Deep mantle storage of the Earth’s missing niobium in late-stage residual melts from a magma ocean

The origin of the observed niobium deficit in the bulk silicate Earth (BSE) compared to chondritic meteorites constitutes a long-standing problem in geochemistry. The deficit requires a large-scale process fractionating niobium from tantalum, and a super-chondritic Nb/Ta reservoir hidden in the deep silicate Earth and/or in the metallic core. The only voluminous super-chondritic Nb/Ta silicate reservoir analysed to date is found in lunar basalts that assimilated highly evolved Fe-rich rocks associated with anorthosites in the lunar crust. These Fe-rich rocks, enriched in incompatible elements, are thought to represent the last fractions of melt remaining at the end of lunar magma ocean crystallization. Here we report high-precision Nb-Ta data for a Fe-rich, late-stage rock suite associated with a terrestrial anorthosite from the Proterozoic Bolangir complex in India. The geochemical characteristics of this rock suite resemble those expected for late-stage residual melts from a terrestrial magma ocean. Samples show extreme, super-chondritic Nb/Ta up to 31.1 and highly elevated Nb concentrations up to 338 ppm. We argue that formation of an early enriched crustal reservoir (EECR) with these characteristics (high Fe, high Nb, superchondritic Nb/Ta) is likely in the course of Hadean late-stage terrestrial magma ocean solidification. Subduction and subsequent permanent deep mantle storage in the D′′ layer of a minor amount (∼0.5% of the BSE mass) of this EECR can readily explain the terrestrial Nb deficit, without the need to invoke core Nb storage. Our model is consistent with short-lived ¹⁴²Nd and long-lived ¹⁷⁶Hf-¹⁴³Nd isotope models for early differentiation of the Earth’s crust. In addition, the inferred Lu/Hf of this EECR implies that this reservoir can also balance the offset of terrestrial Hf isotope ratios compared to the chondritic reservoir. As such, late-stage magma ocean residual melts may constitute the enigmatic parental reservoir of Hadean zircons with low time-integrated Hf isotope compositions.     

The early terrestrial crust

Recent geochemical evidence based on the ¹⁴⁶Sm–¹⁴²Nd system and Hadean zircons shows that the Earth's mantle experienced depletion approximately 100 Ma after the formation of the solar system, and possibly even before (earlier than 30 Ma), due to the extraction of a crust enriched in incompatible elements. Depending on the model ¹⁴²Nd abundance assumed for the Bulk Earth, the early crust may have been stored in the deep mantle, or may have been remixed in the mantle with a timescale of ∼1 Ga. If the Earth is considered to have a ¹⁴²Nd composition identical to that of ordinary chondrites, then it implies that the early crust (or the enriched reservoir) is now present at the core–mantle boundary and has remained isolated from the rest of the Earth for the past 4.5 Ga. If the primordial crust had a basaltic composition, then it is unlikely that this enriched reservoir remained isolated for more than 4.5 Ga due to entrainment; yet, there is no signature of this reservoir in hotspot lavas that should sample this enriched reservoir. In contrast, if the Bulk Earth has an Nd isotopic composition slightly distinct from that of chondrites, then there is no need to invoke a hidden reservoir and the early crust must have been remixed by mantle convection prior to the formation of the modern continents.     

Experimental constraints on crystallization differentiation in a deep magma ocean

Major and trace element mineral/melt partition coefficients are presented for phases on the liquidus of fertile peridotite at 23-23.5 GPa and 2300 °C. Partitioning models, based on lattice-strain theory, are developed for cations in the ‘8-fold’ sites of majorite and Mg-perovskite. Composition-dependant partitioning models are made for cations in the 12-fold site of Ca-perovskite based on previously published data. D^min/melt is extremely variable for many elements in Ca-perovskite and highly correlated with certain melt compositional parameters (e.g. CaO and Al₂O₃ contents). The 8-fold sites in Mg-perovskite and majorite generally have ideal site radii between 0.8 and 0.9 Å for trivalent cations, such that among rare-earth-elements (REE) D^min/melt is maximum for Lu. Lighter REE become increasingly incompatible with increasing ionic radii. The 12-fold site in Ca-perovskite is larger and has an ideal trivalent site radius of ∼1.05 Å, such that the middle REE has the maximum D^min/melt. Trivalent cations are generally compatible to highly compatible in Ca-perovskite giving it considerable leverage in crystallization models. Geochemical models based on these phase relations and partitioning results are used to test for evidence in mantle peridotite of preserved signals of crystal differentiation in a deep, Hadean magma ocean.Model compositions for bulk silicate Earth and convecting mantle are constructed and evaluated. The model compositions for primitive convecting mantle yield superchondritic Mg/Si and Ca/Al ratios, although many refractory lithophile element ratios are near chondritic. Major element mass balance calculations effectively preclude a CI-chondritic bulk silicate Earth composition, and the super-chondritic Mg/Si ratio of the mantle is apparently a primary feature. Mass balance calculations indicate that 10-15% crystal fractionation of an assemblage dominated by Mg-perovskite, but with minor amounts of Ca-perovskite and ferropericlase, from a magma ocean with model peridotite-based bulk silicate Earth composition produces a residual magma that resembles closely the convecting mantle.Partition coefficient based crystal fractionation models are developed that track changes in refractory lithophile major and trace element ratios in the residual magma (e.g. convecting mantle). Monomineralic crystallization of majorite or Mg-perovskite is limited to less than 5% before certain ratios fractionate beyond convecting mantle values. Only trace amounts of Ca-perovskite can be tolerated in isolation due to its remarkable ability to fractionate lithophile elements. Indeed, Ca-perovskite is limited to only a few percent in a deep mantle crystal assemblage. Removal from a magma ocean of approximately 13% of a deep mantle assemblage comprised of Mg-perovskite, Ca-perovskite and ferropericlase in the proportions 93:3:4 produces a residual magma with a superchondritic Ca/Al ratio matching that of the model convecting mantle. This amount of crystal separation generates fractionations in other refractory lithophile elements ratios that generally mimic those observed in the convecting mantle. Further, the residual magma is expected to have subchondritic Sm/Nd and Lu/Hf ratios. Modeling shows that up to 15% crystal separation of the deep mantle assemblage from an early magma ocean could have yielded a convecting mantle reservoir with ¹⁴³Nd/¹⁴⁴Nd and ¹⁷⁶Hf/¹⁷⁷Hf isotopic compositions that remain internal to the array observed for modern oceanic volcanic rocks. If kept in isolation, the residual magma and deep crystal piles would grow model isotopic compositions that are akin to enriched mantle 1 (EM1) and HIMU reservoirs, respectively, in Nd-Hf isotopic space.     

