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.     

Nd and Sr isotope compositions in modern and fossil bones - Proxies for vertebrate provenance and taphonomy

Rare earth elements (REE), while not essential for the physiologic functions of animals, are ingested and incorporated in ppb concentrations in bones and teeth. Nd isotope compositions of modern bones of animals from isotopically distinct habitats demonstrate that the ¹⁴³Nd/¹⁴⁴Nd of the apatite can be used as a fingerprint for bedrock geology or ambient water mass. This potentially allows the provenance and migration of extant vertebrates to be traced, similar to the use of Sr isotopes. Although REE may be enriched by up to 5 orders of magnitude during diagenesis and recrystallization of bone apatite, in vivo¹⁴³Nd/¹⁴⁴Nd may be preserved in the inner cortex of fossil bones or enamel. However, tracking the provenance of ancient or extinct vertebrates is possible only for well-preserved archeological and paleontological skeletal remains with in vivo-like Nd contents at the ppb-level. Intra-bone and -tooth REE analysis can be used to screen for appropriate areas. Large intra-bone Nd concentration gradients of 10¹-10³ are often measured. Nd concentrations in the inner bone cortex increase over timescales of millions of years, while bone rims may be enriched over millenial timescales. Nevertheless, ε_Nd values are often similar within one ε_Nd unit within a single bone. Larger intra-bone differences in specimens may either reflect a partial preservation of in vivo values or changing ε_Nd values of the diagenetic fluid during fossilization. However, most fossil specimens and the outer rims of bones will record taphonomic ¹⁴³Nd/¹⁴⁴Nd incorporated post mortem during diagenesis. Unlike REE patterns, ¹⁴³Nd/¹⁴⁴Nd are not biased by fractionation processes during REE-uptake into the apatite crystal lattice, hence the ε_Nd value is an important tracer for taphonomy and reworking. Bones and teeth from autochthonous fossil assemblages have small variations of ±1 ε_Nd unit only. In contrast, fossil bones and teeth from over 20 different marine and terrestrial fossil sites have a total range of ε_Nd values from -13.0 to 4.9 (n = 80), often matching the composition of the embedding sediment. This implies that the surrounding sediment is the source of Nd in the fossil bones and that the specimens of this study seem not to have been reworked. Differences in ε_Nd values between skeletal remains and embedding sediment may either indicate reworking of fossils and/or a REE-uptake from a diagenetic fluid with non-sediment derived ε_Nd values. The latter often applies to fossil shark teeth, which may preserve paleo-seawater values. Complementary to ε_Nd values, ⁸⁷Sr/⁸⁶Sr can help to further constrain the fossil provenance and reworking.     

Models of diffusion-limited uptake of trace elements in fossils and rates of fossilization

Many fossils are assumed to take up trace elements by a process of combined diffusion plus adsorption (DA), yet in principle composition profiles can be explained by several different diffusion-limited processes, including diffusion plus reaction or recrystallization (DR) and double-medium diffusion (DMD). The DA and DMD models are supported by REE and U composition profiles across fossil teeth, measured by laser-ablation ICP-MS, that show error-function - like diffusion profiles into enamel from the dentine-enamel interface and concentrations in the interior of enamel that are at original biogenic levels or higher. Published composition and age profiles in some Pleistocene bones may be better explained by a DR model. All three diffusion models imply linear behavior between age and distance squared, vastly simplifying U-series dating methods for Pleistocene fossils. Modeled uptake rates for fossil teeth yield a strict minimum bound on durations of about one decade to one century. The similarity of diffusion profiles in teeth, irrespective of depositional ages ranging from ∼30 ka to >30 Ma, implies that uptake occurred quickly, with a maximum duration of a few tens of kyr for typical fossil enamel; faster uptake is implied for typical fossil bone and dentine. Disparities in these uptake estimates compared to some archeological bone may reflect sampling and preservation bias for paleontological vs. archeological materials.     

SHRIMP U-Pb dating, trace elements and the Lu-Hf isotope system of coesite-bearing zircon from amphibolite in the SW Sulu UHP terrane, eastern China

