Hafnium isotope results from mid-ocean ridges and Kerguelen

¹⁷⁶Hf/¹⁷⁷Hf ratios are presented for oceanic volcanics representing both extremes of the range of mantle HfNdSr isotopic variation. Hf from critical mid-ocean ridgebasalts shows that ¹⁷⁶Hf/¹⁷⁷Hf does indeed have a greater variability than ¹⁴³Nd/¹⁴⁴Nd and ⁸⁷Sr/⁸⁶Sr in the depleted mantle. This extra variation is essentially of a random nature, and can perhaps be understood in terms of known Rb/SrSm/NdLu/Hf fractionation relationships. At the other extreme of mantle isotopic composition, ¹⁷⁶Hf/¹⁷⁷Hf ratios for igneous rocks from the Indian Ocean island of Kerguelen show a closely similar variation to published ¹⁴³Nd/¹⁴⁴Nd ratios for the same samples. Comparison of HfNdSr c relationships for Tristan da Cunha, Kerguelen and Samoa reveals divergences in the mantle array for ocean island magma sources, and perhaps suggests that these irregularities are largely the result of an extra component of ⁸⁷Sr/⁸⁶Sr variation.     

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.     

Provenance of Paleozoic–Mesozoic sedimentary rocks in the Inner Zone of Southwest Japan: An evaluation based on Nd model ages

Nd model ages using depleted mantle (TDM) values for the sedimentary rocks in the Inner Zone of the SW Japan and western area of Tanakura Tectonic Line in the NE Japan allow classification into five categories: 2.6–2.45, 2.3–2.05, 1.9–1.55, 1.45–1.25, and 1.2–0.85 Ga. The provenance of each terrane/belt/district is interpreted on the basis of the TDMs, ¹⁴⁷Sm / ¹⁴⁴Nd vs. ¹⁴³Nd / ¹⁴⁴Nd relation, Nd isotopic evolution of the source rocks in East China and U–Pb zircon ages. The provenance of 2.6–1.8 Ga rocks, which are reported from Hida–Oki and Renge belts and Kamiaso conglomerates, is inferred to be the Sino–Korean Craton (SKC). The 2.3–1.55 Ga rocks, mostly from Ryoke, Mino and Ashio belts, are originally related with the SKC and/or Yangtze Craton (YC). The provenances of the sedimentary rocks with 1.45–0.85 Ga, from the Suo belt, Higo and some districts in the Mino and Ashio belts, are different from the SKC and YC. Especially, the Higo with 1.2–0.85 Ga is considered as a fragment of collision zone in East China. Akiyoshi belt probably belongs to the youngest age category of 1.2–0.85 Ga.Some metasedimentary rocks from the Ryoke belt have extremely high ¹⁴⁷Sm / ¹⁴⁴Nd and ¹⁴³Nd / ¹⁴⁴Nd ratios, whose main components are probably derived from mafic igneous rocks within the Ryoke belt itself and from the adjacent Tamba belt.     

Metal sources of the Navan carbonate-hosted base metal deposit, Ireland: Nd and Sr isotope evidence for deep hydrothermal convection

