Search for nucleosynthetic and radiogenic tellurium isotope anomalies in carbonaceous chondrites

Tellurium isotope data acquired by multiple-collector inductively coupled plasma-mass spectrometry (MC-ICPMS) are presented for sequential acid leachates of the carbonaceous chondrites Orgueil, Murchison, and Allende. Tellurium isotopes are produced by a broad range of nucleosynthetic pathways and they are therefore of particular interest given the isotopic anomalies previously identified for other elements in these meteorites. In addition, the data provide new constraints on the initial solar system abundance of the r-process nuclide ¹²⁶Sn, which decays to ¹²⁶Te with a half-life of 234,500 years. The ¹²⁶Te/¹²⁸Te ratios of all leachates were found to be identical, within uncertainty, despite variations in ¹²⁴Sn/¹²⁸Te of between about 0.002 and 1.4. The data define a ¹²⁶Sn/¹²⁴Sn ratio of <7.7 × 10⁻⁵ at the time of last isotopic closure, consistent with the value of <18 × 10⁻⁵ previously reported for bulk carbonaceous chondrites. How close this is to the initial ¹²⁶Sn/¹²⁴Sn ratio of the solar system depends on when the investigated samples last experienced redistribution of Sn and Te. No clear evidence is found for nucleosynthetic anomalies in the abundances of p-, s-, and r-process nuclides. The largest effect detected in this study is a small excess of the r-process nuclide ¹³⁰Te in a nitric acid leachate of Murchison. This fraction displays an anomalous ε¹³⁰Te of +3.5 ± 2.5. Although barely resolvable given the analytical uncertainties, this is consistent with the presence of a small excess r-process component or an s-process deficit. The general absence of anomalies contrasts with previous results obtained for K, Cr, Zr, Mo, and Ba isotopes in similar leachates, which display nucleosynthetic anomalies of up to 3.8%. The reason for this discrepancy is unclear but it may reflect volatility and more efficient mixing of Te in the solar nebula.     

Nucleosynthetic zirconium isotope anomalies in acid leachates of carbonaceous chondrites

Stepwise dissolutions of the carbonaceous chondrites Orgueil (CI), Murchison (CM) and Allende (CV) reveal large nucleosynthetic anomalies for Zr isotopes that contrast with the uniform compositions found in bulk meteorites. Two complementary nucleosynthetic components are observed: one enriched and one depleted in s-process nuclides. The latter component, characterized by excess ⁹⁶Zr, is most distinctive in the acetic acid leachate (up to ε⁹⁶Zr ≈ 50). The excess decreases with increasing acid strength and the final leaching steps of the experiment are depleted in ⁹⁶Zr and thus enriched in s-process nuclides. Presolar silicon carbide grains are likely host phases for part of the anomalous Zr released during these later stages. However, by mass balance they cannot account for the ⁹⁶Zr excesses observed in the early leaching steps and this therefore hints at the presence of at least one additional carrier phase with significant amounts of anomalous Zr. The data provide evidence that average solar system material consists of a homogenized mixture of different nucleosynthetic components, which can be partly resolved by leaching experiments of carbonaceous chondrites.     

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.     

Neutron-capture elements in halo,thick-disk,and thin-disk stars: Neodymium

We have derived the LTE neodymium abundances in 60 cool stars with metallicities [Fe/H] from 0.25 to ?1.71 by applying a synthetic-spectrum analysis to spectroscopic observations of NdII lines with a resolution of λ/Δλ?60 000 and signal-to-noise ratios of 100–200. We have improved the atomic parameters of NdII and blending lines by analyzing the corresponding line pro files in the solar spectrum. Neodymium is overabundant with respect to iron in halo stars, [Nd/Fe]=0.33±0.09, with the [Nd/Fe] ratio decreasing systematically with metallicity when [Fe/H]>?1. This reflects an onset of efficient iron production in type I supernovae during the formation of the thick disk. The [Nd/Ba] and [Nd/Eu] abundance ratios behave differently in halo, thick-disk, and thin-disk stars. The observed abundance ratios in halo stars, [Nd/Ba]=0.34±0.08 and [Nd/Eu]=?0.27±0.05, agree within the errors with the ratios of the elemental yields for the r-process. These results support the conclusion of other authors based on analyses of other elements that the r-process played the dominant role in the synthesis of heavy elements during the formation of the halo. The [Nd/Ba] and [Nd/Eu] ratios for thick-disk stars are almost independent of metallicity ([Nd/Ba]=0.28(±0.03)?0.01(±0.04) [Fe/H] and [Nd/Eu]=?0.13(±0.03)+0.05(±0.04) [Fe/H]) but are smaller in absolute value than the corresponding ratios for halo stars, suggesting that the synthesis of s-process nuclei started during the formation of the thick disk. The s-process is estimated to have contributed ?30% of the neodymium produced during this stage of the evolution of the Galaxy. The [Nd/Ba] ratio decreases abruptly by 0.17 dex in the transition from the thick to the thin disk. The systematic decrease of [Nd/Ba] and increase of [Nd/Eu] with increasing metallicity of thin-disk stars point toward a dominant role of the s-process in the synthesis of heavy elements during this epoch.     