Isotope-geochemical constraints on the formation of the early Earth’ crust

Analysis of isotope-geochemical data obtained for the early crustal complexes of the Earth provided constraints on the formation time, scales of development, and geochemical features of protocrust. Most informative were isotope-geochemical and geochemical data on the oldest zircons with ages up to 4.4 Ga, short-lived ¹⁴⁶Sm/¹⁴²Nd isotope system, and lead isotope composition of the oldest rocks of Greenland. The presence of positive ¹⁴²Nd anomaly in the rocks of West Greenland and negative anomaly in the amphibolites of the oldest Nuvvuagittuq greenstone belt of the Superior province (O’Neil et al., 2008) indicates the early differentiation of the Earth material into depleted mantle and enriched (basaltic) crust (Caro et al., 2006; Benett et al., 2007a, b; O’Neil et al., 2008). Pb-Pb isotopic systematics of the oldest crustal rocks from West Greenland and Labrador testifies that high μ enriched crust (²³⁸U/²⁰⁴Pb = 10.9) of basaltic composition already existed 3.9 Ga ago (Kamber et al., 2003). Based on isotope-geochemical and geochemical features of the oldest zircons in the Late Archean greenstone belts of the Yilgarn block (Western Australia), the crust of intermediate-felsic composition and water on the Earth’s surface already existed 4.4 Ga ago (Wilde et al., 2001).     

Non-chondritic Sm/Nd ratio in the terrestrial planets: Consequences for the geochemical evolution of the mantle-crust system

Super-chondritic ¹⁴²Nd signatures are ubiquitous in terrestrial, Martian and lunar samples, and indicate that the terrestrial planets may have accreted from material with Sm/Nd ratio higher than chondritic. This contradicts the long-held view that chondrites represent a reference composition for the ¹⁴⁷Sm-¹⁴³Nd system. Using coupled ¹⁴⁶Sm-¹⁴²Nd and ¹⁴⁷Sm-¹⁴³Nd systematics in planetary samples, we have proposed a new set of values for the ¹⁴⁷Sm/¹⁴⁴Nd and ¹⁴³Nd/¹⁴⁴Nd ratios of the bulk silicate Earth (Caro et al., 2008). Here, we revise the Bulk Silicate Earth estimates for the ⁸⁷Rb-⁸⁷Sr and ¹⁷⁶Lu-¹⁷⁶Hf systems using coupled Sr-Nd-Hf systematics in terrestrial rocks. These estimates are consistent with Hf-Nd systematics in lunar samples. The implications of a slightly non-chondritic silicate Earth with respect to the geochemical evolution of the mantle-crust system are then examined. We show that the Archean mantle has evolved with a composition indistinguishable from that of the primitive mantle until about 2 Gyr. Positive ε¹⁴³Nd and ε¹⁷⁶Hf values ubiquitous in the Archean mantle are thus accounted for by the non-chondritic Sm/Nd and Lu/Hf composition of the primitive mantle rather than by massive early crustal formation, which solves the paradox that early Archean domains only have a limited extension in the present-day continents. The Sm-Nd and Lu-Hf evolution of the depleted mantle for the past 3.5 Gyr can be entirely explained by continuous extraction of the continents from a well-mixed mantle. Thus, in contrast to the chondritic Earth model, Sm-Nd mass balance relationships can be satisfied without the need to call upon hidden reservoirs or layered mantle convection. This new Sm-Nd mass balance yields a scenario of mantle evolution consistent with trace element and noble gas systematics. The high ³He/⁴He mantle component is associated with ¹⁴³Nd/¹⁴⁴Nd compositions indistinguishable from the bulk silicate Earth, suggesting that the less degassed mantle sources did not experience significant fractionation for moderately incompatible elements.     

The early differentiation history of Mars from W-Nd isotope systematics in the SNC meteorites

We report here the results of an investigation of W and Nd isotopes in the SNC (Shergottite-Nakhlite-Chassignite (martian)) meteorites. We have determined that ε¹⁸²W values in the nakhlites are uniform within analytical uncertainties and have an average value of ∼3. Also, while ε¹⁸²W values in the shergottites have a limited range (from 0.3-0.7), their ε¹⁴²Nd values vary considerably (from −0.2-0.9). There appears to be no correlation between ε¹⁸²W and ε¹⁴²Nd in the nakhlites and shergottites. These results shed new light on early differentiation processes on Mars, particularly on the timing and nature of fractionation in silicate reservoirs. Assuming a two-stage model, the metallic core is estimated to have formed at ∼12 Myr after the beginning of the solar system. Major silicate differentiation established the nakhlite source reservoir before ∼4542 Ma and the shergottite source reservoirs at 4525 Ma. These ages imply that, within the uncertainties afforded by the ¹⁸²Hf-¹⁸²W and ¹⁴⁶Sm-¹⁴²Nd chronometers, the silicate differentiation events that established the source reservoirs of the nakhlites and shergottites may have occurred contemporaneously, possibly during crystallization of a global magma ocean. The distinct ¹⁸²W-¹⁴²Nd isotope systematics in the nakhlites and the shergottites imply the presence of at least three isotopically distinct silicate reservoirs on Mars, two of which are depleted in incompatible lithophile elements relative to chondrites, and the third is enriched. The two depleted silicate reservoirs most likely reside in the Martian mantle, while the enriched reservoir could be either in the crust or the mantle. Therefore, the ¹⁸²W-¹⁴²Nd isotope systematics indicate that the nakhlites and the shergottites originated from distinct source reservoirs and cannot be petrogenetically related. A further implication is that the source reservoirs of the nakhlites and shergottites on Mars have been isolated since their establishment before ∼4.5 Ga. Therefore, there has been no giant impact or efficient global mantle convection to thoroughly homogenize the Martian mantle following the establishment of the SNC source reservoirs.     