Nd and Sr isotope analyses are presented for gangue mineral samples from the giant carbonate-hosted Navan Zn–Pb deposit, Ireland, and for rocks from which Navan metals may have been derived. Analysis of gangue minerals spanning the Navan paragenetic sequence reveals systematic evolution in the composition of the mineralising fluid. Early fluid represented by replacive dolomite exhibits the lowest initial ⁸⁷Sr/⁸⁶Sr ratio (0.7083–0.7086), closest to that of the host limestone and to Lower Carboniferous seawater, and the highest ¹⁴³Nd/¹⁴⁴Nd ratio (0.51161–0.51176). Later generations of dolomite, barite and calcite, which encompass sulphide precipitation, have higher initial ⁸⁷Sr/⁸⁶Sr ratios (maximum 0.7105) and lower initial ¹⁴³Nd/¹⁴⁴Nd ratios (minimum 0.51157). All samples have initial Nd isotope ratios that are too low to have been acquired only from the host limestone. Drill core samples of presumed Ordovician volcanic and sedimentary rocks from beneath the Navan orebody have ¹⁴³Nd/¹⁴⁴Nd and ⁸⁷Sr/⁸⁶Sr ratios at the time of mineralisation of 0.51184–0.51217 and 0.7086–0.7138, respectively. The data are interpreted to indicate mixing of sulphide-rich, limestone-buffered brine, with a metal-bearing hydrothermal fluid, which had passed through sub-Carboniferous rocks, consistent with published fluid inclusion and S isotope data. The ¹⁴³Nd/¹⁴⁴Nd ratio of this basement-derived fluid is too low to have been imparted by flow through the Devonian Old Red Sandstone, as required in models of regional fluid flow in response to Hercynian uplift. Irrespective of whether such regional fluid flow occurred, the hydrothermal Nd must have been derived from sub-Devonian rocks. These conclusions broadly support the hydrothermal convection cell model in which brines, ultimately of surface origin, penetrated to a depth of several kilometres, leaching metals from the rocks through which they passed. The data also support increasing depth of penetration of convection cells with time. Metals were subsequently precipitated in carbonate rocks at sites of mixing with cooler, sulphide-rich fluids. However, comparison of the Navan hydrothermal gangue Nd–Sr isotope data with data from Lower Palaeozoic rocks strongly suggests that the latter cannot alone account for the “basement” signature. As the Navan deposit lies immediately north of the Iapetus Suture, this suggests that the Laurentian margin includes Precambrian basement.     

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.     

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.     

Geochemical and Mineral Characteristics of Jurassic Volcanic Rocks from ODP Sites 304, 1149, and 801: Implications for Magmatic Evolution in the Northwest Pacific

The regular variations in magmatic activities along the Northwest Pacific plate have been little studied in spite of their importance. In this contribution, systematic analyses were conducted on tholeiitic basalts from three Ocean Drilling Program sites (Sites 304, 1149, and 801), including the petrographic features, major and trace elements, Nd isotopic compositions, and mineral structure and compositions of whole rocks. Volcanic rocks from Sites 304, 1149, and 801 belong to tholeiites and exhibit depleted light rare earth elements (LREE), large ion lithophile elemental contents (LILE), and relatively depleted Nd isotopic ratios (143Nd/144Nd=0.513139–0.513211), similar to those of normal mid-ocean ridge basalts (N-MORB). Comprehensive data on mineral compositions, whole-rock geochemistry, and geochronology demonstrate that a regular variation trend exists in the north-south direction along the Northwest Pacific plate. The 143Nd/144Nd values (0.513139–0.513211) and trace-element ratios for whole rocks (Sm/Th=15.35–30.00; Zr/Hf=28.53–35.76; Zr/Y=2.58–3.67; Th/La=0.04–0.06; Th/Y=0.33–0.70), as well as the trace-element ratios (Zr/Hf, La/Yb, Ti/Zr) of clinopyroxenes from Sites 1149 and 801 tholeiites show larger variations compared to those from Site 304 tholeiites (143Nd/144Nd=0.513185–0.513195; Sm/Th=18.19–20.58; Zr/Hf=31.07–33.26; Zr/Y=2.62–3.03; Th/La=0.05–0.06; Th/Y=0.48–0.57). Mineral zoning textures were obvious in tholeiites from Sites 1149 and 801 but were rarely observed in Site 304. These regular features were likely attributed to the differences in the heterogeneity of the magma source, the process of magmatic evolution, the plate-spreading rate, and the effective and ineffective mixing.     

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.     

Magma genesis in the New Britain island-arc: Constraints from Nd and Sr isotopes and trace-element patterns

A selected suite of fresh volcanic rocks from the New Britain island arc has been analyzed for ¹⁴³Nd/¹⁴⁴Nd, ⁸⁷Sr/⁸⁶Sr, major and trace elements to investigate relationships between isotopes, trace elements and petrology, and depth to the underlying Benioff zone. From these relationships inferences about magma generation are made utilizing Nd and Sr isotope systematics in possible source materials. Lavas ranging in composition from basalt to rhyolite show minimal variation of ¹⁴³Nd/¹⁴⁴Nd. Small variations in ⁸⁷Sr/⁸⁶Sr do not correlate with depth to the Benioff zone, but are related to magma type. Nd-Sr isotopes suggest that island arc lavas in general are derived from a mixture of suboceanic mantle and hydrothermally altered mid-ocean ridge-type basalt, but the New Britain magma source appears homogeneous with little indication of either the involvement of oceanic crust or mantle inhomogeneity. Trace element patterns in New Britain lavas are not consistent with Nd isotope data for currently accepted petrologic and trace element models of magma genesis. Mafic lavas from New Britain and other island arcs have anomalously high Sr/Nd, possibly due to components derived from subducted oceanic crust.     