In this study, we link mineral inclusion data, trace element analyses, U-Pb age and Hf isotope composition obtained from distinct zircon domains of complex zircon to unravel the origin and multi-stage metamorphic evolution of amphibolites from the Sulu ultrahigh-pressure (UHP) terrane, eastern China. Zircon grains separated from amphibolites from the CCSD-MH drill hole (G12) and Niushan outcrop (G13) were subdivided into two main types based on cathodoluminescence (CL) and Laser Raman spectroscopy: big dusty zircons with inherited cores and UHP metamorphic rims and small clear zircons. Weakly zoned, grey-white luminescent inherited cores preserve mineral inclusions of Cpx + Pl + Ap ± Qtz indicative of a mafic igneous protolith. Dark grey luminescent overgrowth rims contain the coesite eclogite-facies mineral inclusion assemblage Coe + Grt + Omp + Phe + Ap, and formed at T = 732-839 °C and P = 3.0-4.0 GPa. In contrast, white luminescent small clear zircons preserve mineral inclusions formed during retrograde HP quartz eclogite to LP amphibolite-facies metamorphism (T = 612-698 °C and P = 0.70-1.05 GPa). Inherited zircons from both samples yield SHRIMP ²⁰⁶Pb/²³⁸U ages of 695-520 Ma with an upper intercept age of 800 ± 31 Ma. The UHP rims yield consistent Triassic ages around 236-225 and 239-225 Ma for G12 and G13 with weighted means of 229 ± 3 and 231 ± 3 Ma, respectively. Small clear zircons from both samples give ²⁰⁶Pb/²³⁸U ages around 219-210 Ma with a weighted mean of 214 ± 3 Ma, interpreted as the age of retrograde quartz eclogite-facies metamorphism. Matrix amphibole from both samples indicate Ar-Ar ages of 209 ± 0.7 and 207 ± 0.7 Ma, respectively, probably dating late amphibolite-facies retrogression. The data suggest subduction of Neoproterozoic mafic igneous rocks to UHP conditions in Middle Triassic (∼230 Ma) times and subsequent exhumation to an early HP (∼214 Ma) and a late LP stage (∼208 Ma) over a period of ∼16 and 6 Myr, respectively. Thus, early exhumation from a mantle depth of 120-100 km to about 60 km occurred at an average rate of 0.3 cm/y, while subsequent exhumation to a middle crustal level took place at approximately 0.54 cm/y. These exhumation rates are considerably slower than those obtained for UHP rocks in the Dora Maira and Kokchetav massifs (2-3 cm/y).Based on similar P-T estimates and trace element and Hf isotope compositions, Sulu amphibolites can be identified as retrograde UHP eclogites. The εHf₍₈₀₀₎ of +8 implies a significant input from the depleted mantle to the Sulu-Dabie terrane during the middle Neoproterozoic. Overgrown rims are characterized by a distinct trace element composition with low Lu/Hf and Th/U and significantly higher ¹⁷⁶Hf/¹⁷⁷Hf ratios than inherited cores, consistent with formation during/after garnet (re-)crystallization and fractionation of the Lu-Hf system during UHP metamorphism. The combined dataset suggests homogenization of the ¹⁷⁶Hf/¹⁷⁷Hf ratio within the metamorphic mineral assemblage and during protolith formation. Observed variations are explained by mixing of material from both domains during laser ablation, e.g., due to partial recrystallization of inherited cores.     

High-resolution records of location and stratigraphic provenance from the rare earth element composition of fossil bones

Bone apatite acts as a natural, timed sampling device, scavenging trace elements from local pore waters over timescales of ca. 1-50 ka. The rare earth element (REE) and U/Th composition of fossil bones reflects associated pore water compositions during the period of recrystallisation. The REE composition of fossil bones is controlled by partitioning of REE between pore waters and particle surfaces, and the REE composition of fossil bones reflects the REE composition of pore waters which vary spatially and temporally. Light REE are preferentially sorped onto particle surfaces, thus the high La/Yb values seen in many bones from coastal marine and aeolian environments are best explained by release of REE from light REE-enriched particles to local pore waters and subsequent immobilisation in recrystallising bones. The REE compositions of bones recovered from pedogenically altered diatomite sediments of the Olorgesailie Formation of southern Kenya vary over spatial scales of less than 10 m. Location accounts for 48% of the observed variation in bone chemistry and bones recovered from eight discrete excavations within the same time-equivalent stratigraphic layer can be assigned to their excavation location with >70% accuracy based on a discriminant analysis of REE, U, and Th composition. Despite this within-layer variation, bones recovered from different stratigraphic horizons within the Olorgesailie Formation can also be distinguished on the basis of their trace element composition. Bones recovered from four stratigraphic horizons spanning ca. 0.5 million years were assigned to their correct stratigraphic layer with >90% accuracy. Where sedimentological conditions are favourable, the trace element composition of fossil bone may be used to test stratigraphic provenance and burial location in excavated bone with a temporal resolution of <10 ka and a spatial resolution of <10 m. The trace element composition of fossil bone may also be used to investigate the accumulation history of vertebrate assemblages and to reconstruct pore water variability across land surfaces.     

U-Pb, Hf and O isotope evidence for two episodes of fluid-assisted zircon growth in marble-hosted eclogites from the Dabie orogen

A combined study of internal structure, U-Pb age, and Hf and O isotopes was carried out for metamorphic zircons from ultrahigh-pressure eclogite boudins enclosed in marbles from the Dabie orogen in China. CL imaging identifies two types of zircon that are metamorphically new growth and recrystallized domain, respectively. The metamorphic zircons have low Th and U contents with low Th/U ratios, yielding two groups of ²⁰⁶Pb/²³⁸U age at 245 ± 3 to 240 ± 2 Ma and 226 ± 4 to 223 ± 2 Ma, respectively. Anomalously high δ¹⁸O values were obtained for refractory minerals, with 9.9 to 21.4‰ for garnet and 16.9‰ for zircon. This indicates that eclogite protolith is sedimentary rocks capable of liberating aqueous fluid for zircon growth during continental subduction-zone metamorphism. Most of the zircons are characterized by very low ¹⁷⁶Lu/¹⁷⁷Hf ratios of 0.000001-0.000028, indicating their growth in association with garnet recrystallization. A few of them falling within the older age group have comparatively high ¹⁷⁶Lu/¹⁷⁷Hf ratios of 0.000192-0.000383, suggesting their growth prior to the formation of garnet in the late stage of subduction. The variations in the Lu/Hf ratios for zircons can thus be used to correlate with garnet growth during eclogite-facies metamorphism. In either case, the zircons have variable ε_Hf (t) values for individual samples, suggesting that their protolith is heterogeneous in Hf isotope composition with localized fluid availability in the bulk processes of orogenic cycle. Nevertheless, a positive correlation exists between ²⁰⁶Pb/²³⁸U ages and Lu-Hf isotope ratios for the metamorphically recrystallized zircons, suggesting that eclogite-facies metamorphism in the presence of fluid has the identical effect on zircon Lu-Hf and U-Th-Pb isotopic systems. We conclude that the zircons of the older group grew in the presence of fluid during the subduction prior to the onset of peak ultrahigh-pressure metamorphism, whereas the younger zircons grew in the presence of fluid released during the initial exhumation toward high-pressure eclogite-facies regime.     