In search of a hidden long-term isolated sub-chondritic Nd/Nd reservoir in the deep mantle: Implications for the Nd isotope systematics of the Earth

Here we search for evidence of the existence of a sub-chondritic ¹⁴²Nd/¹⁴⁴Nd reservoir that balances the Nd isotope chemistry of the Earth relative to chondrites. If present, it may reside in the source region of deeply sourced mantle plume material. We suggest that lavas from Hawai’i with coupled elevations in ¹⁸⁶Os/¹⁸⁸Os and ¹⁸⁷Os/¹⁸⁸Os, from Iceland that represent mixing of upper mantle and lower mantle components, and from Gough with sub-chondritic ¹⁴³Nd/¹⁴⁴Nd and high ²⁰⁷Pb/²⁰⁶Pb, are favorable samples that could reflect mantle sources that have interacted with an Early-Enriched Reservoir (EER) with sub-chondritic ¹⁴²Nd/¹⁴⁴Nd.High-precision Nd isotope analyses of basalts from Hawai’i, Iceland and Gough demonstrate no discernable ¹⁴²Nd/¹⁴⁴Nd deviation from terrestrial standards. These data are consistent with previous high-precision Nd isotope analysis of recent mantle-derived samples and demonstrate that no mantle-derived material to date provides evidence for the existence of an EER in the mantle.We then evaluate mass balance in the Earth with respect to both ¹⁴²Nd/¹⁴⁴Nd and ¹⁴³Nd/¹⁴⁴Nd. The Nd isotope systematics of EERs are modeled for different sizes and timing of formation relative to ε¹⁴³Nd estimates of the reservoirs in the μ¹⁴²Nd = 0 Earth, where μ¹⁴²Nd is ((measured ¹⁴²Nd/¹⁴⁴Nd/terrestrial standard ¹⁴²Nd/¹⁴⁴Nd)−1 * 10⁻⁶) and the μ¹⁴²Nd = 0 Earth is the proportion of the silicate Earth with ¹⁴²Nd/¹⁴⁴Nd indistinguishable from the terrestrial standard. The models indicate that it is not possible to balance the Earth with respect to both ¹⁴²Nd/¹⁴⁴Nd and ¹⁴³Nd/¹⁴⁴Nd unless the μ¹⁴²Nd = 0 Earth has a ε¹⁴³Nd within error of the present-day Depleted Mid-ocean ridge basalt Mantle source (DMM). The 4567 Myr age ¹⁴²Nd-¹⁴³Nd isochron for the Earth intersects μ¹⁴²Nd = 0 at ε¹⁴³Nd of +8 ± 2 providing a minimum ε¹⁴³Nd for the μ¹⁴²Nd = 0 Earth. The high ε¹⁴³Nd of the μ¹⁴²Nd = 0 Earth is confirmed by the Nd isotope systematics of Archean mantle-derived rocks that consistently have positive ε¹⁴³Nd.If the EER formed early after solar system formation (0-70 Ma) continental crust and DMM can be complementary reservoirs with respect to Nd isotopes, with no requirement for significant additional reservoirs. If the EER formed after 70 Ma then the μ¹⁴²Nd = 0 Earth must have a bulk ε¹⁴³Nd more radiogenic than DMM and additional high ε¹⁴³Nd material is required to balance the Nd isotope systematics of the Earth.     

Hf-W isotope systematics of chondrites, eucrites, and martian meteorites: Chronology of core formation and early mantle differentiation in Vesta and Mars

The timescale of accretion and differentiation of asteroids and the terrestrial planets can be constrained using the extinct ¹⁸²Hf-¹⁸²W isotope system. We present new Hf-W data for seven carbonaceous chondrites, five eucrites, and three shergottites. The W isotope data for the carbonaceous chondrites agree with the previously revised ¹⁸²W/¹⁸⁴W of chondrites, and the combined chondrite data yield an improved ?_W value for chondrites of −1.9 ± 0.1 relative to the terrestrial standard. New Hf-W data for the eucrites, in combination with published results, indicate that mantle differentiation in the eucrite parent body (Vesta) occurred at 4563.2 ± 1.4 Ma and suggest that core formation took place 0.9 ± 0.3 Myr before mantle differentiation. Core formation in asteroids within the first ∼5 Myr of the solar system is consistent with the timescales deduced from W isotope data of iron meteorites. New W isotope data for the three basaltic shergottites EETA 79001, DaG 476, and SAU 051, in combination with published ¹⁸²W and ¹⁴²Nd data for Martian meteorites reveal the preservation of three early formed mantle reservoirs in Mars. One reservoir (Shergottite group), represented by Zagami, ALH77005, Shergotty, EETA 79001, and possibly SAU 051, is characterized by chondritic ¹⁴²Nd abundances and elevated ?_W values of ∼0.4. The ¹⁸²W excess of this mantle reservoir results from core formation. Another mantle reservoir (NC group) is sampled by Nakhla, Lafayette, and Chassigny and shows coupled ¹⁴²Nd-¹⁸²W excesses of 0.5-1 and 2-3 ? units, respectively. Formation of this mantle reservoir occurred 10-20 Myr after CAI condensation. Since the end of core formation is constrained to 7-15 Myr, a time difference between early silicate mantle differentiation and core formation is not resolvable for Mars. A third early formed mantle reservoir (DaG group) is represented by DaG 476 (and possibly SAU 051) and shows elevated ¹⁴²Nd/¹⁴⁴Nd ratios of 0.5-0.7 ? units and ?_W values that are indistinguishable from the Shergottite group. The time of separation of this third reservoir can be constrained to 50-150 Myr after the start of the solar system. Preservation of these early formed mantle reservoirs indicates limited convective mixing in the Martian mantle as early as ∼15 Myr after CAI condensation and suggests that since this time no giant impact occurred on Mars that could have led to mantle homogenization. Given that core formation in planetesimals was completed within the first ∼5 Myr of the solar system, it is most likely that Mars and Earth accreted from pre-differentiated planetesimals. The metal cores of Mars and Earth, however, cannot have formed by simply combining cores from these pre-differentiated planetesimals. The ¹⁸²W/¹⁸⁴W ratios of the Martian and terrestrial mantles require late effective removal of radiogenic ¹⁸²W, strongly suggesting the existence of magma oceans on both planets. Large impacts were probably the main heat source that generated magma oceans and led to the formation metallic cores in the terrestrial planets. In contrast, decay of short-lived ²⁶Al and ⁶⁰Fe were important heat sources for melting and core formation in asteroids.     

