay either along the periphery of Rodinia or off the supercontinent with the age of convergent plate margin magmatism coinciding with breakup of the supercontinent.     

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.     

Archaean fluid-assisted crustal cannibalism recorded by low δ<Superscript>18</Superscript>O and negative ε<Subscript>Hf(T)</Subscript> isotopic signatures of West Greenland granite zircon

The role of fluids during Archaean intra-crustal magmatism has been investigated via integrated SHRIMP U–Pb, δ¹⁸O and LA-MC-ICPMS ¹⁷⁶Hf isotopic zircon analysis. Six rock samples studied are all from the Nuuk region (southern West Greenland) including two ~3.69 Ga granitic and trondhjemitic gneisses, a 3.64 Ga granitic augen gneiss, a 2.82 Ga granodioritic Ikkattoq gneiss, a migmatite with late Neoarchaean neosome and a homogeneous granite of the 2.56 Ga Qôrqut Granite Complex (QGC). All zircon grains were thoroughly imaged to facilitate analysis of magmatic growth domains. Within the zircon analysed, there is no evidence for metamictization. Initial ε_Hf zircon values (n = 63) are largely sub-chondritic, indicating the granitic host magmas were generated by the remelting of older, un-radiogenic crustal components. Zircon from some granite samples displays more than one ²⁰⁷Pb/²⁰⁶Pb age, and correlated with ¹⁷⁶Hf/¹⁷⁷Hf compositions can trace multiple phases of remelting or recrystallization during the Archaean. Model ages calculated using Lu/Hf arrays for each sample indicate that the crustal parental rocks to the granites, granodiorites and trondhjemites segregated from a chondrite-like reservoir at an earlier time during the Archaean, corresponding to known formation periods of more primitive tonalite–trondhjemite–granodiorite (TTG) gneisses. Zircon from the ~3.69 Ga granite, the migmatite and QGC granite contains Eoarchaean cores with chondritic ¹⁷⁶Hf/¹⁷⁷Hf and mantle-like δ¹⁸O compositions. The age and geochemical signatures from these inherited components are identical to those of surrounding tonalitic gneisses, further suggesting genesis of these granites by remelting of broadly tonalitic protoliths. Zircon oxygen isotopic compositions (n = 62) over nine age populations (six igneous and three inherited) have weighted mean or mean δ¹⁸O values ranging from 5.8 ± 0.6 to 3.7 ± 0.5‰. The 3.64 Ga granitic augen gneiss sample displays the highest δ¹⁸O with a mildly supra-mantle composition of 5.8 ± 0.6‰. Inherited Eoarchaean TTG-derived zircon shows mantle-like values. Igneous zircon from all other samples, spanning more than a billion years of Archaean time, record low δ¹⁸O sub-mantle compositions. These are the first low δ¹⁸O signatures reported from Archaean zircon and represent low δ¹⁸O magmas formed by the remelting and metamorphism of older crustal rocks following high-temperature hydrothermal alteration by meteoric water. Meteoric fluid ingress coupled with crustal extension, associated high heat flow and intra-crustal melting are a viable mechanism for the production of the low δ¹⁸O granites, granodiorites and trondhjemites reported here. Both high and low δ¹⁸O magmas may have been generated in extensional environments and are distinct in composition from Phanerozoic I-type granitic plutonic systems, which are typified by increasing δ¹⁸O during intra-crustal reworking. This suggests that Archaean magmatic processes studied here were subtly different from those operating on the modern Earth and involved extensional tectonic regimes and the predominance of remelting of hydrothermally altered crystalline basement.     

Terrestrial alteration of carbonate in a suite of Antarctic CM chondrites: Evidence from oxygen and carbon isotopes

The oxygen (δ¹⁸O, δ¹⁷O) and carbon (δ¹³C, FMOD¹⁴C-the fraction of modern ¹⁴C) isotopic compositions of carbonate were measured for a set of paired Antarctic CM chondrites (EET 96006, EET 96016, EET 96017, and EET 96019). While the oxygen isotopic compositions do not plot on the terrestrial fractionation line and indicate that a component of the carbonate minerals has an extraterrestrial origin, they also do not fall on the array defined for carbonates by CM falls and are thus consistent with the presence of a terrestrial carbonate component. The δ¹³C and FMOD¹⁴C measurements of carbonate suggest the presence of at least two carbon sources: carbonate derived from atmospheric CO₂ that is inferred to have been produced as a result of silicate weathering reactions and carbonate derived from another carbon source that is either old or non-atmospheric. The relationships between oxygen and carbon isotope data provide additional constraints on the weathering process, and allow the possibility that rock-dominated weathering of the meteorite caused the oxygen isotopic composition of Antarctic water added to the meteorite to evolve away from the terrestrial mass-fractionation array, leading to formation of low temperature terrestrial alteration products that do not lie on the terrestrial fractionation line.     