Trace element systematics and Sm-Nd and Lu-Hf ages of Larkman Nunatak 06319: Closed-system fractional crystallization of an enriched shergottite magma

Combined ¹⁴⁷Sm-¹⁴³Nd and ¹⁷⁶Lu-¹⁷⁶Hf chronology of the martian meteorite Larkman Nunatak (LAR) 06319 indicates an igneous crystallization age of 193 ± 20 Ma (2σ weighted mean). The individual ¹⁴⁷Sm-¹⁴³Nd and ¹⁷⁶Lu-¹⁷⁶Hf internal isochron ages are 183 ± 12 Ma and 197 ± 29 Ma, respectively, and are concordant with two previously determined ¹⁴⁷Sm-¹⁴³Nd and ⁸⁷Rb-⁸⁷Sr internal isochron ages of 190 ± 26 Ma and 207 ± 14 Ma, respectively (Shih et al., 2009). With respect to the ¹⁴⁷Sm-¹⁴³Nd isotope systematics, maskelynite lies above the isochron defined by primary igneous phases and is therefore not in isotopic equilibrium with the other phases in the rock. Non-isochronous maskelynite is interpreted to result from shock-induced reaction between plagioclase and partial melts of pyroxene and phosphate during transformation to maskelynite, which resulted in it having unsupported ¹⁴³Nd relative to its measured ¹⁴⁷Sm/¹⁴⁴Nd ratio. The rare earth element (REE) and high field strength element (HFSE) compositions of major constituent minerals can be modeled as the result of progressive crystallization of a single magma with no addition of secondary components. The concordant ages, combined with igneous textures, mineralogy, and trace element systematics indicate that the weighted average of the radiometric ages records the true crystallization age of this rock. The young igneous age for LAR 06319 and other shergottites are in conflict with models that advocate for circa 4.1 Ga crystallization ages of shergottites from Pb isotope compositions, however, they are consistent with updated crater counting statistics indicating that young volcanic activity on Mars is more widespread than previously realized (Neukum et al., 2010).     

Metamorphic growth and recrystallization of zircons in extremely O-depleted rocks during eclogite-facies metamorphism: Evidence from U-Pb ages, trace elements, and O-Hf isotopes

A combined in situ SIMS and LA-(MC)-ICPMS study of U-Pb ages, trace elements, O and Lu-Hf isotopes was conducted for zircon from eclogite-facies metamorphic rocks in the Sulu orogen. The two microbeam techniques sampled various depths of zircon domains, revealing different element and isotope relationships between residual magmatic cores and new metamorphic rims and thus the geochemical architecture of metamorphic zircons which otherwise cannot be recognized by the single microbeam technique. This enables discrimination of metamorphic growth from different subtypes of metamorphic recrystallization. Magmatic cores with U-Pb ages of 769 ± 9 Ma have positive δ¹⁸O values of 0.1-10.1‰, high Th/U and ¹⁷⁶Lu/¹⁷⁷Hf ratios, high REE contents, and steep MREE-HREE patterns with negative Eu anomalies. They are interpreted as crystallizing from positive δ¹⁸O magmas during protolith emplacement. In contrast, newly grown domains have concordant U-Pb ages of 204 ± 4 to 252 ± 7 Ma and show negative δ¹⁸O values of −10.0‰ to −2.2‰, low Th/U and ¹⁷⁶Lu/¹⁷⁷Hf ratios, low REE contents, and flat HREE patterns with weak to no Eu anomalies. They are interpreted as growing from negative δ¹⁸O fluids that were produced by metamorphic dehydration of high-T glacial-hydrothermally altered rocks during continental subduction-zone metamorphism. Differences in δ¹⁸O between different domains within single grains vary from 0.8‰ to 12.5‰, suggesting different degrees of O isotope exchange between the positive δ¹⁸O magmatic core and the negative δ¹⁸O metamorphic fluid during the metamorphism. The magmatic zircons underwent three subtypes of metamorphic recrystallization, depending on their accessibility to negative δ¹⁸O fluids. The zircons recrystallized in solid-state maintained positive δ¹⁸O values, and REE and Lu-Hf isotopes of protolith zircon, but their U-Pb ages are lowered. The zircons recrystallized through dissolution exhibit negative δ¹⁸O values similar to the metamorphic growths, almost completely reset U-Pb ages, and partially reset REE systems. The zircons recrystallized through replacement show variably negative δ¹⁸O values, and partially reset REE, and U-Pb and Lu-Hf isotopic systems. Therefore, this study places robust constraints on the origin of metamorphic zircons in eclogite-facies rocks and provides a methodological framework for linking the different types of metamorphic zircons to petrological processes during continental collision.     

Growth rate of the preserved continental crust: II. Constraints from Hf and O isotopes in detrital zircons from Greater Russian Rivers