Molybdenum Isotopic Composition of Individual Presolar Silicon Carbide Grains from the Murchison Meteorite

We report the isotopic composition of molybdenum in twenty-three presolar SiC grains from the Murchison meteorite which have been measured by resonant ionization mass spectrometry (RIMS). Relative to terrestrial abundance (and normalized to s-process-only ⁹⁶Mo), the majority of the analyzed grains show strong depletions in the p-process isotopes ⁹²Mo and ⁹⁴Mo and the r-process isotope ¹⁰⁰Mo. Sixteen of these grains have δ-values <−600% for these three isotopes. The observed isotopic patterns of Mo from mainstream SiC grains clearly reveal the signature of s-process nucleosynthesis. Three-isotope plots of all grain data (δⁱMo vs. δ⁹²Mo) show strong linear correlations with characteristic slopes. This finding suggests mixing of solar-like material and pure s-process material in the parent stars. Comparison with evolutionary calculations of nucleosynthesis and mixing in red giants suggests that low-mass thermally-pulsed symptotic giant branch (TP-AGB) stars are the most likely site for the observed s-process nucleosynthesis.     

In search of live Cm in the early solar system

The r-process only nuclide ²⁴⁷Cm decays to ²³⁵U with a characteristic half-life of ∼16 million years. ²⁴⁷Cm is presently extinct, but offers considerable potential as a short-lived r-process chronometer, providing constraints on the time interval between the last r-process nucleo-synthetic event and the formation of the solar system. The existence of “live” ²⁴⁷Cm in the early solar system should be manifested today as variations in ²³⁵U/²³⁸U, provided Cm was chemically fractionated from U when solids formed in the early solar system. Using multiple-collector ICPMS and a high-purity mixed ²³³U-²³⁶U spike to monitor instrumental mass fractionation, we are able to resolve variations in ²³⁵U/²³⁸U at the 1-2 epsilon level (2σ_M; 1 epsilon = 1 part in 10,000) on sample sizes consisting of 20 ng of uranium. Data can be acquired on smaller (<10 ng) samples with ±2-3 epsilon 2σ uncertainties. Uranium isotopic measurements and U, Nd and Sm concentrations were acquired on bulk samples of a suite of carbonaceous chondrites, unequilibrated and equilibrated ordinary chondrites and eucrites, for which conflicting results had previously been obtained. Our results show no well-resolved excursions in ²³⁵U/²³⁸U away from the terrestrial value at the ∼2 epsilon level, and constrain the amount of ²⁴⁷Cm-produced excess ²³⁵U atoms to less than ∼1 × 10⁸ atoms per gram of chondritic meteorite, with respect to terrestrial ²³⁵U/²³⁸U. Large (permil- level) anomalies in ²³⁵U/²³⁸U could, however, be artificially generated in the ordinary chondrites during laboratory processing. Therefore, U may be more susceptible to isotopic fractionation during chemical processing than previously recognized, and may reconcile some of the highly conflicting ε²³⁵U results reported by previous workers for chondritic meteorites. Our results indicate that a timescale of ∼1-2 × 10⁸ years between the last actinide producing r-process event and the formation of the solar system may not be unreasonable based on the ²⁴⁷Cm-²³⁵U system. However, this conclusion is far from robust at this stage because the only bulk meteorites analysed that display strong Nd/U fractionation are highly metamorphosed chondrites that may have experienced a protracted history of redistribution and re-equilibration. The search for “live” ²⁴⁷Cm in the early solar system can now be extended to early-formed condensates and mineral phases displaying strong Cm-U fractionations.     