High precision iron isotope measurements of terrestrial and lunar materials

We present the analytical methods that have been developed for the first high-precision Fe isotope analyses that clearly identify naturally-occurring, mass-dependent isotope fractionation. A double-spike approach is used, which allows rigorous correction of instrumental mass fractionation. Based on 21 analyses of an ultra pure Fe standard, the external precision (1-SD) for measuring the isotopic composition of Fe is ±0.14 ‰/mass; for demonstrated reproducibility on samples, this precision exceeds by at least an order of magnitude that of previous attempts to empirically control instrumentally-produced mass fractionation (Dixon et al., 1993). Using the double-spike method, 15 terrestrial igneous rocks that range in composition from peridotite to rhyolite, 5 high-Ti lunar basalts, 5 Fe-Mn nodules, and a banded iron formation have been analyzed for their iron isotopic composition. The terrestrial and lunar igneous rocks have the same isotopic compositions as the ultra pure Fe standard, providing a reference Fe isotope composition for the Earth and Moon. In contrast, Fe-Mn nodules and a sample of a banded iron formation have iron isotope compositions that vary over a relatively wide range, from δ⁵⁶Fe = +0.9 to −1.2 ‰; this range is 15 times the analytical errors of our technique. These natural isotopic fractionations are interpreted to reflect biological (“vital”) effects, and illustrate the great potential Fe isotope studies have for studying modern and ancient biological processes.     

Isotopic composition (δ<Superscript>13</Superscript>C and δ<Superscript>18</Superscript>O) and genesis of carbonates from the famennian manganiferous formation of Pai-Khoi

The results of isotope-geochemical studies of carbonates of different mineral types from manganese and host rocks of the Famennian manganiferous formation of Pai-Khoi are reported. Kutnahorite ores are characterized by δ¹³C values from–6.6 to 1.3‰ and δ¹⁸O from 20.0 to 27.4‰. Rhodonite–rhodochrosite rocks of the Silovayakha ore occurrence have δ¹³C from–5.2 to–2.9 and δ¹⁸O from 25.4 to 24.3‰. Mineralogically similar rocks of the Nadeiyakha ore occurrence show the lighter carbon and oxygen isotopic compositions: δ¹³C from–16.4 to–13.1 and δ¹⁸O from 24.8 to 22.5‰. Similar isotopic compositions were also obtained for rhodochrosite–kutnahorite rocks of this ore occurrence: δ¹³C from–13.0 to–10.4‰ and δ¹⁸O from 24.6 to 21.7‰. Siderorodochrosite ores differ in the lighter oxygen and carbon isotopic compositions: δ¹⁸O from 18.7 to 17.6‰ and δ¹³C from–10.2 to–9.3‰, respectively. In terms of the carbon and oxygen isotopic compositions, host rocks in general correspond to marine sedimentary carbonates. Geological-mineralogical and isotope data indicate that the formation of the manganese carbonates was related to the hydrothermal ore-bearing fluids with the light isotopic composition of oxygen and carbon dissolved in CO₂. The isotopic features indicate an authigenic formation of manganese carbonates under different isotopegeochemical conditions.     

Sub-arc mantle heterogeneity in oxygen isotopes: evidence from Permian mafic–ultramafic intrusions in the Central Asian Orogenic Belt