Detrital zircons from the Ob, Yenisey, Lena, Amur, Volga, Dnieper, Don and Pechora rivers have been analyzed for U-Th-Pb, O and Lu-Hf isotopes to constrain the growth rate of the preserved continental crust in Greater Russia. Four major periods of zircon crystallization, 0.1-0.55, 0.95-1.3, 1.45-2.0 and 2.5-2.9 Ga, were resolved from a compilation of 1366 zircon U/Pb ages. The Archean zircons have δ¹⁸O values lying between 4.53‰ and 7.33‰, whereas Proterozoic and Phanerozoic zircons have a larger range of δ¹⁸O values in each of the recognized U/Pb time intervals with maximum δ¹⁸O values up to 12‰. We interpret the zircons with δ¹⁸O between 4.5‰ and 6.5‰ to have been derived from a magmatic precursor that contains little or no sedimentary component. The variable δ¹⁸O values of the zircons were used to constrain the ¹⁷⁶Lu/¹⁷⁷Hf ratios of the crustal source region of the zircons, which, in turn, were used to calculate Hf model ages (T_DM^V). The crustal incubation time, the time difference between primitive crust formation (dated by T_DM^V) and crustal melting (dated by zircon U/Pb age), varies between 300 to 1000 Myr for the majority of analyzed zircon grains, but can be up to 2500 Myr. The average T_DM^V Hf model age weighted by the fraction of zircons in the river load is 2.12 Ga, which is in reasonable agreement with the area-weighted average of 2.25 Ga. The T_DM^V Hf model age crustal growth curve for zircons with mantle-like δ¹⁸O values (4.5-6.5‰), weighted by area, shows that growth of the Great Russian continental crust started at 4.2 Ga, and that there are two principal periods of crustal growth, 3.6-3.3 Ga and 0.8-0.6 Ga, which are separated by an interval of low but more or less continuous growth. An alternative interpretation, in which the average ¹⁷⁶Lu/¹⁷⁷Hf ratio (0.0115) of the continental crust is used for the Paleoproterozoic zircons from the Lena River, lowers the average T_DM^V age of these grains by about 500 Myr and delays the onset of significant crustal growth to 3.5 Ga.The two principal growth periods recognized in Greater Russia differ from those identified from the Gondwana and the Mississippi river basin, which show peaks at 1.7-1.9 and 2.9-3.1 Ga (Hawkesworth and Kemp, 2006a) and 1.6-2.2 and 2.9-3.4 Ga (Wang et al., 2009), respectively. The older 3.6-3.3 Ga or 3.5-3.3 Ga peak for Greater Russia is slightly older than the older Gondwana-Mississippi peaks, whereas the younger 0.8-0.6 Ga peak is distinctly younger than the youngest peak in either Gondwana or the Mississippi river basin. This suggests that the two major peaks of crustal growth identified in Gondwana and the Mississippi river basin may not be global periods of enhanced continental growth and that the major periods of crustal growth may differ from continent to continent.     

The effect of tissue structure and soil chemistry on trace element uptake in fossils

Trace element profiles for common divalent cations (Sr, Zn, Ba), rare-earth elements (REE), Y, U, and Th were measured in fossil bones and teeth from the c. 25 ka Merrell locality, Montana, USA, by using laser-ablation ICP-MS. Multiple traverses in teeth were transformed into 2-D trace element maps for visualizing structural influences on trace element uptake. Trace element compositions of different soils from the fossil site were also analyzed by solution ICP-MS, employing progressive leaches that included distilled H₂O, 0.1 M acetic acid, and microwave digestion in concentrated HCl-HNO₃. In teeth, trace element uptake in enamel is 2-4 orders of magnitude slower than in dentine, forming an effective trace element barrier. Uptake in dentine parallel to the dentine-enamel interface is enhanced by at least 2 orders of magnitude compared to transverse, causing trace element “plumes” down the tooth core. In bone, U, Ba and Sr are nearly homogeneous, implying diffusivities ∼5 orders of magnitude faster than in enamel and virtually complete equilibration with host soils. In contrast all REE show strong depletions inward, with stepwise linear segments in log-normal or inverse complementary error function plots; these data require a multi-medium diffusion model, with about 2 orders of magnitude difference in slowest vs. fastest diffusivities. Differences in REE diffusivities in bone (slow) vs. dentine (fast) reflect different partition coefficients (K_d’s). Although acid leaches and bulk digestion of soils yield comparable fossil-soil K_d’s among different elements, natural solutions are expected to be neutral to slightly basic. Distilled H₂O leachates instead reveal radically different K_d’s in bone for REE than for U-Sr-Ba, suggest orders of magnitude lower effective diffusivities for REE, and readily explain steep vs. flat profiles for REE vs. U-Sr-Ba, respectively. Differences among REE K_d’s and diffusivities may explain inward changes in Ce anomalies. Acid washes and bulk soil compositions yield misleading K_d’s for many trace elements, especially the REE, and H₂O-leaches are preferred. Patterns of trace element distributions indicate diagenetic alteration at all scales, including enamel, and challenge the use of trace elements in paleodietary studies.     

Protracted diagenetic alteration of REE contents in fossil bioapatites: Direct evidence from Lu-Hf isotope systematics

Fossil bones and teeth are potentially important repository for geochemical proxy data and a target for radiometric dating. The concentration of many trace elements in bones and teeth increases by orders of magnitude after death and it is this diagenetic incorporation that forms the basis for several areas of geochemical study. The use of bones and teeth in this context relies on two assumptions: first, that target metal ions are incorporated rapidly after death, reflecting a known environmental signal, and second, that after early incorporation, the bone or tooth remains as an essentially closed system, resistant to later diagenetic change. A wide literature has developed exploring these assumptions, but relatively little direct evidence has been used to assess the long-term diagenetic stability of trace elements within bones and teeth. In this study, we use the Lu-Hf isotope system to show that bones and teeth of Cretaceous and Triassic age from both terrestrial and marine settings experience continued, long-term diagenetic change, most likely through gradual addition of trace elements. Modelling suggests that diagenetic addition after initial recrystallisation may account for >50% of the total REE content in the sampled bones, the extent depending on initial uptake conditions. Tooth enamel and enameloid may be more resistant to late diagenetic changes, but dentine is probably altered to the same extent as bone. These results have significant implications for the use of bones and teeth as hosts of chronological, palaeoceanographic, palaeoenvironmental and taphonomic information, particularly in Mesozoic and Palaeozoic contexts.     

