Hf and Nd isotopes in marine sediments: Constraints on global silicate weathering

The combined use of Lu–Hf and Sm–Nd isotope systems potentially offers a unique perspective for investigating continental erosion, but little is known about whether, and to what extent, the Hf–Nd isotope composition of sediments is related to silicate weathering intensity. In this study, Hf and Nd elemental and isotope data are reported for marine muds, leached Fe-oxide fractions and zircon-rich turbidite sands collected off the Congo River mouth, and from other parts of the SE Atlantic Ocean. All studied samples from the Congo fan (muds, Fe-hydroxides, sands) exhibit indistinguishable Nd isotopic composition (ε_Nd ~ ? 16), indicating that Fe-hydroxides leached from these sediments correspond to continental oxides precipitated within the Congo basin. In marked contrast, Hf isotope compositions for the same samples exhibit significant variations. Leached Fe-hydroxide fractions are characterized by ε_Hf values (from ? 1.1 to + 1.3) far more radiogenic than associated sediments (from ? 7.1 to ? 12.0) and turbidite sands (from ? 27.2 to ? 31.6). ε_Hf values for Congo fan sediments correlate very well with Al/K (i.e. a well-known index for the intensity of chemical weathering in Central Africa). Taken together, these results indicate that (1) silicate weathering on continents leads to erosion products having very distinctive Hf isotope signatures, and (2) a direct relationship exists between ε_Hf of secondary clay minerals and chemical weathering intensity.These results combined with data from the literature have global implications for understanding the Hf–Nd isotope variability in marine precipitates and sediments. Leached Fe-hydroxides from Congo fan sediments plot remarkably well on an extension of the ‘seawater array’ (i.e. the correlation defined by deep-sea Fe–Mn precipitates), providing additional support to the suggestion that the ocean Hf budget is dominated by continental inputs. Fine-grained sediments define a diffuse trend, between that for igneous rocks and the ‘seawater array’, which we refer to as the ‘zircon-free sediment array’ (ε_Hf = 0.91 ε_Nd + 3.10). Finally, we show that the Hf–Nd arrays for seawater, unweathered igneous rocks, zircon-free and zircon-bearing sediments (ε_Hf = 1.80 ε_Nd + 2.35) can all be reconciled, using Monte Carlo simulations, with a simple weathering model of the continental crust.     

Hafnium and neodymium isotopes in seawater and in ferromanganese crusts: The “element perspective”

Hafnium and Nd isotopes are increasingly used as paleoceanographic proxies. Comparing the “mantle–crust array” and the “seawater array” in plots of ε_Hf vs. ε_Nd, it has been observed that for a given ε_Nd value the corresponding ε_Hf value is higher for seawater than it is for terrestrial rocks. While this difference had initially been explained by significant hydrothermal input of mantle Hf into seawater, the currently favoured explanation is incongruent weathering of continental rocks producing radiogenic riverine Hf input.We here address this topic from the perspective of the behaviour of these two elements in seawater and in ferromanganese (Fe–Mn) crusts. We distinguish between a “truly dissolved” and a “dissolved” Hf and Nd pool, the latter being comprised of truly dissolved and colloid-bound (“colloidal”) Hf and Nd. While there exists a hydrothermal pathway for colloid-bound dissolved mantle Hf into the oceans, there is, in marked contrast to Nd, no important riverine pathway for colloidal or truly dissolved continental Hf. Owing to their respective chemical speciation in seawater, there exists truly dissolved Nd in the ocean, while the amount of truly dissolved Hf is insignificant.Neodymium is in exchange equilibrium between local seawater and both, the hydrous Fe and Mn oxides hydrogenetic Fe–Mn crusts are composed of. Due to continuous ad- and desorption there is continuous isotopic re-equilibration and the isotopic composition of Nd in a Fe–Mn crust reflects that of truly dissolved Nd in local ambient seawater. In contrast, Hf is only associated with the hydrous Fe oxides on which it forms surface precipitates that do not exchange with seawater. Due to this lack of isotopic re-equilibration, the isotopic composition of Hf in a Fe–Mn crust is the average of that of all the Hf scavenged during the lifetime of the hydrous Fe oxide particles. Since the Hf-bearing hydrous Fe oxides in a Fe–Mn crust do not form from local ambient seawater at the crust's growth site but are advected as colloids or fine particles, their Hf isotopic composition depends on the origin and migration pathway of these colloids. Hence, while Nd isotopes in Fe–Mn crusts provide reliable information on truly dissolved Nd in local ambient seawater, Hf isotopes rather indicate the origin and pathway of hydrous Fe oxide colloids, and might differ from truly dissolved Hf in local ambient seawater. This may explain the occasional decoupling of Nd and Hf isotopes in Fe–Mn crusts and supports the notion of a significant hydrothermal mantle signal of Hf in seawater.     