Integrated zircon–olivine O–Hf isotope data have been successfully used to unravel the nature of the source mantle for the early Permian post-collisional mafic–ultramafic intrusive rocks in the southern margin of the Central Asian Orogenic Belt in NW China. Olivine crystals with forsterite (Fo) contents varying from 91 to 87 mol% from the Permian Pobei mafic–ultramafic complex in the region yield highly elevated δ¹⁸O from 6.0 to 7.2‰. These values are much higher than typical mantle values (~?5.3‰) and are apparently at odds with the mantle-like ε_Nd(t) values of whole rocks (4.9–5.4). Magmatic zircon crystals from troctolite and gabbroic rocks show divergent oxygen and hafnium isotopic compositions: mantle-like ε_Hf(t) values from 5.1 to 11.9 and crust-like δ¹⁸O values from 7.6 to 10.1‰. The observed increase of δ¹⁸O values from olivine (an early crystallizing phase) to zircon (a late crystallizing phase) in the mafic–ultramafic rocks is generally consistent with an AFC process. However, this process cannot fully explain the highly elevated δ¹⁸O values (6–7‰) for the most primitive olivine containing Fo as high as mantle olivine (>?90 mol%) and the mantle-like Hf isotope composition of zircon. Mixing calculation indicates that such highly unusual isotope compositions can be explained by the previous source mantle contamination with subducted sediment-derived melts and slab-derived fluids. Our results show that the combination of zircon O–Hf isotopes and olivine oxygen isotopes is more effective than the data of zircon or olivine alone to distinguish the effect of AFC process from source contamination. The results from this study provide a new line of evidence that the sub-arc mantle is not homogeneous in oxygen isotopes.     

Isotopic compositions of oxygen, iron, chromium, and nickel in cosmic spherules: Toward a better comprehension of atmospheric entry heating effects

Large, correlated, mass-dependent enrichments in the heavier isotopes of O, Cr, Fe, and Ni are observed in type-I (metal/metal oxide) cosmic spherules collected from the deep sea. Limited intraparticle variability of oxygen isotope abundances, typically <5‰ in δ¹⁸O, indicates good mixing of the melts and supports the application of the Rayleigh equation for the calculation of fractional evaporative losses during atmospheric entry. Fractional losses for oxygen evaporation from wüstite, assuming a starting isotopic composition equal to that of air (δ¹⁸O = 23.5‰; δ¹⁷O = 11.8‰), are in the range 55%-77%, and are systematically smaller than evaporative losses calculated for Fe (69%-85%), Cr (81%-95%), and especially Ni (45%-99%). However, as δ¹⁸O values increase, fractional losses for oxygen approach those of Fe, Cr, and Ni indicating a shift in the evaporating species from metallic to oxidized forms as the spherules are progressively oxidized during entry heating. The observed unequal fractional losses of O and Fe can be reconciled by allowing for a kinetic isotope mass-dependent fractionation of atmospheric oxygen during the oxidation process and/or that some metallic Fe may have undergone Rayleigh evaporation before oxidation began.In situ measurements of oxygen isotopic abundances were also performed in 14 type-S (silicate) cosmic spherules, 13 from the Antarctic ice and one from the deep sea. Additional bulk Fe and Cr isotopic abundances were determined for two type-S deep-sea spherules. The isotopic fractionation of Cr isotopes suggest appreciable evaporative loss of Cr, perhaps as a sulfide. The oxygen isotopic compositions for the type-S spherules range from δ¹⁸O = −2‰ to + 27‰. The intraspherule isotopic variations are typically small, ∼5% relative, except for the less-heated porphyritic spherules which have preserved large isotopic heterogeneities in at least one case. A plot of δ¹⁷O vs. δ¹⁸O values for these spherules defines a broad parallelogram bounded at higher values of δ¹⁷O by the terrestrial fractionation line, and at lower values of δ¹⁷O by a line parallel to it and anchored near the isotopic composition of δ¹⁸O = −2.5‰ and δ¹⁷O = −5‰. Lack of independent evidence for substantial evaporative losses suggests that much of this variation reflects the starting isotopic composition of the precursor materials, which likely resembled CO, CM, or CI chondrites. However, the enrichments in heavy isotopes indicate that some mixing with atmospheric oxygen was probably involved during atmospheric entry for some of the spherules. Isotopic fractionation due to evaporation of incoming grain is not required to explain most of the oxygen isotopic data for type-S spherules. However spherules with barred olivine textures that are thought to have experienced a more intense heating than the porphyritic ones might have undergone some distillation. Two cosmic spherules, one classified as a radial pyroxene type and the other showing a glassy texture, show unfractionated oxygen isotopic abundances. They are probably chondrule fragments that survived atmospheric entry unmelted.Possible reasons type-I spherules show larger degrees of isotopic fractionation than type-S spherules include: a) the short duration of the heating pulse associated with the high volatile content of the type-S spherule precursors compared to type-I spherules; b) higher evaporation temperatures for at least a refractory portion of the silicates compared to that of iron metal or oxide; c) lower duration of heating of type-S spherules compared to type-I spherules as a consequence of their lower densities.     