Hafnium isotope homogenization during metamorphic zircon growth in amphibolite-facies rocks: Examples from the Shackleton Range (Antarctica)

Hafnium isotope analyses of a large number of metamorphic zircon grains of two garnet-kyanite-staurolite schist samples from the Shackleton Range yielded ¹⁷⁶Hf/¹⁷⁷Hf of 0.28160 ± 0.00003 and 0.28142 ± 0.00003, respectively. The variations of these analyses are less than ±1.2 epsilon units and indicate that all metamorphic zircon grains in the two rocks formed in environments with nearly homogenous Hf isotopic composition. The metamorphic origin of the zircon grains is constrained by textures as well as by their low Th/U (<0.2), ¹⁷⁶Lu/¹⁷⁷Hf (<0.0003), and ¹⁷⁶Yb/¹⁷⁷Hf ratios (<0.009), indicating that they grew in the presence of garnet. Furthermore, the grains yield Pb-Pb ages of c. 1.7 Ga, which is the time of amphibolite-facies metamorphism. In combination with petrological results, it is suggested that the observed ¹⁷⁶Hf/¹⁷⁷Hf homogeneity was caused by a fluid- and deformation-assisted dissolution of detrital zircon grains, followed by new zircon re-precipitation that was accompanied by Hf transport on at least a hand-specimen scale. This interpretation is supported by results obtained from an additional paragneiss sample that contains zoned zircon grains with xenocrystic cores formed at 2.6-1.8 Ga and metamorphic rims with a U-Pb age of 1.7 Ga. The ¹⁷⁶Hf/¹⁷⁷Hf variation of the zircon rims is mostly at ±0.0003, which is much less than that of the magmatic cores (±0.0019). The metamorphic fluid for the dissolution-homogenization-re-precipitation process most likely resulted from prograde reactions among the minerals chlorite-muscovite-biotite-garnet-staurolite-apatite, in agreement with thin section observations and P-T pseudosection calculations.     

γ-ray irradiation in the early Solar System and the conundrum of the Lu decay constant

When recent geological calibrations of the ¹⁷⁶Lu decay constant are used, the ¹⁷⁶Lu-¹⁷⁶Hf ages of chondrites are consistently 4% too old (∼4.75 Ga). Here, we suggest that this discrepancy reflects the photoexcitation of the long-lived ¹⁷⁶Lu ground state to the short-lived isomeric state (T_1/2 = 3.7 h) by γ-rays irradiating early condensates. Irradiation may have been of solar origin and taking place at the inner edge of the nebular disk. Alternatively, the source of γ-rays could have been one or more supernova(e) exploding in the vicinity of the solar nebula. Such photoexcitation has been experimentally observed, but requires γ-ray photons that have energies in excess of 838 keV. At this stage, we cannot assess whether the Hf isotope composition of the Bulk Silicate Earth differs from that of chondrites, eucrites, and the 4.56 Ga old Martian meteorite ALH84001, and therefore, whether the precursor material for these different planetary bodies received comparable fluences of γ-rays.     

U-Th-Pb and Lu-Hf isotopic constraints on the evolution of sub-continental lithospheric mantle, French Massif Central

We have carried out a Pb double-spike and Lu-Hf isotope study of clinopyroxenes from spinel-facies mantle xenoliths entrained in Cenozoic intraplate continental volcanism of the French Massif Central (FMC). U-Th-Pb and Lu-Hf isotope systematics verify the existence of different lithospheric domains beneath the northern and southern FMC. Northern FMC clinopyroxenes have extreme Lu/Hf ratios and ultra-radiogenic Hf (ε_Hf = +39.6 to +2586) that reflect ∼15-25% partial melting in Variscan times (depleted mantle model ages ∼360 Ma). Zr, Hf and Th abundances in these clinopyroxenes are low and unaffected by hydrous/carbonatitic metasomatism that overprinted LILE and light REE abundances and caused decoupling of Lu/Hf-Sm/Nd ratios and Nd-Hf isotopes (ε_Nd = +2.1 to +91.2). Pb isotopes of northern FMC clinopyroxenes are radiogenic (²⁰⁶Pb/²⁰⁴Pb > 19), and typically more so than the host intraplate volcanic rocks. ²³⁸U/²⁰⁴Pb ratios range from 17 to 68, and most samples have distinctively low ²³²Th/²³⁸U (<1) and ²³²Th/²⁰⁴Pb (3-22). Clinopyroxenes from southern FMC lherzolites are generally marked by overall incompatible trace element enrichment including Zr, Hf and Th abundances, and have Pb isotopes that are similar to or less radiogenic than the host volcanic rocks. Hf isotope ratios are less radiogenic (ε_Hf = +5.4 to +41.5) than northern FMC mantle and have been overprinted by silicate-melt-dominated metasomatism that affected this part of FMC mantle. Major element and Lu concentrations of clinopyroxenes from southern FMC harzburgites are broadly similar to northern FMC clinopyroxenes and suggest they experienced similar degrees of melt extraction as northern FMC mantle. ²³⁸U/²⁰⁴Pb (53-111) and ²³²Th/²⁰⁴Pb ratios (157-355) of enriched clinopyroxenes from the southern FMC are extreme and significantly higher than the intraplate volcanic rocks. In summary, mantle peridotites from different parts of the FMC record depletion at ∼360 Ma during Variscan subduction, followed by differing styles of enrichment. Northern FMC mantle was overprinted by a fluid/carbonatitic metasomatic agent that carried elements like U, Pb, Sr and light REE. In contrast, much of the southern FMC mantle was metasomatised by a small-degree partial silicate melt resulting in enrichment of all incompatible trace elements. The extreme mantle ²³⁸U/²⁰⁴Pb (northern and southern FMC), ²³²Th/²³⁸U (northern FMC) and ²³²Th/²⁰⁴Pb ratios (southern FMC), coupled with unremarkable present-day Pb isotope ratios, constrain the timing of enrichment. Mantle metasomatism is a young feature related to melting of the upwelling mantle responsible for Cenozoic FMC volcanism, rather than subduction-related metasomatism intimately associated with mantle depletion during the Variscan orogeny. The varying metasomatic styles relate to pre-existing variations in the thickness of the continental lithospheric lid, which controlled the extent to which upwelling mantle could ascend and melt. In the northern FMC, a thicker and more refractory lithospheric lid (?80 km) only allowed incipient degrees of melting resulting in fluid/carbonatitic metasomatism of the overlying sub-continental lithospheric mantle. The thinner lithospheric lid of the southern FMC (?70 km) allowed larger degrees of melting and resulted in silicate-melt-dominated metasomatism, and also focused the location of the volcanic fields of the FMC above this region.     