Neodymium isotopic variations in seawater

New data for the direct measurement of the isotopic composition of neodymium in Atlantic Ocean seawater are compared with previous measurements of Pacific Ocean seawater and ferromanganese sediments from major ocean basins. Data for Atlantic seawater are in excellent agreement with Nd isotopic measurements made on Atlantic ferromanganese sediments and are distinctly different from the observed compositions of Pacific samples. These results clearly demonstrate the existence of distinctive differences in the isotopic composition of Nd in the waters of the major ocean basins and are characteristic of the ocean basin sampled. The average ε_Nd(0) values for the major oceans as determined by data from seawater and ferromanganese sediments are as follows: Atlantic Ocean,ε_Nd(0) ? ?12 ± 2; Indian Ocean,ε_Nd(0) ? ?8 ± 2; Pacific Ocean,ε_Nd(0) ? ?3 ± 2. These values are considerably less than ε_Nd(0) value sources with oceanic mantle affinities indicating that the REE in the oceans are dominated by continental sources. The difference in the absolute abundance of¹⁴³Nd between the Pacific and Atlantic Oceans corresponds to ～10⁶ atoms¹⁴³Nd per gram of seawater. The correspondence between the¹⁴³Nd/¹⁴⁴Nd in seawater and in the associated sediments suggests the possible application of this approach to paleo-oceanography.Distinctive differences in ε_Nd(0) values are observed in the Atlantic Ocean between deep-ocean water associated with North Atlantic Deep Water and near-surface water. This suggests that North Atlantic Deep Water may be relatively well mixed with respect to Nd isotopic composition whereas near-surface water may be quite heterogeneous, reflecting different sources for surface waters relative to deep water. This suggests that it may be possible to distinguish the sources of water masses within an ocean basin on the basis of Nd isotopic composition.The Nd isotopic variations in seawater are used to relate the residence time of Nd and mixing rates between the oceans.     

Low-degree melting of a metasomatized lithospheric mantle for the origin of Cenozoic Yulong monzogranite-porphyry,east Tibet: Geochemical and Sr–Nd–Pb–Hf isotopic constraints