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.     

利用套柱法快速分离提纯Sr和Nd元素

样品放射性成因Sr-Nd同位素比值受控于源区初始同位素组成、放射性元素母体与子体相对丰度,以及衰变时间等因素。它们具有极强的示踪能力,因而在地质学领域有广泛的应用。传统的Sr-Nd同位素分析使用的是阳离子树脂,提纯Nd元素时往往涉及有机试剂以及调节pH值等操作,其分析效率较低。近年来特效树脂的出现使得分离这些元素变得简单,但是受硫酸根等因素影响,特效树脂使用次数有限。为了提高分析效率,缩短分析时间,本文开发了一种套柱法,该方法结合阳离子树脂和特效树脂,实现了Sr-Nd元素的快速分离,并且能延长特效树脂的使用寿命。实验采用阳离子树脂、Sr特效树脂和LN稀土特效树脂对玄武岩BCR-2标样进行了分析。Sr-Nd回收率均90%,BCR-2玄武岩~(87)Sr/~(86)Sr比值为0.705016±0.000016(n=36,1SD),~(143)Nd/~(144)Nd比值为0.512624±0.000012(n=39,1SD),与前人TIMS法获得的结果吻合(~(87)Sr/~(86)Sr:0.705000～0.705023;~(143)Nd/~(144)Nd:0.512630～0.512650)。最终分离提纯的溶液中~(85)Rb/~(86)Sr值小于0.01,~(147)Sm/~(144)Nd值小于0.001,表明该方法可以高效分离Rb-Sr和Sm-Nd,实现Sr、Nd同位素的准确分析。     

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.     

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.     

Zircon U-Pb Age and Geochemistry of the Ore-hosting Ultramafic Complex of Zhou’an PGE-Cu-Ni Deposit, Henan Province, Central China

The Zhou’an PGE-Cu-Ni deposit was recently discovered in the Qinling orogenic belt bound by the Yangtze and the North China Cratons. It is a blind deposit thoroughly covered by the Cenozoic alluvial sediments in the Nanyang Basin. As the first large PGE-Cu-Ni deposit discovered in the Qinling-Dabie-Sulu orogenic belt, its geological and geochemical characteristic, isotope age, genesis and tectonic setting are of wide concern in both scientific studies and ore exploration. In this contribution, we report the results obtained from a pioneering study. The Zhou’an ultramafic complex is ferruginous, with m/f?=?4.79–5.08, and shows the nature of tholeiite series. It is rich in light rare earth elements, Rb, Th, U, La, Sm, Zr and Hf, and poor in heavy rare earth elements, Nd and Ta, suggesting an intraplate setting. It has high 87Sr/86Sr and low 143Nd/144Nd ratios. The ratios of Zr/Nb, La/Nb, Ba/Nb, Rb/Nb, Th/Nb, Th/La and Ba/La, suggest the magma originated from lithosphere mantle. The Fo values of olivine and Pd/Ir-Ni/Cu diagram suggest primary magma was High Mg basalt. The laser ablation inductively coupled plasma atomic emission spectroscopy zircon U-Pb age is 641.5?±?3.7 Ma.     

Early Mesozoic lamproites and monzonitoids of southeastern Gorny Altai: geochemistry,Sr-Nd isotope composition,and sources of melts

Small intrusions of lamprophyres and lamproites (Chuya complex) and K-monzonitoids (Tarkhata and Terandzhik complexes) are widespread in southeastern Gorny Altai. Geochronological (U-Pb and Ar-Ar) isotope studies show their formation in the Early-Middle Triassic (~ 234-250 Ma). Lamproites have been revealed within two magmatic areas and correspond in geochemical parameters to the classical Mediterranean and Tibet orogenic lamproites. According to isotope data ((⁸⁷Sr/⁸⁶Sr)_T = 0.70850-0.70891, (¹⁴³Nd/¹⁴⁴Nd)_T = 0.512157-0.512196, ²⁰⁶Pb/²⁰⁴Pb = 17.95-18.05) and Th/La and Sm/La values, the Chuya lamproites and lamprophyres melted out from the enriched lithospheric mantle with the participation of DM, EM1, EM2, and SALATHO. The monzonitoid series of the Tarkhata and Terandzhik complexes are similar in petrographic and geochemical compositions but differ significantly in Sr-Nd isotope composition: The Tarkhata monzonitoids are close to the Chuya lamproites, whereas the Terandzhik ones show a higher portion of DM ((⁸⁷Sr/⁸⁶Sr)_T = 0.70434-0.70497, (¹⁴³Nd/¹⁴⁴Nd)_T = 0.512463-0.512487) in their source, which suggests its shallower depth of occurrence and the higher degree of its partial melting as compared with the derivates of the Chuya and Tarkhata complexes. The studied rock associations tentatively formed in the postcollisional setting under the impact of the Siberian superplume.     