High Precision Sr‐Nd‐Hf‐Pb Isotopic Compositions of USGS Reference Material BCR‐2

The Lamont‐Doherty Earth Observatory radiogenic isotope group has been systematically measuring Sr‐Nd‐Pb‐Hf isotopes of USGS reference material BCR‐2 (Columbia River Basalt 2), as a chemical processing and instrumental quality control monitor for isotopic measurements. BCR‐2 is now a widely used geochemical inter‐laboratory reference material (RM), with its predecessor BCR‐1 no longer available. Recognising that precise and accurate data on RMs is important for ensuring analytical quality and for comparing data between different laboratories, we present a compilation of multiple digestions and analyses made on BCR‐2 during the first author's dissertation research. The best estimates of Sr, Nd and Hf isotope ratios and measurement reproducibilities, after filtering at the 2s level for outliers, were ⁸⁷Sr/⁸⁶Sr = 0.705000 ± 11 (2s, 16 ppm, n = 21, sixteen digestions, one outlier), ¹⁴³Nd/¹⁴⁴Nd = 0.512637 ± 13 (2s, 25 ppm, n = 27, thirteen digestions, one outlier) and ¹⁷⁶Hf/¹⁷⁷Hf = 0.282866 ± 11 (2s, 39 ppm, n = 25, thirteen digestions, no outliers). Mean Nd and Hf values were within error of those reported by Weis et al. (2006, 2007) in their studies of RMs; mean Sr values were just outside the 2s uncertainty range of both laboratories. Moreover, a survey of published Sr‐Nd‐Hf data shows that our results fall within the range of reported values, but with a smaller variability. Our Pb isotope results on acid leached BCR‐2 aliquots (n = 26, twelve digestions, two outliers) were ²⁰⁶Pb/²⁰⁴Pb = 18.8029 ± 10 (2s, 55 ppm), ²⁰⁷Pb/²⁰⁴Pb = 15.6239 ± 8 (2s, 52 ppm), ²⁰⁸Pb/²⁰⁴Pb = 38.8287 ± 25 (2s, 63 ppm). We confirm that unleached BCR‐2 powder is contaminated with Pb, and that sufficient leaching prior to digestion is required to achieve accurate values for the uncontaminated Pb isotopic compositions.     

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.     

Patterns of Nd and Sr isotopic ratios produced by magmatic and post-magmatic processes in the Shiant Isles Main Sill, Scotland

The Shiant Isles Main Sill of the British Tertiary Igneous Province is a classic example of a differentiated, alkaline basic sill. Four separate intrusions, each emplaced internally in rapid succession, form a 165-m-thick sill hosted by Lower Jurassic sedimentary rocks. Extensive Nd and Sr isotopic studies were conducted on samples from a vertical section through the sill where the relationships of samples to one another are well defined. The results illuminate patterns of modification of isotopic ratios and clarify the petrogenesis (magma sources, crustal contamination), magmatic processes (bulk mixing, interstitial liquid mixing), and post-magmatic alteration (hydrothermal effects on Sr and Nd). Overall, the whole-rock initial ⁸⁷Sr/⁸⁶Sr ratios range from ∼0.7037 to 0.7061 while initial ¹⁴³Nd/¹⁴⁴Nd ratios vary from ∼0.51243 to 0.51286 (ɛ_Nd∼−0.7 to +5.7) – values that contrast markedly with those of the country rock. Acid leaching (HCl) of the whole-rock samples that removes analcime indicates that most of the scatter in the ⁸⁷Sr/⁸⁶Sr is caused by the ubiquitous sub-solidus, aqueous alteration during which more-radiogenic Sr was introduced into the sill, especially along the margins, and also reveals magmatic isotopic ratios. In contrast, Nd was immobile during fluid interaction so that the sill ¹⁴³Nd/¹⁴⁴Nd ratios were not affected, even <1 m from the country-rock contact. Using leached rock values, ⁸⁷Sr/⁸⁶Sr and ¹⁴³Nd/¹⁴⁴Nd ratios are inversely correlated from magmatic processes. Magmas with two distinct isotopic compositions were involved: a more primitive one with ¹⁴³Nd/¹⁴⁴Nd ∼0.51285 and ⁸⁷Sr/⁸⁶Sr ∼0.7035 that produced the first two intrusions and a more evolved one (with 0.51252 and 0.7048) that produced the third intrusion. Mixing of the two magmas was very limited, restricted to near contacts between units, and apparently occurred by interstitial melt migration. The more evolved crinanitic magma was probably produced from a batch of the more primitive picritic melt by a small degree of crustal contamination and crystal fractionation during a short crustal residence prior to ascent and emplacement. Received: 20 December 1999 / Accepted: 5 May 2000     