Oxygen and iron isotope constraints on near-surface fractionation effects and the composition of lunar mare basalt source regions

Oxygen and iron isotope analyses of low-Ti and high-Ti mare basalts are presented to constrain their petrogenesis and to assess stable isotope variations within lunar mantle sources. An internally-consistent dataset of oxygen isotope compositions of mare basalts encompasses five types of low-Ti basalts from the Apollo 12 and 15 missions and eight types of high-Ti basalts from the Apollo 11 and 17 missions. High-precision whole-rock δ¹⁸O values (referenced to VSMOW) of low-Ti and high-Ti basalts correlate with major-element compositions (Mg#, TiO₂, Al₂O₃). The observed oxygen isotope variations within low-Ti and high-Ti basalts are consistent with crystal fractionation and match the results of mass-balance models assuming equilibrium crystallization. Whole-rock δ⁵⁶Fe values (referenced to IRMM-014) of high-Ti and low-Ti basalts range from 0.134‰ to 0.217‰ and 0.038‰ to 0.104‰, respectively. Iron isotope compositions of both low-Ti and high-Ti basalts do not correlate with indices of crystal fractionation, possibly owing to small mineral-melt iron fractionation factors anticipated under lunar reducing conditions.The δ¹⁸O and δ⁵⁶Fe values of low-Ti and the least differentiated high-Ti mare basalts are negatively correlated, which reflects their different mantle source characteristics (e.g., the presence or absence of ilmenite). The average δ⁵⁶Fe values of low-Ti basalts (0.073 ± 0.018‰, n = 8) and high-Ti basalts (0.191 ± 0.020‰, n = 7) may directly record that of their parent mantle sources. Oxygen isotope compositions of mantle sources of low-Ti and high-Ti basalts are calculated using existing models of lunar magma ocean crystallization and mixing, the estimated equilibrium mantle olivine δ¹⁸O value, and equilibrium oxygen-fractionation between olivine and other mineral phases. The differences between the calculated whole-rock δ¹⁸O values for source regions, 5.57‰ for low-Ti and 5.30‰ for high-Ti mare basalt mantle source regions, are solely a function of the assumed source mineralogy. The oxygen and iron isotope compositions of lunar upper mantle can be approximated using these mantle source values. The δ¹⁸O and δ⁵⁶Fe values of the lunar upper mantle are estimated to be 5.5 ± 0.2‰ (2σ) and 0.085 ± 0.040‰ (2σ), respectively. The oxygen isotope composition of lunar upper mantle is identical to the current estimate of Earth’s upper mantle (5.5 ± 0.2‰), and the iron isotope composition of the lunar upper mantle overlaps within uncertainty of estimates for the terrestrial upper mantle (0.044 ± 0.030‰).     

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.     

威海地区超高压变质花岗片麻岩锆石U-Pb定年和氧同位素研究

在苏鲁超高压变质带东北端山东威海地区皂埠镇发现锆石δ18O值低至-7.8‰左右的花岗片麻岩, 与前人在苏鲁超高压变质带西南端江苏东海青龙山地区发现的锆石δ18O值为-7‰~-9‰左右的花岗片麻岩一致.对这些低δ18O值花岗片麻岩进行了锆石SHRIMP法UPb定年和系统的激光氟化法矿物氧同位素分析, 结果对低δ18O值锆石成因和花岗片麻岩的原岩性质提供了制约.研究得到: (1) 这些低δ18O值锆石以新元古代岩浆锆石为主, 但部分岩浆锆石在印支期超高压变质作用过程中发生了不同程度的重结晶作用.δ18O值为-7.08‰的岩浆核锆石UPb定年得到的花岗片麻岩原岩谐和年龄和不一致线上交点年龄分别为(760±49) Ma和(751±27) Ma, 变质谐和年龄和不一致线下交点年龄分别为(232±4) Ma和(241±33) Ma, 指示其原岩为新元古代花岗岩并经历了印支期变质作用; (2) 锆石δ18O值在局部范围内变化于-7.76‰~5.40‰之间, 低δ18O值岩浆锆石表明它们是从新元古代低δ18O值岩浆中直接结晶形成, 锆石δ18O值的局部变化表明其原岩岩浆的氧同位素组成具有不均一性, 指示低δ18O值岩浆源区物质曾经在地表与极度亏损18O的大气降水发生过不同程度的高温水岩反应; (3) 低δ18O值花岗片麻岩在印支期板块俯冲和折返过程中基本没有与外部发生显著的氧同位素交换, 在退变质作用过程中花岗片麻岩内部缓冲流体对原岩岩浆锆石的δ18O值影响不大.威海皂埠镇地区和东海青龙山地区的花岗片麻岩在原岩时代、变质时代和氧同位素组成等方面基本相同, 指示它们应具有相同的原岩性质, 并经历了相同的变质作用和水岩相互作用过程.因此, 极度亏损18O的新元古代双峰式基性-酸性岩浆岩可能分布于整个大别-苏鲁造山带.      