Rate of growth of the preserved North American continental crust: Evidence from Hf and O isotopes in Mississippi detrital zircons

Detrital zircons from the Mississippi River have been analyzed for U-Th-Pb, Lu-Hf and O isotopes to constrain the rate of growth of the preserved North American continental crust. One hundred and forty two concordant zircon U/Pb dates on grains mounted in epoxy, obtained by Excimer laser ablation ICP-MS method, resolved six major periods of zircon crystallization: 0-0.25, 0.3-0.6, 0.95-1.25, 1.3-1.5, 1.65-1.95 and 2.5-3.0 Ga. These age ranges match the ages of the recognized lithotectonic units of the North American continent in the hinterland of the Mississippi River. Ninety-six zircons mounted on tape, which show no age zonation and were within 7.5% of concordance, were selected to represent the six U/Pb age time intervals and analyzed for Lu-Hf and O isotope by laser ablation MC-ICP-MS and SHRIMP II, respectively. The δ¹⁸O values of the zircons show a small step increase in the maximum δ¹⁸O values at the Archean-Proterozoic boundary from 7.5‰ in the Archean to 9.5‰, and rarely 13‰, in the Proterozoic and Phanerozoic. However, the average value of δ¹⁸O in zircons changes little with time, showing that the increase in the maximum δ¹⁸O values between 2.5 and 2.0 Ga, which can be attributed to an increase in the sediment content of the source regions of younger granitoids, is largely balanced by an increase in zircons with anomalously low δ¹⁸O, which can be attributed to hydrothermally altered crust in the granitoid source region.εHf_i values for the zircons range from 13.1 to −26.9. Zircons derived from juvenile crust, which we define as having mantle δ¹⁸O (4.5-6.5‰) and lying within error of the Hf depleted mantle growth curve, are rare or absent in the Mississippi basin. The overwhelming majority of zircons crystallized from melted pre-existing continental crust, or mantle-derived magmas that were contaminated by continental crust. The average time difference between primitive crust formation and remelting for each of the recognized lithotectonic time intervals, which is defined as crustal incubation time in this study, is 890 ± 460 Myr. There is also a suggestion that the crustal incubation time increases with decreasing age in the Mississippi basin, which is consistent with the declining role of radioactive heat production in the lower crust with time.The average Hf model age (1.94 Ga), weighted by fraction of zircons in the river load is in reasonable agreement with the Nd model age (1.7 Ga) for the Mississippi River. However, if the zircons are weighted by the area of North America covered by the six recognized periods of zircon crystallization the average model age is 2.35 Ga, which compares favorably with an area weighted Nd model age of 2.36 Ga. Our preferred approach is to use the measured O isotope values to constrain variations in the ¹⁷⁶Lu/¹⁷⁷Hf ratio of the granitic source region from which the zircons crystallized, making the assumption that zircons with mantle-like O isotopic ratios have higher ¹⁷⁶Lu/¹⁷⁷Hf than zircons with higher O isotope values. This method gives an average Hf model age of 2.53 Ga, which is 180 Myr older than the constant ¹⁷⁶Lu/¹⁷⁷Hf calculation.The area weighted zircon Hf model ages show two distinct periods of crust formation for the North American continent, 1.6-2.2 and 2.9-3.4 Ga. At least 50% of the preserved North American continental crust was extracted from the mantle by 2.9 Ga and 90% by 1.6 Ga. Two similar periods of crustal growth are also recognized in Gondwana (Hawkesworth C. J. and Kemp A. I. S. (2006) Using hafnium and oxygen isotopes in zircons to unravel the record of crustal evolution. Chem. Geol.226, 144-162.), suggesting that these may be periods of global continental crustal growth. However, we stress that more data from other continents are required before the hypothesis of episodic global continental growth can be accepted with confidence.     

An alternative model for silica enrichment in the Kaapvaal subcontinental lithospheric mantle