Determination of Hf–Sr–Nd isotopic ratios by MC-ICP-MS using rapid acid digestion after flux-free fusion in geological materials

In this study, we established a rapid acid digestion for determining Hf–Sr–Nd isotopic ratios of geological samples by using MC-ICP-MS. Conditions of 1600 °C for 1 min and 1400 °C for 1 min were adopted for fusing intrusive rocks and extrusive rocks, respectively. The rapid acid digestion technique is superior in digestion time compared with high-pressure PTFE bomb method. The procedural blanks of the method were also lower than that flux fusion. Replicate analyses of international certified reference materials (CRMs) indicate that isotopic ratios of ¹⁷⁶Hf/¹⁷⁷Hf, ⁸⁷Sr/⁸⁶Sr and ¹⁴³Nd/¹⁴⁴Nd agree well with previously published data. The external reproducibility (2SD, n = 5) of ten CRMs are ±0.000030 for ⁸⁷Sr/⁸⁶Sr, ±0.000030 for ¹⁴³Nd/¹⁴⁴Nd, and ±0.000018 for ¹⁷⁶Hf/¹⁷⁷Hf.     

湘西渣滓溪钨锑矿床白钨矿的Sm-Nd和Sr同位素地球化学

渣滓溪钨锑矿床位于湘西雪峰山弧形构造带的中段,是我国典型的脉状充填型锑矿床。本文对渣滓溪矿区不同产状产出的白钨矿进行了Sm-Nd和Sr同位素研究。研究表明,渣滓溪矿区白钨矿Sm/Nd变化范围相对较宽（0.36~0.63）,143Nd/144Nd为0.51211~0.51288;在147Sm/144Nd-143Nd/144Nd图解中,该矿白钨矿样品没有明显的线性分布趋势,无法厘定出该矿的准确成矿时间。该矿白钨矿的Nd(t)明显可分为两组（-10.2~-14.7和-3.79~+0.01）,其成矿流体中的Nd主要有两个来源,一部分可能来自晚元古代地层或下伏陆壳基底的碎屑岩,另一部分很可能与冷家溪群的基性、超基性岩有关。与Nd同位素不同,渣滓溪成矿流体中Sr同位素组成均一化程度较高,该矿白钨矿87Sr/86Sr为0.7304~0.7329;该矿这种明显富放射成因87Sr的成矿热液,排除了成矿流体来自海水和赋矿围岩作为唯一矿源层的可能性,下伏陆壳的结晶基底很可能是这种高放射成因Sr的提供者。沃溪和渣滓溪矿区白钨矿Sr-Nd同位素组成的对比研究表明,两矿区的成矿物质来源有所不同,前者应来自一种更古老、更成熟、更富放射成因Sr的下伏陆壳基底。     

Fluorite as an Sm–Nd geochronometer of hydrothermal processes: Dating of mineralization hosted in the Strel’tsovka uranium ore field,eastern Baikal region