Hf-W chronology of the accretion and early evolution of asteroids and terrestrial planets

The ¹⁸²Hf-¹⁸²W systematics of meteoritic and planetary samples provide firm constraints on the chronology of the accretion and earliest evolution of asteroids and terrestrial planets and lead to the following succession and duration of events in the earliest solar system. Formation of Ca,Al-rich inclusions (CAIs) at 4568.3 ± 0.7 Ma was followed by the accretion and differentiation of the parent bodies of some magmatic iron meteorites within less than ∼1 Myr. Chondrules from H chondrites formed 1.7 ± 0.7 Myr after CAIs, about contemporaneously with chondrules from L and LL chondrites as shown by their ²⁶Al-²⁶Mg ages. Some magmatism on the parent bodies of angrites, eucrites, and mesosiderites started as soon as ∼3 Myr after CAI formation and may have continued until ∼10 Myr. A similar timescale is obtained for the high-temperature metamorphic evolution of the H chondrite parent body. Thermal modeling combined with these age constraints reveals that the different thermal histories of meteorite parent bodies primarily reflect their initial abundance of ²⁶Al, which is determined by their accretion age. Impact-related processes were important in the subsequent evolution of asteroids but do not appear to have induced large-scale melting. For instance, Hf-W ages for eucrite metals postdate CAI formation by ∼20 Myr and may reflect impact-triggered thermal metamorphism in the crust of the eucrite parent body. Likewise, the Hf-W systematics of some non-magmatic iron meteorites were modified by impact-related processes but the timing of this event(s) remains poorly constrained.The strong fractionation of lithophile Hf from siderophile W during core formation makes the Hf-W system an ideal chronometer for this major differentiation event. However, for larger planets such as the terrestrial planets the calculated Hf-W ages are particularly sensitive to the occurrence of large impacts, the degree to which impactor cores re-equilibrated with the target mantle during large collisions, and changes in the metal-silicate partition coefficients of W due to changing fO₂ in differentiating planetary bodies. Calculated core formation ages for Mars range from 0 to 20 Myr after CAI formation and currently cannot distinguish between scenarios where Mars formed by runaway growth and where its formation was more protracted. Tungsten model ages for core formation in Earth range from ∼30 Myr to >100 Myr after CAIs and hence do not provide a unique age for the formation of Earth. However, the identical ¹⁸²W/¹⁸⁴W ratios of the lunar and terrestrial mantles provide powerful evidence that the Moon-forming giant impact and the final stage of Earth’s core formation occurred after extinction of ¹⁸²Hf (i.e., more than ∼50 Myr after CAIs), unless the Hf/W ratios of the bulk silicate Moon and Earth are identical to within less than ∼10%. Furthermore, the identical ¹⁸²W/¹⁸⁴W of the lunar and terrestrial mantles is difficult to explain unless either the Moon consists predominantly of terrestrial material or the W in the proto-lunar magma disk isotopically equilibrated with the Earth’s mantle.Hafnium-tungsten chronometry also provides constraints on the duration of magma ocean solidification in terrestrial planets. Variations in the ¹⁸²W/¹⁸⁴W ratios of martian meteorites reflect an early differentiation of the martian mantle during the effective lifetime of ¹⁸²Hf. In contrast, no ¹⁸²W variations exist in the lunar mantle, demonstrating magma ocean solidification later than ∼60 Myr, in agreement with ¹⁴⁷Sm-¹⁴³Nd ages for ferroan anorthosites. The Moon-forming giant impact most likely erased any evidence of a prior differentiation of Earth’s mantle, consistent with a ¹⁴⁶Sm-¹⁴²Nd age of 50-200 Myr for the earliest differentiation of Earth’s mantle. However, the Hf-W chronology of the formation of Earth’s core and the Moon-forming impact is difficult to reconcile with the preservation of ¹⁴⁶Sm-¹⁴²Nd evidence for an early (<30 Myr after CAIs) differentiation of a chondritic Earth’s mantle. Instead, the combined ¹⁸²W-¹⁴²Nd evidence suggests that bulk Earth may have superchondritic Sm/Nd and Hf/W ratios, in which case formation of its core must have terminated more than ∼42 Myr after formation of CAIs, consistent with the Hf-W age for the formation of the Moon.     

High-precision Nd/Nd measurements in terrestrial rocks: Constraints on the early differentiation of the Earth’s mantle

We present new ultra-high precision ¹⁴²Nd/¹⁴⁴Nd measurements of early Archaean rocks using the new generation thermal ionization mass spectrometer Triton. Repeated measurements of the Ames Nd standard demonstrate that the ¹⁴²Nd/¹⁴⁴Nd ratio can be determined with external precision of 2 ppm (2σ), allowing confident resolution of anomalies as small as 5 ppm. A major analytical improvement lies in the elimination of the double normalization procedure required to correct our former measurements from a secondary mass fractionation effect. Our new results indicate that metasediments, metabasalts, and orthogneisses from the 3.6 to 3.8 Ga West Greenland craton display positive ¹⁴²Nd anomalies ranging from 8 to 15 ppm. Using a simple two-stage model with an initial ε¹⁴³Nd value of 1.9 ± 0.6 ε-units, coupled ¹⁴⁷Sm-¹⁴³Nd and ¹⁴⁶Sm-¹⁴²Nd chronometry constrains mantle differentiation to 50-200 Ma after formation of the solar system. This chronological constraint is consistent with differentiation of the Earth’s mantle during the late stage of crystallization of a magma ocean. We have developed a two-box model describing ¹⁴²Nd and ¹⁴³Nd isotopic evolution of depleted mantle during the subsequent evolution of the crust-mantle system. Our results indicate that early terrestrial protocrust had a lifetime of ca. 0.7-1 Ga in order to produce the observed Nd isotope signature of Archaean rocks. In the context of this two box mantle-crust system, we model the evolution of isotopic and chemical heterogeneity of depleted mantle as a function of the mantle stirring time. Using the dispersion of ¹⁴²Nd/¹⁴⁴Nd and ¹⁴³Nd/¹⁴⁴Nd ratios observed in early Archaean rocks, we constrain the stirring time of early Earth’s mantle to 100-250 Ma, a factor of 5 shorter than the stirring time inferred from modern oceanic basalts.     