The Mg- and Si-rich nature of the sub-cratonic lithospheric mantle (SCLM) beneath the Kaapvaal Craton indicates extensive melt depletion, followed by a Si-enrichment process. Six highly silica enriched peridotites from Kimberley containing high amounts of orthopyroxene (Opx) or garnet (Grt) that are locally concentrated in clots, were investigated to constrain the timing and nature of the Si-enrichment process. A clinopyroxene-bearing lherzolite containing an Opx-clot was studied to quantify the effects of recent metasomatism on the Si-enriched samples. Minerals from the lherzolite, together with Opx from harzburgites and Opx- and Grt-clots have Hf-Nd isotope ratios at the time of kimberlite eruption, 90 Ma, comparable to group I kimberlites and are close to trace element equilibrium with kimberlitic melts. This implies the xenoliths underwent major interaction with kimberlitic melts close to the time of kimberlite eruption.Harzburgites and mineral clots record equilibration pressures and temperatures of, respectively, between 3.5-4.3 GPa and 930-1060 °C. The garnets in Opx-clots have low Lu/Hf and ε_Hf(t) −15, whereas garnets from Grt-clots have high Lu/Hf and ε_Hf(t) +10. In contrast, Grt from both Grt- and Opx-clots have low Sm/Nd and ε_Nd −10. The whole rock platinum group element (PGE) concentrations are an order of magnitude higher in the Grt-clot than the Opx-clot. Measured ¹⁸⁷Os/¹⁸⁸Os range from 0.1085 to 0.1222. The Grt-clot bearing sample yields Nd-Hf-Os isotope model ages that suggest formation in the Neoproterozoic (∼650 Ma). In contrast, an Opx-clot yields T_RD ages of 2.8 Ga, which is interpreted as the time of formation of the host harzburgite. The Opx-clots and host harzburgites have comparable Lu-Hf isotope systematics that imply Opx growth at ∼1.3 Ga and hence their formation is not related to the Grt-clots.Garnets from Opx- and Grt-clots have elevated high-field strength element (HFSE) concentrations, and lack HFSE depletion relative to other trace elements with comparable degrees of incompatibility in the mantle (La/Nb < 0.5). In addition, calculated melts in equilibrium with Grt have strongly fractionated REE (Nd/Yb > 300) and HREE depletion (Yb_N < 0.1) suggesting equilibration with a hydrous melt that is more HREE depleted than a kimberlitic melt. Previous models that related Si-enrichment to subduction are inconsistent with the lack of HFSE depletion (La/Nb < 0.5). Therefore the favoured model for Opx- and Grt-clot formation is infiltration of a hydrous melt in a within plate geodynamical environment associated with volcanism in the Mid-proterozoic and Neoproterozoic, respectively. This implies that Si-enrichment of the Kaapvaal SCLM may be a consequence of numerous localised magmatic events rather than a single craton-wide process.     

Paleozoic ages and excess Ar in garnets from the Bixiling eclogite in Dabieshan, China: New insights from Ar/Ar dating by stepwise crushing

The ⁴⁰Ar/³⁹Ar stepwise crushing technique is applied for the first time to date garnet from ultra-high-pressure metamorphic (UHPM) eclogites. Three garnet samples from the Bixiling eclogites analyzed by ⁴⁰Ar/³⁹Ar stepwise crushing yield regular, predictable age spectra, and a clear separation between excess ⁴⁰Ar and concordant plateau and isochron ages. All three age spectra begin with high apparent ages followed by step by step decreasing ages, and finally age plateaux with apparent ages in the range from 427 ± 20 to 444 ± 10 Ma. The data points constituting the age plateaux yield excellent isochrons with radiogenic intercept ages ranging from 448 ± 34 to 459 ± 58 Ma, corresponding to initial ⁴⁰Ar/³⁶Ar ratios from 292.1 ± 4.5 to 294.5 ± 6.7, statistically indistinguishable from the modern air. The high initial ages are interpreted to derive from secondary fluid inclusions containing excess ⁴⁰Ar, whereas the plateau ages are attributed to gas from small primary fluid inclusions without significant excess ⁴⁰Ar. The plateau ages are interpreted to approximate the time of garnet growth during initial UHPM metamorphism. Phengite analyzed by laser stepwise heating yielded a complicated two-saddle age spectrum with a scattered isochron corresponding to age of 463 ± 116 Ma and initial ⁴⁰Ar/³⁶Ar ratio of 1843 ± 1740 indicative of the presence of extraneous ⁴⁰Ar within phengite. These concordant isochron ages measured on minerals diagnostic of eclogite grade metamorphism strongly suggest that Dabie UHPM eclogites were first formed in the early Paleozoic, during the same event that caused the Qinling-Northern Qaidam Basin-Altyn Tagh eclogites.     

Metamorphic growth and recrystallization of zircon: Distinction by simultaneous in-situ analyses of trace elements,U–Th–Pb and Lu–Hf isotopes in zircons from eclogite-facies rocks in the Sulu orogen

Simultaneous in-situ analyses of trace elements, U–Th–Pb and Lu–Hf isotopes were carried out on distinct domains of zircons in ultrahigh-pressure (UHP) eclogite-facies metamorphic rocks from the main hole of the Chinese Continental Scientific Drilling (CCSD) in the Sulu orogen. For the first time, trace elements are directly linked to Lu–Hf isotopes in metamorphic zircons with reference to their U–Pb dates. This enables methodological integration to distinguish four types of metamorphic zircon: solid-state, replacement and dissolution recrystallizations of protolith zircons, and new growth from the aqueous fluid. Metamorphically grown zircons are characterized by concordant U–Pb ages for the metamorphism, flat HREE patterns typical of the garnet effect, low contents of REE (especially HREE), Y, Nb + Ta and Th + U, high contents of Hf, low (Lu/Gd)_N, Lu/Hf and Th/U (< 0.1) ratios, and elevated ¹⁷⁶Hf/¹⁷⁷Hf ratios relative to solid-state recrystallized zircons. This suggests the effects of both garnet and fluid on the growth of metamorphic zircons. In contrast, metamorphic recrystallization has reset the U–Th–Pb isotope system of protolith zircons to different extents, depending on the extents of fluid action during metamorphism. Solid-state recrystallized zircons exhibit the lowest degrees of resetting and thus almost inherit all geochemical features from the protolith zircons, which are characterized by discordant U–Pb ages close to or below the protolith age, steep MREE–HREE patterns typical of magmatic origin, high contents of trace elements and their ratios, and low ¹⁷⁶Hf/¹⁷⁷Hf ratios. On the other hand, dissolution recrystallized zircons show the highest degrees of reworking and thus have concordant or nearly concordant U–Pb ages for the metamorphism, steep MREE–HREE patterns, lowered contents of trace elements such as REE, Th, U, Y, Nb, Ta and Ti relative to the protolith zircons, and almost unchanged Hf isotope ratios. Replacement recrystallized zircons display intermediate degrees of reworking and thus have their many features of elements and isotopes in between. While the metamorphic growth in the presence of both garnet and fluid is characterized by both depletion of HREE with flat pattern and the low contents of trace elements, the metamorphic recrystallization in the presence of aqueous fluid is indicated by gradual decreases of MREE to HREE without the flat HREE pattern. Therefore, the simultaneous in-situ analyses of metamorphic zircons have the advantage over single-term analyses in making distinction between the new growth and the different types of recrystallization.     