Production and Certification of the Reference Material GSB 04‐3258‐2015 as a 143Nd/144Nd Isotope Ratio Reference

A new certified reference material, labelled GSB 04‐3258‐2015, for use as a ¹⁴³Nd/¹⁴⁴Nd isotope ratio reference has been prepared by the Institute of Geology, Chinese Academy of Geological Sciences, Beijing. Standardization Administration of the People's Republic of China provided the certification for this reference material. This report presents the reference ¹⁴³Nd/¹⁴⁴Nd isotope ratio and supporting production and certification procedures. The reference value was determined by an interlaboratory comparison of results from eleven participating laboratories using MC‐TIMS or MC‐ICP‐MS. The calibration of mass fractionation was conducted by using the exponential law, and the ¹⁴³Nd/¹⁴⁴Nd isotope ratios were normalised to the ¹⁴⁶Nd/¹⁴⁴Nd isotope ratio value of 0.7219. Isobaric interference of ¹⁴⁴Sm on ¹⁴⁴Nd was corrected using an interference‐free ¹⁴⁷Sm/¹⁴⁹Sm isotope ratio value for mass fractionation. GSB 04‐3258‐2015 shows sufficient homogeneity and stability for use as an international isotopic reference material. The certified value was calculated from the unweighted means of the results submitted by the participating laboratories. The ¹⁴³Nd/¹⁴⁴Nd isotope ratio value for GSB 04‐3258‐2015 is 0.512438, with a combined expanded uncertainty (k = 2) of 5 × 10^?6. Reference material GSB 04‐3258‐2015 is available upon request from the Institute of Geology, Chinese Academy of Geological Sciences, and may be used for accurate interlaboratory calibration of Nd isotope analysis.     

Sr and Nd isotope data of apatite,calcite and dolomite as indicators of source,and the relationships of phoscorites and carbonatites from the Kovdor massif,Kola peninsula,Russia

A detailed Sr−Nd isotopic study of primary apatite, calcite and dolomite from phoscorites and carbonatites of the Kovdor massif (380 Ma), Kola peninsula, Russia, reveals a complicated evolutionary history. At least six types of phoscorites and five types of carbonatite have been identified from Kovdor by previous investigators based on relative ages and their major and accessory minerals. Isotopic data from apatite define at least two distinct groups of phoscorite and carbonatite. Apatite from the earlier phoscorites and carbonatites (group 1) are characterized by relatively low⁸⁷Sr/⁸⁶Sr (0.70330–0.70349) and¹⁴³Nd/¹⁴⁴Nd initial ratios (0.51230–0.51240) with F=2.01–2.23 wt%, Sr=2185–2975 ppm, Nd=275–660 ppm and Sm=31.7–96.2 ppm. Apatite from the second group has higher⁸⁷Sr/⁸⁶Sr (0.70350–0.70363) and¹⁴³Nd/¹⁴⁴Nd initial ratios (0.51240–0.51247) and higher F (2.63–3.16 wt%), Sr (4790–7500 ppm), Nd (457–1074 ppm) and Sm (68.7–147.6 ppm) contents. This group corresponds to the later phoscorites and carbonatites. One apatite sample from a carbonatite from the earlier group fits into neither of the two groups and is characterized by the highest initial⁸⁷Sr/⁸⁶Sr (0.70385) and lowest¹⁴³Nd/¹⁴⁴Nd (0.51229) of any of the apatites. Within both groups initial⁸⁷Sr/⁸⁶Sr and¹⁴³Nd/¹⁴⁴Nd ratios show negative correlations. Strontium isotope data from coexisting calcite and dolomite support the findings from the apatite study. The Sr and Nd isotopic similarities between carbonatites and phoscorites indicate a genetic relationship between the two rock types. Wide variations in Sr and Nd isotopic composition within some of the earlier carbonatites indicate several distinct intrusive phases. Oxygen isotopic data from calcite and dolomite (δ¹⁸O=+7.2 to +7.7‰ SMOW) indicate the absence of any low-temerature secondary processes in phoscorites and carbonatites, and are consistent with a mantle origin for their parental melts. Apatite data from both groups of phoscorite plot in the depleted quadrant of an ε_Nd versus ε_Sr diagram. Data for the earlier group lie along the Kola Carbonatite Line (KCL) as defined by Kramm (1993) and data from the later group plot above the KCL. The evolution of the phoscorites and carbonatites cannot be explained by simple magmatic differentiation assuming closed system conditions. The Sr−Nd data can best be explained by the mixing of three components. Two of these are similar to the end-members that define the Kola Carbonatite Line and these were involved in the genesis of the early phoscorites and carbonatites. An additional component is needed to explain the isotopic characteristics of the later group. Our study shows that apatite from rocks of different mineralogy and age is ideal for placing constraints on mantle sources and for monitoring the Sr−Nd evolution of carbonatites. Editorial responsibility: W. Schreyer     