Re-evaluating Nd/Nd in lunar mare basalts with implications for the early evolution and bulk Sm/Nd of the Moon

The Moon likely accreted from melt and vapor ejected during a cataclysmic collision between Proto-Earth and a Mars-sized impactor very early in solar system history. The identical W, O, K, and Cr isotope compositions between materials from the Earth and Moon require that the material from the two bodies were well-homogenized during the collision process. As such, the ancient isotopic signatures preserved in lunar samples provide constraints on the bulk composition of the Earth. Two recent studies to obtain high-precision ¹⁴²Nd/¹⁴⁴Nd ratios of lunar mare basalts yielded contrasting results. In one study, after correction of neutron fluence effects imparted to the Nd isotope compositions of the samples, the coupled ¹⁴²Nd-¹⁴³Nd systematics were interpreted to be consistent with a bulk Moon having a chondritic Sm/Nd ratio [Rankenburg K., Brandon A. D. and Neal C. R. (2006) Neodymium isotope evidence for a chondritic composition of the Moon. Science312, 1369-1372]. The other study found that their data on the same and similar lunar mare basalts were consistent with a bulk Moon having a superchondritic Sm/Nd ratio [Boyet M. and Carlson R. W. (2007) A highly depleted Moon or a non-magma origin for the lunar crust? Earth Planet. Sci. Lett.262, 505-516]. Delineating between these two potential scenarios has key ramifications for a comprehensive understanding of the formation and early evolution of the Moon and for constraining the types of materials available for accretion into large terrestrial planets such as Earth.To further examine this issue, the same six lunar mare basalt samples measured in Rankenburg et al. [Rankenburg K., Brandon A. D. and Neal C. R. (2006) Neodymium isotope evidence for a chondritic composition of the Moon. Science312, 1369-1372] were re-measured for high-precision Nd isotopes using a multidynamic routine with reproducible internal and external precisions to better than ±3 ppm (2σ) for ¹⁴²Nd/¹⁴⁴Nd ratios. The measurements were repeated in a distinct second analytical campaign to further test their reproducibility. Evaluation of accuracy and neutron fluence corrections indicates that the multidynamic Nd isotope measurements in this study and the 3 in Boyet and Carlson [Boyet M. and Carlson R. W. (2007) A highly depleted Moon or a non-magma origin for the lunar crust? Earth Planet. Sci. Lett.262, 505-516] are reproducible, while static measurements in the previous two studies show analytical artifacts and cannot be used at the resolution of 10 ppm to determine a bulk Moon with either chondritic or superchondritic Sm/Nd ratios. The multidynamic data are best explained by a bulk Moon with a superchondritic Sm/Nd ratio that is similar to the present-day average for depleted MORB. Hafnium isotope data were collected on the same aliquots measured for their ¹⁴²Nd/¹⁴⁴Nd isotope ratios in order to assess if the correlation line for ¹⁴²Nd-¹⁴³Nd systematics reflect mixing processes or times at which lunar mantle sources formed. Based on the combined ¹⁴²Nd-¹⁴³Nd-¹⁷⁶Hf obtained we conclude that the ¹⁴²Nd-¹⁴³Nd correlation line measured in this study is best interpreted as an isochron with an age of 229⁺²⁴₋₂₀Ma after the onset of nebular condensation. The uncertainties in the data permit the sources of these samples to have formed over a 44 Ma time interval. These new results for lunar mare basalts are thus consistent with a later Sm-Nd isotope closure time of their source regions than some recent studies have postulated, and a superchondritic bulk Sm/Nd ratio of the Moon and Earth. The superchondritic Sm/Nd signature was inherited from the materials that accreted to make up the Earth-Moon system. Although collisional erosion of crust from planetesimals is favored here to remove subchondritic Sm/Nd portions and drive the bulk of these bodies to superchondritic in composition, removal of explosive basalt material via gravitational escape from such bodies, or chondrule sorting in the inner solar system, may also explain the compositional features that deviate from average chondrites that make up the Earth-Moon system. This inferred superchondritic nature for the Earth similar to the modern convecting mantle means that there is no reason to invoke a missing, subchondritic reservoir to mass balance the Earth back to chondritic for Sm/Nd ratios. However, to account for the subchondritic Sm/Nd ratios of continental crust, a second superchondritic Sm/Nd mantle reservoir is required.     

Early Archean crustal evolution of the Jack Hills Zircon source terrane inferred from Lu-Hf, Pb/Pb, and δO systematics of Jack Hills zircons

Several lines of isotopic evidence - the most direct of which is from Hadean Jack Hills zircons - suggest a very early history of crust formation on Earth that began by about 4.5 Ga. To constrain both the fate of the reservoir for this crust and the nature of crustal evolution in the sediment source region of the Jack Hills, Western Australia, during the early Archean, we report here initial ¹⁷⁶Hf/¹⁷⁷Hf ratios and δ¹⁸O systematics for <4 Ga Jack Hills zircons. In contrast to the significant number of Hadean zircons which contain highly unradiogenic ¹⁷⁶Hf/¹⁷⁷Hf requiring a near-zero Lu/Hf reservoir to have separated from the Earth’s mantle by 4.5 Ga, Jack Hills zircons younger than ca. 3.6 Ga are more radiogenic than -13ε (CHUR) at 3.4 Ga in contrast to projected values at 3.4 Ga of -20ε for the unradiogenic Hadean reservoir indicating that some later juvenile addition to the crust is required to explain the more radiogenic younger zircons. The shift in the Lu-Hf systematics together with a narrow range of mostly mantle-like δ¹⁸O values among the <3.6 Ga zircons (in contrast to the spread towards sedimentary δ¹⁸O among Hadean samples) suggests a period of transition between 3.6 and 4 Ga in which the magmatic setting of zircon formation changed and the highly unradiogenic low Lu/Hf Hadean crust ceased to be available for intracrustal reworking. Constraining the nature of this transition provides important insights into the processes of crustal reworking and recycling of the Earth’s Hadean crust as well as early Archean crustal evolution.     