The possibility of using hydrothermal fluorite as an Sm–Nd geochronometer is based on the results of an REE pattern study of this mineral (Chernyshev et al., 1986). As a result of REE fractionation, in many cases, the Sm/Nd ratio achieves a multifold increase compared with its level in terrestrial rocks, and the radiogenic shift of the ¹⁴³Nd/¹⁴⁴Nd isotope ratio reaches 10–20 ε_Nd units over a short time interval (as soon as tens of Ma). This is a necessary prerequisite for Sm–Nd isochron dating of fluorite. Zonal polychrome fluorite from a vein referred to the final stage of large-scale uranium mineralization at the Sterl’tsovka deposit in the ore field of the same name located in the eastern Transbaikal region has been dated using the ¹⁴³Nd/¹⁴⁴Nd method. To optimize isochron construction, local probes with high and contrasting Sm/Nd ratios have been sampled from the polished surfaces of two samples, taking into account the REE pattern of zonal fluorite. Sm–Nd isochron dating has been carried out separately for each sample. The ¹⁴⁷Sm/¹⁴⁴Nd и ¹⁴³Nd/¹⁴⁴Nd ratios vary within the intervals 0.5359–2.037 and 0.512799–0.514105, respectively. Two isochrons, each based on six fluorite probes, have been obtained with the following parameters, which coincide within 2σ uncertainty limits: (1) t = 134.8 ± 1.3 Ma, (¹⁴³Nd/¹⁴⁴Nd)₀ = 0.512310 ± 13, MWSD = 0.43 and (2) t = 135.8 ± 1.6 Ma, (¹⁴³Nd/¹⁴⁴Nd)₀ = 0.512318 ± 10, MWSD = 1.5. The mean age of fluorite based on two isochron datings is 135.3 ± 1 Ma. Comparison of this value with the most precise dating of pitchblende related to the ore stage in the Strel’tsovka ore field (135.5 ± 1 Ma) shows that four mineralization stages, distinguished by geological and mineralogical data, that were completed with the formation of polychrome fluorite veins 135.3 ± 1 Ma ago, represent a single and indivisible hydrothermal process whose duration does not exceed 1 Ma.     

Constraints from geochemistry and Sr–Nd isotopes for the origin of albitite deposits from Central Sardinia (Italy)

Major- and trace-element contents and Sr–Nd isotope ratios were determined in albitite, albitized and unaltered late-Variscan granitoid samples from the world-class Na-feldspar deposits of central Sardinia, Italy. The albite deposit of high economic grade has geological, textural, and chemical features typical of metasomatic alteration affecting the host granitoids. Albitization, locally accompanied by chloritization and epidotization, was characterized by strong leaching of Mg, Fe, K, and geochemically similar trace elements, and by a significant increase of Na. Ca, and P were moderately leached in the most metasomatized rocks. Other major (Si, Ti, Ca) and trace elements (U, Th, Y, and Zr), along with light (LREE) and middle (MREE) rare-earth elements, behaved essentially immobile at the deposit scale. The Nd-isotope ratios (0.512098 to 0.512248) do not provide information on the emplacement age of the unaltered late-Variscan granitoids. On the other hand, their Sr-isotope ratios fit an errorchron of 274±29 Ma (1σ error), in fair agreement with all published ages of Sardinian Variscan granitoids. The very low Rb content of albitized rocks precludes application of the Rb–Sr radiometric system to determine the age of albitization. The Sm–Nd system is not applicable either, because the ¹⁴³Nd/¹⁴⁴Nd ratios of albitized rocks and unaltered granitoids overlap. The overlap confirms that Sm and Nd were substantially immobile during albitization. On the other hand, the measured ⁸⁷Sr/⁸⁶Sr ratios of the albitized rocks are appreciably lower than those of the unaltered host granitoids, whereas, their initial Sr-isotope ratios are higher. This seems to suggest that a) albitization was induced by non-magmatic fluids rich in radiogenic Sr, and b) albitization occurred shortly after the granitoid emplacement. This conclusion is supported by Nd isotopes, because unaltered granitoids and albitites fit the same reference isochron at 274 Ma. The fluids acquired radiogenic Sr by circulation through the Lower Paleozoic metasedimentary basement. Specifically, it is estimated that Sr supplied by the non-carbonatic basement represents about 22 wt% of total Sr in albitite.     