Hf-W mineral isochron for Ca,Al-rich inclusions: Age of the solar system and the timing of core formation in planetesimals

Application of ¹⁸²Hf-¹⁸²W chronometry to constrain the duration of early solar system processes requires the precise knowledge of the initial Hf and W isotope compositions of the solar system. To determine these values, we investigated the Hf-W isotopic systematics of bulk samples and mineral separates from several Ca,Al-rich inclusions (CAIs) from the CV3 chondrites Allende and NWA 2364. Most of the investigated CAIs have relative proportions of ¹⁸³W, ¹⁸⁴W, and ¹⁸⁶W that are indistinguishable from those of bulk chondrites and the terrestrial standard. In contrast, one of the investigated Allende CAIs has a lower ¹⁸⁴W/¹⁸³W ratio, most likely reflecting an overabundance of r-process relative to s-process isotopes of W. All other bulk CAIs have similar ¹⁸⁰Hf/¹⁸⁴W and ¹⁸²W/¹⁸⁴W ratios that are elevated relative to average carbonaceous chondrites, probably reflecting Hf-W fractionation in the solar nebula within the first ∼3 Myr. The limited spread in ¹⁸⁰Hf/¹⁸⁴W ratios among the bulk CAIs precludes determination of a CAI whole-rock isochron but the fassaites have high ¹⁸⁰Hf/¹⁸⁴W and radiogenic ¹⁸²W/¹⁸⁴W ratios up to ∼14 ε units higher than the bulk rock. This makes it possible to obtain precise internal Hf-W isochrons for CAIs. There is evidence of disturbed Hf-W systematics in one of the CAIs but all other investigated CAIs show no detectable effects of parent body processes such as alteration and thermal metamorphism. Except for two fractions from one Allende CAI, all fractions from the investigated CAIs plot on a single well-defined isochron, which defines the initial ε¹⁸²W = −3.28 ± 0.12 and ¹⁸²Hf/¹⁸⁰Hf = (9.72 ± 0.44) × 10⁻⁵ at the time of CAI formation. The initial ¹⁸²Hf/¹⁸⁰Hf and ²⁶Al/²⁷Al ratios of the angrites D’Orbigny and Sahara 99555 are consistent with the decay from initial abundances of ¹⁸²Hf and ²⁶Al as measured in CAIs, suggesting that these two nuclides were homogeneously distributed throughout the solar system. However, the uncertainties on the initial ¹⁸²Hf/¹⁸⁰Hf and ²⁶Al/²⁷Al ratios are too large to exclude that some ²⁶Al in CAIs was produced locally by particle irradiation close to an early active Sun. The initial ¹⁸²Hf/¹⁸⁰Hf of CAIs corresponds to an absolute age of 4568.3 ± 0.7 Ma, which may be defined as the age of the solar system. This age is 0.5-2 Myr older than the most precise ²⁰⁷Pb-²⁰⁶Pb age of Efremovka CAI 60, which does not seem to date CAI formation. Tungsten model ages for magmatic iron meteorites, calculated relative to the newly and more precisely defined initial ε¹⁸²W of CAIs, indicate that core formation in their parent bodies occurred in less than ∼1 Myr after CAI formation. This confirms earlier conclusions that the accretion of the parent bodies of magmatic iron meteorites predated chondrule formation and that their differentiation was triggered by heating from decay of abundant ²⁶Al. A more precise dating of core formation in iron meteorite parent bodies requires precise quantification of cosmic-ray effects on W isotopes but this has not been established yet.     

Late Holocene radiocarbon and aspartic acid racemization dating of deep-sea octocorals

Primnoa resedaeformis is a deep-sea gorgonian coral with a two-part skeleton of calcite and gorgonin (a fibrillar protein), potentially containing long-term records of valuable paleo-environmental information. For various reasons, both radiocarbon and U/Th dating of these corals is problematic over the last few centuries. This paper explores aspartic acid racemization dating of the gorgonin fraction in modern and fossil specimens collected from the NW Atlantic Ocean. Radiocarbon dating of the fossil specimen indicates a lifespan of 700 ± 100 years, the longest yet documented for any octocoral. Gorgonin amino acid compositions were identical in the fossil and modern specimens, indicating resistance to organic diagenesis. Similar to bone collagen, the fibrillar protein of gorgonin may impose conformational constraints on the racemization of Asp at low temperatures. The rate of racemization of aspartic acid (d/l-Asp) was similar to previously published results from an 1800 year old anemone (Gerardia). The age equation was: age (years BP 2000 AD) = [(d/l − 0.020 (±.002))/.0011 (±.0001)]² (r² = 0.97, p < .001). The error in an age estimate calculated by d/l-Asp was marginally better than that for ¹⁴C dating over the most recent 50-200 years, although the dating error may be improved by inclusion of more samples over a broader time range. These results suggest that d/l-Asp dating may be useful in augmenting ¹⁴C dating in cases where ¹⁴C calibrations yield two or more intercept ages, or in screening samples for further ¹⁴C or U/Th dating.