Application of precise 142Nd/144Nd analysis of small samples to inclusions in diamonds (Finsch,South Africa) and Hadean Zircons (Jack Hills,Western Australia)

¹⁴⁶Sm–¹⁴²Nd and ¹⁴⁷Sm–¹⁴³Nd systematics were investigated in garnet inclusions in diamonds from Finsch (S. Africa) and Hadean zircons from Jack Hills (W. Australia) to assess the potential of these systems as recorders of early Earth evolution. The study of Finsch inclusions was conducted on a composite sample of 50 peridotitic pyropes with a Nd model age of 3.3 Ga. Analysis of the Jack Hills zircons was performed on 790 grains with ion microprobe ²⁰⁷Pb/²⁰⁶Pb spot ages from 3.95 to 4.19 Ga. Finsch pyropes yield 100 × ?¹⁴²Nd = ? 6 ± 12 ppm, ?¹⁴³Nd = ? 32.5, and ¹⁴⁷Sm/¹⁴⁴Nd = 0.1150. These results do not confirm previous claims for a 30 ppm ¹⁴²Nd excess in South African cratonic mantle. The lack of a ¹⁴²Nd anomaly in these inclusions suggests that isotopic heterogeneities created by early mantle differentiation were remixed at a very fine scale prior to isolation of the South African lithosphere. Alternatively, this result may indicate that only a fraction of the mantle experienced depletion during the first 400 Myr of its history. Analysis of the Jack Hills zircon composite yielded 100 × ?¹⁴²Nd = 8 ± 10 ppm, ?¹⁴³Nd = 45 ± 1, and ¹⁴⁷Sm/¹⁴⁴Nd = 0.5891. Back-calculation of this present-day ?¹⁴³Nd yields an unrealistic estimate for the initial ?¹⁴³Nd of ? 160 ?-units, clearly indicating post-crystallization disturbance of the ¹⁴⁷Sm–¹⁴³Nd system. Examination of ^146,147Sm–^142,143Nd data reveals that the Nd budget of the Jack Hills sample is dominated by non-radiogenic Nd, possibly contained in recrystallized zircon rims or secondary subsurface minerals. This secondary material is characterized by highly discordant U–Pb ages. Although the mass fraction of altered zircon is unlikely to exceed 5–10% of total sample, its high LREE content precludes a reliable evaluation of ¹⁴⁶Sm–¹⁴²Nd systematics in Jack Hills zircons.     

A high field strength element perspective on early lunar differentiation

Lunar rocks are inferred to tap the different fossil cumulate layers formed during crystallisation of a lunar magma ocean (LMO). A coherent dataset, including Zr isotope data and high precision HFSE (W, Nb, Ta, Zr, Hf) and REE (Nd, Sm, Lu) data, all obtained by isotope dilution, can now provide new insights into the processes active during LMO crystallisation and during the petrogenesis of lunar magmas. Measured ⁹²Zr and ⁹¹Zr abundances agree with the terrestrial value within 0.2 ε-units. Incompatible-trace-element enriched rocks from the Procellarum KREEP Terrane (PKT) display Nb/Ta and Zr/Hf above the bulk lunar value (ca. 17), and mare basalts display lower ratios, generally confirming the presence of complementary enriched and depleted mantle reservoirs on the Moon. The full compositional spectrum of lunar basalts, however, also requires interaction with ilmenite-rich layers in the lunar mantle. Notably, the high-Ti mare basalts analysed display the lowest Nb/Ta and Zr/Hf of all lunar rocks, and also higher Sm/Nd at similar Lu/Hf than low-Ti basalts. The high-Ti basalts also exhibit higher and strongly correlated Ta/W (up to 25) and Hf/W (up to 140), at similar W contents, which is difficult to reconcile with ortho- and clinopyroxene-controlled melting. Altogether, these patterns can be explained via assimilation of up to ca. 20% of ilmenite- and clinopyroxene-rich LMO cumulates by more depleted melts from the lower lunar mantle. Direct melting of ilmenite-rich cumulates or the possible presence of residual metals in the lunar mantle both cannot easily account for the observed Ta/W and Hf/W patterns. Cumulate assimilation is also a viable mechanism that can partially buffer the Lu/Hf of mare basalts at relatively low values while generating variable Sm/Nd. Thus, the dichotomy between low Lu/Hf of lunar basalts and high time integrated source Lu/Hf as inferred from Hf isotope compositions can potentially be explained. The proposed assimilation model also has important implications for the short-lived nuclide chronology of the Earth-Moon system. The new Hf/W and Ta/W data, together with a compilation of existing W-Th-U data for lunar rocks, indicate that the terrestrial and lunar mantles are indistinguishable in their Hf/W. Virtually identical εW and Hf/W in the terrestrial and lunar mantle suggest a strong link between final core-mantle equilibration on Earth and the Moon forming giant impact. Previously, linear arrays of lunar samples in ¹⁸²W vs. Hf/W and ¹⁴²Nd vs. Sm/Nd spaces have been interpreted as isochrons, arguing for LMO crystallisation as late as 250 Myrs after solar system formation. Based on the proposed assimilation model, the ¹⁸²W and ¹⁴²Nd in many lunar magmas can be shown to be decoupled from their ambient Hf/W and Sm/Nd source compositions. As a consequence, the ¹⁸²W vs. Hf/W and ¹⁴²Nd vs. Sm/Nd arrays would constitute mixing lines rather than isochrons. Hence, the lunar ¹⁸²Hf-¹⁸²W and ¹⁴⁶Sm-¹⁴²Nd data would be fully consistent with an “early” crystallisation age of the LMO, even as early as 50 Myrs after solar system formation when the Moon was probably formed.     