Barium isotopes in individual presolar silicon carbide grains from the Murchison meteorite

Barium isotopic compositions of single 2.3-5.3 μm presolar SiC grains from the Murchison meteorite were measured by resonant ionization mass spectrometry. Mainstream SiC grains are enriched in s-process barium and show a spread in isotopic composition from solar to dominantly s-process. In the relatively coarse grain size fraction analyzed, there are large grain-to-grain variations of barium isotopic composition. Comparison of single grain data with models of nucleosynthesis in asymptotic giant branch (AGB) stars indicates that the grains most likely come from low mass carbon-rich AGB stars (1.5 to 3 solar masses) of about solar metallicity and with approximately solar initial proportions of r- and s-process isotopes. Measurements of single grains imply a wide variety of neutron-to-seed ratios, in agreement with previous measurements of strontium, zirconium and molybdenum isotopic compositions of single presolar SiC grains.     

Geochemical variations in Andean basaltic and silicic lavas from the Villarrica-Lanin volcanic chain (39.5° S): an evaluation of source heterogeneity,fractional crystallization and crustal assimilation

At 39.5° S in the southern volcanic zone of the Andes three Pleistocene-recent stratovolcanoes, Villarrica, Quetrupillan and Lanin, form a trend perpendicular to the strike of the Andes, 275 to 325 km from the Peru-Chile trench. Basalts from Villarrica and Lanin are geochemically distinct; the latter have higher incompatible element abundances and La/Sm but lower Ba/La and alkali metal/La ratios. These differences are consistent with our previously proposed models involving: a) a west to east decrease in an alkali metal-rich, high Ba/La slab-derived component which causes an across strike decrease in degree of melting; or b) a west to east increase in the contamination of subduction-related magma by enriched subcontinental lithospheric mantle. Silicic and mafic lavas from the stratovolcanoes have overlapping Sr, Nd and O isotopic ratios. Silicic lavas also have geochemical differences that parallel those of their associated basalts, e.g., rhyolite from Villarrica has lower La/Sm and incompatible element contents than high-SiO₂ andesite from Lanin. At each volcano the most silicic lavas can be modelled by closed system fractional crystallization while andesites are best explained by magma mixing. Apparently crustal contamination was not an important process in deriving the evolved lavas. Basaltic flows from small scoria cones, 20–35 km from Villarrica volcano have high incompatible element contents and low Ba/La, like Lanin basalts, but trend to higher K/Rb (356–855) and lower ⁸⁷Sr/ ⁸⁶Sr (0.70361–0.70400) than basalts from either stratovolcano. However all basalts have similar Nd, Pb and O isotope ratios. The best explanation for the unique features of the cones is that the sources of SVZ magmas, e.g., slab-derived fluids or melts of the subcontinental lithospheric mantle, have varying alkali metal and radiogenic Sr contents. These heterogeneities are not manifested in stratovolcano basalts because of extensive subcrustal pooling and mixing. This model is preferable to one involving crustal contamination because it can account for variable Sr isotope ratios and uniform Nd and Pb isotope ratios among the basalts, and the divergence of the cones from across-strike geochemical trends defined by the stratovolcanoes.     