Determination of Sm‐Nd Isotopic Compositions in Fifteen Geological Materials Using Laser Ablation MC‐ICP‐MS and Application to Monazite Geochronology of Metasedimentary Rock in the North China Craton

In this study, we report both ¹⁴³Nd/¹⁴⁴Nd and ¹⁴⁷Sm/¹⁴⁴Nd values in twelve minerals (apatite, titanite, monazite and eudialyte) based on analyses over 4 years using LA‐MC‐ICP‐MS. The positive correlation between the measured β_Sm and β_Nd (r² = 0.9981) over this time in our laboratory demonstrates the excellent long‐term stability of the method. Compared with the normal method, Sm and Nd signal intensities were improved by a factor of 2.9 with the use of X skimmer and Jet sample cones in combination with the addition of nitrogen at 3–6 ml min^?1 to the central gas flow. The enhancement of signal intensity benefits the accurate in situ determination of the Sm‐Nd isotopes of samples poor in these elements. ¹⁴³Nd/¹⁴⁴Nd values were also determined in two manganese nodules and GSMC Co‐rich crust with low mass fractions of Nd (94–293 μg g^?1). Generally, most of the obtained Sm‐Nd isotopic compositions in these geological materials are consistent with published values. ‘External reproducibility’ (2s) of ¹⁴³Nd/¹⁴⁴Nd and ¹⁴⁷Sm/¹⁴⁴Nd was typically better than 0.06‰ and 2.5‰, respectively, demonstrating that the Durango, Otter Lake, NW‐1 and MAD apatites, the Khan, and OLT‐1 titanites, MGMH#117531 monazite and LV01 eudialyte are promising candidate reference materials for in situ Sm‐Nd isotopic determinations. The Trebilcock, Mae Klang and 44069 monazites are only suitable for in situ Nd isotopic determinations because of their heterogeneous Sm/Nd compositions. The heterogeneous Sm‐Nd composition of titanite BLR‐1 demonstrates that it is not a suitable reference material for in situ Sm‐Nd isotopic determinations. Deep‐sea samples (NOD‐A‐1 and NOD‐P‐1 manganese nodule, GSMC Co‐rich crust) with low mass fractions of Nd also show homogenous Nd isotopic compositions. Sm‐Nd isotopic ratios of a monazite (MQG‐22) from the North China Craton were measured as a case study and gave a ¹⁴⁷Sm‐¹⁴³Nd isochron age of 1792 ± 35 Ma (MSWD = 3.2) consistent with the published metamorphic age of the host metasedimentary rocks. The results for both candidate reference materials and geological samples demonstrate that the in situ LA‐MC‐ICP‐MS analytical protocol described is feasible and robust for research in geological evolution.     

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.     

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.     

Sr,Nd, and Hf Isotope Composition of Rocks of the Reft Gabbro–Diorite–Tonalite Complex (Eastern Slope of the Middle Urals): Petrological and Geological Implications

This paper reports Rb–Sr and Sm–Nd isotope data on the gabbro–diorite–tonalite rock association of the Reft massif (eastern margin of the Middle Urals) and Lu–Hf isotope data on zircon populations from these rocks. In terms of Nd and Hf isotope composition, the rocks of the studied association are subdivided into two distinctly different groups. The first group consists of gabbros and diorites, as well as plagioclase granites from thin dikes and veins cutting across the gabbros. In terms of ⁴³Nd/¹⁴⁴Nd _i = 0.512518–0.512573 (ε_Nd(T) = +8.6...+9.7) and ¹⁷⁶Hf/¹⁷⁷Hf _i = 0.282961–0.283019 (ε_Hf(T) = +15.9...+17.9), these rocks are practically identical to depleted mantle. Their Nd and Hf model ages show wide variations, but in general are close to their crystallization time. The second group is represented by tonalites and quartz diorites, which compose a large body occupying over half of the massif area. These rocks are characterized by the lower values of ¹⁴³Nd/¹⁴⁴Nd _i = 0.512265–0.512388 (ε_Nd(T) = +3.7...+6.0) and ¹⁷⁶Hf/¹⁷⁷Hf _i = 0.282826–0.282870 (ε_Hf(T) = +11.1...+12.7). The T_DM values of the second group are much (two–three times) higher than their geological age (crystallization time), which indicates sufficiently long crustal residence time of their source. The initial ⁸⁷Sr/⁸⁶Sr in the rocks of both the groups varies from 0.70348 to 0.70495. This is likely explained by the different saturation of melts with fluid enriched in radiogenic Sr. The source of this fluid could be seawater that was buried in a subduction zone with oceanic sediments and released during slab dehydration. Obtained data make it possible to conclude that the formation of the studied gabbro–diorite–tonalite association is a result of spatially and temporally close magma formation processes in the crust and mantle, with insignificant contribution of differentiation of mantle basite magma.