Petrogenesis of 3.15 Ga old Banasandra komatiites from the Dharwar craton,India: Implications for early mantle heterogeneity

Spinifex-textured.magnesian(MgO 25 wt.%) komatiites from Mesoarchean Banasandra greenstone belt of the Sargur Group in the Dharwar craton,India were analysed for major and trace elements and~(147,146)Sm-~(143,142)Nd systematics to constrain age,petrogenesis and to understand the evolution of Archean mantle.Major and trace element ratios such as CaO/Al_2O_3.Al_2O_3/TiO_2,Gd/Yb,La/Nb and Nb/Y suggest aluminium undepleted to enriched compositional range for these komatiites.The depth of melting is estimated to be varying from 120 to 240 km and trace-element modelling indicates that the mantle source would have undergone multiple episodes of melting prior to the generation of magmas parental to these komatiites.Ten samples of these komatiites together with the published results of four samples from the same belt yield ~(147)Sm-~(143)Nd isochron age of ca.3.14 Ga with an initial ε_(Nd)(f) value of+3.5.High precision measurements of ~(142)Nd/~(144)Nd ratios were carried out for six komatiite samples along with standards AMES and La Jolla.All results are within uncertainties of the terrestrial samples.The absence of~(142)Nd/~(144)Nd anomaly indicates that the source of these komatiites formed after the extinction of ~(146)Sm,i.e.4.3 Ga ago.In order to evolve to the high ε_(Nd)(t) value of +3.5 by 3.14 Ga the time-integrated ratio of~(147)Sm/~(144)Nd should be 0.2178 at the minimum.This is higher than the ratios estimated,so far,for mantle during that time.These results indicate at least two events of mantle differentiation starting with the chondritic composition of the mantle.The first event occurred very early at ~4.53 Ga to create a global early depleted reservoir with superchondritic Sm/Nd ratio.The source of Isua greenstone rocks with positive ~(142)Nd anomaly was depleted during a second differentiation within the life time of ~(146)Sm,i.e.prior to 4.46 Ga.The source mantle of the Banasandra komatiite was a result of a differentiation event that occurred after the extinction of the ~(146)Sm,i.e.at 4.3 Ga and prior to 3.14 Ga.Banasandra komatiites therefore provide evidence for preservation of heterogeneities generated during mantle differentiation at4.3 Ga.     

The Earth’s tungsten budget during mantle melting and crust formation

During silicate melting on Earth, W is one of the most incompatible trace elements, similar to Th, Ba or U. As W is also moderately siderophile during metal segregation, ratios of W and the lithophile Th and U in silicate rocks have therefore been used to constrain the W abundance of the Earth’s mantle and the Hf-W age of core formation. This study presents high-precision W concentration data obtained by isotope dilution for samples covering important silicate reservoirs on Earth. The data reveal significant fractionations of W from other highly incompatible lithophile elements such as Th, U, and Ta. Many arc lavas exhibit a selective enrichment of W relative to Th, U, and Nb-Ta, reflecting W enrichment in the sub-arc mantle via fluid-like components derived from subducting plates. In contrast, during enrichment by melt-like subduction components, W is generally slightly depleted relative to Th and U, but is still enriched relative to Ta. Hence, all arc rocks and the continental crust exhibit uniformly low Ta/W (ca. 1), whereas W/Th and W/U may show opposite fractionation trends, depending on the role of fluid- and melt-like subduction components. Further high-precision W data for OIBs and MORBs reveal a systematic depletion of W in both rock types relative to other HFSE, resulting in high Ta/W that are complementary to the low Ta/W observed in arc rocks and the continental crust. Similar to previous interpretations based on Nb/U and Ce/Pb systematics, our Ta/W data confirm a depletion of the depleted upper mantle (DM) in fluid mobile elements relative to the primitive mantle (PRIMA). The abundance of W in the depleted upper mantle relative to other immobile and highly incompatible elements such as Nb and Ta is therefore not representative of the bulk silicate Earth. Based on mass balance calculations using Ta-W systematics in the major silicate reservoirs, the W abundance of the Earth’s primitive mantle can be constrained to 12 ppb, resulting in revised ratios of W-U and W-Th of 0.53 and 0.14, respectively. The newly constrained Hf-W ratio of the silicate Earth is 25.8, significantly higher than previously estimated (18.7) and overlaps within error the Hf-W ratio proposed for the Moon (ca. 24.9). The ¹⁸²Hf-¹⁸²W model age for the formation of the Earth’s core that is inferred from the ¹⁸²W abundance and the Hf/W of the silicate Earth is therefore younger than previously calculated, by up to 5 Myrs after solar system formation depending on the accretion models used. The similar Hf/W ratios and ¹⁸²W compositions of the Earth and the silicate Moon suggest a strong link between the Moon forming giant impact and final metal-silicate equilibration on the Earth.     

Trace-element characteristics of east–west mantle geochemical hemispheres

Recent statistical analyses on the isotopic compositions of oceanic, arc, and continental basalts have revealed that the Earth's mantle is broadly divided into eastern and western hemispheres. The present study aimed to characterize the isotopically defined east–west geochemical hemispheres using trace-element concentrations. Basalt data with Rb, Sr, Nd, Sm, Pb, Th, and U in addition to the isotopic ratios ⁸⁷Sr/⁸⁶Sr, ¹⁴³Nd/¹⁴⁴Nd, ²⁰⁶Pb/²⁰⁴Pb, ²⁰⁷Pb/²⁰⁴Pb, and ²⁰⁸Pb/²⁰⁴Pb were selected mostly from the GEOROC and PetDB databases. A total of 4787 samples were used to investigate the global geochemical variations. The results show that the wide trace-element variations are broadly explained by the melting of melt-metasomatized and fluid-metasomatized mantle sources. The larger amount of the fluid component derived from subducted plates in the eastern hemisphere than that in the western hemisphere is inferred from the basalts. These characteristics support the hypothesis that focused subduction towards the supercontinent created the mantle geochemical hemispheres.     