The geochemistry of potassic lavas from Vulsini,central Italy and implications for mantle enrichment processes beneath the Roman region

Major and trace element and ¹⁴³Nd/¹⁴⁴Nd (0.51209–0.51216) and ⁸⁷Sr/⁸⁶Sr (0.70879–0.71105) isotope analyses are presented on a representative group of lavas from the Vulsini district of the Roman magmatic province. Three distinct series are identified; the high-K and low-K series are similar to those described from other Italian volcanoes, while the third is represented by a group of relative ly undifferentiated leucite basanites which are thought to be near-primary mantle melts. Major and trace element variations within the high-K series are consistent with fractional crystallisation from a parental magma similar to the most magnesian leucitites. Crustal contamination resulted in an increase in ⁸⁷Sr/⁸⁶Sr with increasing fractionation, but it was superimposed on magmas which had already inherited a range of incompatible element and isotope ratios from enrichment processes in the sub-continental mantle. These are reviewed using the available results from Vulsini, Roccamonfina and Ernici. Transition element abundances and Ta/Yb ratios indicate that the pre-enrichment mantle was similar to that of E-type MORB, and that these elements were not mobilised by the enrichment process. Mixing calculations suggest that three components were involved in the enrichment process; mantle comparable with the source of MORB, and two other components rich in trace elements. One, the low-K component, had high Sr/Nd, Th/Ta and Ba/Nb and no europium anomaly while the second had lower Sr/Nd, a negative europium anomaly and very high Th/Ta. It was also characterised by low Nb/Ba and high Rb/Ba ratios, similar to those reported from phlogopite-rich peridotite xenoliths. The trace element enrichment processes are therefore thought to have occurred in the mantle wedge above a subduction zone with the trace element characteristics of the high-K end-member reflecting the subduction of sediments and the stabilisation of mantle phlogopite.     

Elemental and isotopic variations in subduction related basalts: evidence for a three component model

Subduction related basalts display wide ranges in large ion lithophile element ratios (e.g., Rb/Ba and Rb/ Sr) which are unlikely to result from mixing, but suggest a role for small degree partial melting of a relatively Rb-poor mantle wedge source. However, these variations do not correlate with other trace element criteria, such as the depletions of high field strength elements (HFSE) and light rare earth elements (LREE) relative to the LILE, which characterise subduction related magmatism. Integration of radiogenic isotope and trace element data demonstrates that the elemental enrichment cannot be simply related to two component mixtures inferred from isotopic variations. Thus a minimum of three components is required to describe the geochemistry of subduction zone basalts. Two are subduction related: high Sr/Nd material is derived from the dehydration of subducted basaltic ocean crust, and a low Sr/Nd component is thought to be from subducted terrigenous sediment. The third component is in the mantle wedge, it is usually similar to the source of MORB, particularly in its isotopic composition. However, in some cases, notably continental areas, more enriched mantle wedge material with relatively high ⁸⁷Sr/⁸⁶Sr, low ¹⁴³Nd/¹⁴⁴Nd and elevated incompatible trace element contents may be involved Mixing of these three components is capable of producing both the entire range of Sr, Nd and Pb isotope signatures observed in destructive margin basalts, and their distinctive trace element compositions. The isotope differences between Atlantic and Pacific island arc basalts are attributed to the isotope compositions of sediments in the two oceans.     

Case studies on the origin of basalt: III. Petrogenesis of the Mauna Ulu eruption,Kilauea, 1969–1971