Temperature and Hf-O isotope correlations of young erupted zircons from Tengchong (SE Tibet): Assimilation fractional crystallization during monotonic cooling

Young zircons from crystal-poor volcanic rocks provide the best samples for the investigations of pre-eruption magmatic processes and for testing a possible relationship between zircon Eu anomalies and crustal thickness. We report trace element chemistry and Hf-O isotope compositions of young zircons from 3 Holocene volcanoes in the Tengchong volcanic field, SE Tibet, in order to provide insights into magma evolution processes and conditions for high-K calc-alkaline volcanic rocks in a post-collisional setting. As decreasing zircon Ti content and falling temperature, zircon Hf content and Yb/Sm increase whereas zircon Eu anomaly and Th/U decrease, indicating fractional crystallization of plagioclase and zircon during magma cooling. More importantly, zircon Hf isotope ratio (ε_Hf values) increases with decreasing zircon Ti content and falling temperature (T), suggesting gradually increasing incorporation of relatively high ε_Hf juvenile materials in the crystallizing zircons during magma evolution. Negative correlations between zircon ε_Hf and zircon δ¹⁸O also support open-system magma evolution. Our data suggest fractional crystallization of a magma with simultaneous contamination by high ε_Hf and low δ ¹⁸O juvenile (immature) crustal materials during monotonic cooling after zircon saturation. The low-T, high-ε_Hf and low- δ ¹⁸O zircons may indicate the involvement of the early Cretaceous juvenile granitic country rocks during shallow magma evolution. Average Eu anomalies in zircons from young Tengchong lavas yield crustal thickness of 40.7 ± 6.8 km, consistent with present crustal thickness (42.5 km) determined by geophysical methods.     

Isotopic geochemistry of burial-metamorphosed volcanogenic sediments,Great Valley sequence,northern California

Isotopic and mineralogic data from an 8500-m thick section of the Great Valley sequence, northern California, indicate that changes in the δ¹⁸O values of authigenic minerals resulted from the conversion of smectite to a 10 Å clay-mineral as temperature increased with burial in the Jurassic- Cretaceous outer-arc basin. The clay-mineral assemblage in mudstone is characterized by a proportional increase of the 10 Å clay-mineral with increasing stratigraphic depth, and by a depletion in the δ¹⁸O value of the mixed-layer smectite/10 Å clay-mineral with descending stratigraphic position from +21.9 to + 15.5%. SMOW. Modeling of the oxygen isotopic data from authigenic phases, based on equilibrium fractionation during clay-mineral diagenesis, indicates that δ¹⁸O values of calcite in mudstones and of calcite cements in sandstone precipitated along a temperature gradient of about 25°C/km during maximum burial to about 6–7 km. δD values of the mixed-layer smectite/10 Å clay-mineral range between ?69 to ?44%. SMOW. Using temperatures calculated from the oxygen isotopic data, the deuterium and oxygen isotopic data indicate that the smectite underwent late-stage dehydration and probably buffered the composition of formation waters from sea water values to isotopic compositions of δ¹⁸O ≈ +8%. SMOW and δD ≈ ?25%. SMOW. The δ¹³C values of calcite from mudstone and sandstone imply that crystallization of authigenic calcite was linked to organic diagenesis during which dissolved HCO^t-₃ was continuously enriched in ¹³C as temperature increased with burial. At the base of the sequence and immediately overlying the ophiolitic basement rocks, several hundred meters of strata were altered by more oxygen-depleted (δ¹⁸O ? +4 to +5%.) hydrothermal fluids emanating from the ophiolitic rocks, probably at maximum burial depth.