Correlated nucleosynthetic isotopic variability in Cr, Sr, Ba, Sm, Nd and Hf in Murchison and QUE 97008

Acid leaching of the primitive C-chondrite Murchison and O-chondrite QUE 97008 reveal nucleosynthetic anomalies in Cr, Sr, Ba, Nd, Sm and Hf. The anomalies in all but Cr and Sm are best explained by variable additions of pure s-process nuclides to a background nebular composition slightly enriched in r-process isotopes compared to average Solar System material. Leaching leaves a residue in Murchison that is strongly enriched in s-process nuclides with depletions of over 0.1% in ¹³⁵Ba and seven parts in 10,000 in ⁸⁴Sr. If there are p-process anomalies in these two elements, they are lost in the variability caused by different r-, s-process contributions to the normalizing isotopes. The concentration and isotope systematics are consistent with the Ba and Sr isotopic composition in the Murchison residue being strongly influenced by s-process-rich presolar SiC. In general, the nucleosynthetic isotope anomalies are 2- to 5-fold smaller in QUE 97008 than in Murchison. The different magnitudes of isotope anomalies are similar to the difference in matrix abundance between CM and O chondrites consistent with the suggestion that the carriers of nucleosynthetically anomalous material preferentially reside in the matrix and that some of this material has been distributed throughout the O-chondrite minerals as a result of thermal metamorphism.Neodymium, Sm and Hf display variable s-, r-process nuclide abundances as in Ba and Sr, but the anomalies are much smaller (e.g. ε¹⁴⁸Nd, ε¹⁴⁸Sm = −5.7, 2.1, respectively, in Murchison and −0.43, 0.16, respectively in QUE 97008 residues). After correcting Nd and Sm for s-, r-process variability, Sm in whole rock chondrites shows variable relative abundances of the p-process isotope ¹⁴⁴Sm that correlate weakly with ¹⁴²Nd suggesting that the direct p-process contribution to ¹⁴²Nd is small (∼7-9%). Nucleosynthetic variability in Nd explains the range in ¹⁴²Nd/¹⁴⁴Nd seen between C and O, E-chondrites, but not the difference between chondrites and all modern Earth rocks, leaving decay of ¹⁴⁶Sm and a superchondritic Sm/Nd ratio as the likely explanation for Earth’s high ¹⁴²Nd/¹⁴⁴Nd.     

A depleted, not ideally chondritic bulk Earth: The explosive-volcanic basalt loss hypothesis

It has long been customary to assume that in the bulk composition of the Earth, all refractory-lithophile elements (including major oxides Al₂O₃ and CaO, all of the REE, and the heat-producing elements Th and U) occur in chondritic, bulk solar system, proportion to one another. Recently, however, Nd-isotopic studies (most notably Boyet M. and Carlson R. W. (2006) A new geochemical model for the Earth’s mantle inferred from ¹⁴⁶Sm-¹⁴²Nd systematics. Earth Planet. Sci. Lett.250, 254-268) have suggested that at least the outer portion of the planet features a Nd/Sm ratio depleted to ∼0.93 times the chondritic ratio. The primary reaction to this type of evidence has been to invoke a “hidden” reservoir of enriched matter, sequestered into the deepest mantle as a consequence of primordial differentiation. I propose a hypothesis that potentially explains the evidence for Nd/Sm depletion in a very different way. Among the handful of major types of differentiated asteroidal meteorites, two (ureilites and aubrites) are ultramafic restites so consistently devoid of plagioclase that meteoriticists were once mystified as to how all the complementary plagioclase-rich matter (basalt) was lost. The explanation appears to be basalt loss by graphite-fueled explosive volcanism on roughly 100-km sized planetesimals; with the dispersiveness of the process dramatically enhanced, relative to terrestrial experience, because the pyroclastic gases expand into vacuous space (Wilson L. and Keil K. (1991) Consequences of explosive eruptions on small Solar System bodies: the case of the missing basalts on the aubrite parent body. Earth Planet. Sci. Lett.104, 505-512). By analogy with lunar pyroclastic products, the typical size of pyroclastic melt/glass droplets under these circumstances will be roughly 0.1 mm. Once separated from an asteroidal or planetesimal gravitational field, droplets of this size will generally spiral toward the Sun, rather than reaccrete, because drag forces such the Poynting-Robertson effect quickly modify their orbits (the semimajor axis, in a typical scenario, is reduced by several hundred km during the first trip around the Sun). Assuming a similar process occurred on many of the Earth’s precursor planetesimals while they were still roughly 100 km in diameter, the net effect would be a depleted composition for the final Earth. I have modeled the process of trace-element depletion in the planetesimal mantles, assuming the partial melting was nonmodal and either batch or dynamic in terms of the melt-removal style. Assuming the process is moderately efficient, typical final-Earth Nd/Sm ratios are 0.93-0.96 times chondritic. Depletion is enhanced by a relatively low assumed residual porosity in batch-melting scenarios, but dampened by a relatively high value for “continuous” residue porosity in dynamic melting scenarios. Pigeonite in the source matter has a dampening effect on depletion. There are important side effects to the Nd/Sm depletion. The heat-producing elements, Th, U and K, might be severely depleted. The Eu/Eu^∗ ratio of the planet is unlikely to remain precisely chondritic. One of the most inevitable side effects, depletion of the Al/Ca ratio, is consistent with an otherwise puzzling aspect of the composition of the upper mantle. A perfectly undepleted composition for the bulk Earth is dubious.     

浙闽沿海早白垩世玄武岩锶、钕、铅同位素特征——古老富集型地幔的证据

浙闽沿海大面积出露的中生代酸性火山岩区有少量早白垩世玄武岩分布,它们具典型钾富集和铌等元素亏损特征,其同位素组成表现为较高ISr(0.7055-0.7106)、低的εNd(1.2--10.6,大多介于-3.2--10.6之间)及富放射性成因铅(²⁰⁶Pb/²⁰⁴Pb=18.355-18.726,²⁰⁷Pb/²⁰⁴Pb=15.455-15.799,²⁰⁸Pb/²⁰⁴Pb=38.530-39.319).这些特征表明玄武岩源区为一富集型的陆下岩石圈地幔,由古老的俯冲地壳物质再循环进入并交代地幔而形成。没有证据表明本区早白垩世基性和酸性岩浆之间发生过大规模的化学混合,但不排除同位素之间的交换以及局部的化学和机械混合。壳-幔混合与地壳混染仅在少数玄武岩的形成过程中起着较重要的作用。