During the Mauna Ulu flank eruption on Kilauea, Hawaii, the concentrations in the lavas of the minor elements K, P, Na and Ti, and the incompatible trace elements (analyzed by isotope dilution) K, Rb, Cs, Ba, Sr, and the REE (except Yb) decreased monotonically and linearly with the time (or date) of the eruption. At the same time, the concentrations of the major elements and of Yb, and the ratios of K/Rb, K/Cs, Ba/Rb, ⁸⁷Sr/⁸⁶Sr and ¹⁴³Nd/¹⁴⁴Nd remained constant. Most of the scatter in the raw concentration data is removed by a simple correction for olivine (plus chromite) fractionation previously established by Wright et al. (1975). These results are explained by simple equilibrium partial melting of a uniform source. The degree of melting increased by about 20% of the initial value during the course of the eruption. The trace element data are inverted by the method originated by Minster and Allègre (1978) and simplified by Hofmann and Feigenson (1983). The source has the following element (or isotope) ratios: K/Rb=501±7, Ba/Rb=14.0±0.5, Rb/Cs=95±7, Rb/Sr=0.0193 (+0.0045, –0.0090), (Ce/Ba)_CN= 1.1±0.1, (Sr/Ba)_CN=1.19 (+0.30, –0.19), ⁸⁷Sr/⁸⁶Sr=0.703521±0.000016, and ¹⁴³Nd/¹⁴⁴Nd=0.512966±0.000008. The REE pattern of the source has a nearly flat or slightly negative slope (=relative LREE enrichment) between Ce and Dy and a strongly positive slope between Dy and Yb. However, this relative HREE enrichment is poorly constrained by the analytical data, is highly model dependent and may not be a true source feature. The Yb concentration in the source is particularly poorly constrained because it is essentially constant in the melts. On the other hand, this special feature demonstrates that Yb must be buffered by a mineral phase with a high partition coefficient for Yb, namely garnet. The calculated clinopyroxene/garnet ratio in the source is roughly equal to one. In contrast, the source of Kohala volcano had previously been found to contain little or no garnet.     

Geochemistry and petrogenesis of carbonatites from South Nam Xe,Lai Chau area,northwest Vietnam

This paper presents a study of the petrography, mineral chemistry, geochemistry, and Sr–Nd–Pb–C–O isotope systematics of carbonatite dykes and associated rocks from the northeastern part of the Song Da intracontinental rift in South Nam Xe (northwest Vietnam) aimed at constraining the origin of the carbonatite magmas. The carbonatites are characterized by SiO₂ < 12.18 wt.% and by wide ranges in FeO, MgO and CaO content that define them as calciocarbonatite and ferrocarbonatite. On U–Th–Pb isochron diagrams, whole rocks and mineral separates from the ferrocarbonatites form linear arrays corresponding to ages of 30.2–31.6 Ma (Rupelian, Oligocene). The South Nam Xe carbonatites are extremely enriched in Sr, Ba, and light rare earth elements (LREE), and depleted in high field strength elements (HFSE) (e.g. Ti, Nb, Ta, Zr and Hf). The age–corrected Sr–Nd–Pb isotope ratios and C isotope data are relatively uniform (⁸⁷Sr/⁸⁶Sr_(t) = 0.708193–0.708349; ¹⁴³Nd/¹⁴⁴Nd_(t) = 0.512250–0.512267; ε_Nd(t) = ?6.46 to ?6.80; ²⁰⁶Pb/²⁰⁴Pb_(t) = 18.26–18.79; ²⁰⁷Pb/²⁰⁴Pb_(t) = 15.62–15.64; ²⁰⁸Pb/²⁰⁴Pb_(t) = 38.80–39.38; δ¹³C_V-PDB = –2.7?‰ to ?4.1?‰). These isotopic compositions indicate source contamination that occurred before the production of the carbonatite magmas, and did not change noticeably during or after emplacement. The variation in oxygen isotopes is consistent with the change in mineral compositions and trace element abundances: the lower δ¹⁸O values (9.1–11.0?‰) coupled with Sr-rich, Mn-poor calcite, and igneous textures such as triple junctions among calcite grain boundaries, define a magmatic origin. However, the elevated δ¹⁸O values of the ferrocarbonatites (12.0–13.3?‰) coupled with a volatile-bearing mineral assemblages (including REE fluorcarbonates, sulfates, sulfides and fluorite) may be due to interaction with meteoric water during low-temperature alteration. High δ¹³C values and Sr–Pb ratios, and low Rb/Sr (0.00014–0.00301), Sm/Nd (0.089–0.141) and ¹⁴³Nd/¹⁴⁴Nd ratios, coupled with very high Sr-Nd concentrations, suggest the involvement of an enriched mantle component, which probably resulted from metasomatism due to the migration of subducted material. Because of the lack of tectonic data and the limited number of samples studied, this conclusion is still ambiguous and requires further study.