SHRIMP zircon U–Pb dating, mineral chemical, element geochemical and Sr–Nd–Pb–Hf isotopic data have been determined for the Yulong monzogranite-porphyry in the eastern Tibet, China. The Yulong porphyry was emplaced into Triassic strata at about 39 Ma. The rocks are weakly peraluminous and show shoshonitic affinity, i.e., alkalis-rich, high K₂O contents with high K₂O / Na₂O ratios, enrichment in LREE and LILE. They also show some affinities with the adakite, e.g., high SiO₂ and Al₂O₃, and low MgO contents, depleted in Y and Yb, and enrichment in Sr with high Sr / Y and La / Yb ratios, and no Eu anomalies. The Yulong porphyry has radiogenic ⁸⁷Sr / ⁸⁶Sr (0.7063–0.7070) and unradiogenic ¹⁴³Nd / ¹⁴⁴Nd (ε_Nd = − 2.0 to − 3.0) ratios. The Pb isotopic compositions of feldspar phenocrysts separated from the Yulong porphyry show a narrow range of ²⁰⁶Pb / ²⁰⁴Pb ratios (18.71–18.82) and unusually radiogenic ²⁰⁷Pb / ²⁰⁴Pb (15.65–15.67) and ²⁰⁸Pb / ²⁰⁴Pb (38.87–39.00) ratios. In situ Hf isotopic composition of zircons that have been SHRIMP U–Pb dated is characterized by clearly positive initial ε_Hf values, ranging from + 3.1 to + 5.9, most between + 4 and + 5. Phenocryst clinopyroxene geothermometry of the Yulong porphyry indicates that the primary magmas had anomalously high temperature (> 1200 °C). The source depth for the Yulong porphyry is at least 100 km inferred by the metasomatic volatile phase (phlogopite–carbonate) relations. Detailed geochemical and Sr–Nd–Pb–Hf isotopic compositions not only rule out fractional crystallization or assimilation-fractional crystallization processes, but also deny the possibility of partial melting of subducted oceanic crust or basaltic lower crust. Instead, low degree (1–5%) partial melting of a metasomatized lithosphere (phlogopite–garnet clinopyroxenite) is compatible with the data. This example gives a case study that granite can be derived directly by partial melting of an enriched lithospheric mantle, which is important to understand the source and origin of diverse granites.     

Lu-Hf and Sm-Nd isotopic systematics in chondrites and their constraints on the Lu-Hf properties of the Earth

Sm-Nd and Lu-Hf isotopic data are presented for 19 chondritic meteorites: six carbonaceous chondrites, five L-chondrites, seven H-chondrites, and a single enstatite chondrite. The primary goal of the study is to better define the Bulk Silicate Earth (BSE) reference values for Hf isotopes. Except for one sample with lower Sm/Nd, the Sm-Nd data define a cluster around the accepted reference values for chondrites and terrestrial planets, giving a mean ¹⁴⁷Sm/¹⁴⁴Nd of 0.1960±0.0005, and a mean ¹⁴³Nd/¹⁴⁴Nd of 0.512631±0.000010 (uncertainties are two standard errors). It seems appropriate to retain the presently accepted Sm-Nd reference parameters, ¹⁴⁷Sm/¹⁴⁴Nd=0.1966 and ¹⁴³Nd/¹⁴⁴Nd=0.512638 (when fractionation-corrected to ¹⁴⁶Nd/¹⁴⁴Nd=0.7219).Lu-Hf isotopic data are not clustered, but spread along an approximate 4.5-Ga isochron trend, with a range of ¹⁷⁶Lu/¹⁷⁷Hf from 0.0301 to 0.0354. The data are similar to many of the samples of chondrites presented by Bizzarro et al. [Nature 421 (2003) 931], but lack the range to lower Lu/Hf shown by those authors. Our chondrite data define a regression line of 4.44±0.34 Ga when 1.867×10⁻¹¹ year⁻¹ is used for the decay constant of ¹⁷⁶Lu [Science 293 (2001) 683; Earth Planet. Sci. Lett. 219 (2004) 311-324]. Combining our data with the main population of analyses from Bizzarro et al. [Nature 421 (2003) 931] yields 4.51±0.24 Ga. Unless samples of eucrite meteorites and deviating replicates of chondrites with ¹⁷⁶Lu/¹⁷⁷Hf less than 0.030 are employed, no combination of the main population of chondrite Lu-Hf data yields a regression with sufficiently low error to constrain the decay constant of ¹⁷⁶Lu. Sample heterogeneity seems to hinder the acquisition of reproducible Lu-Hf analyses from small, manually ground pieces of chondrites, and we suggest that analysis of powders prepared from large volumes of meteorite will be needed to adequately characterize the Lu-Hf isotope systematics of chondritic reservoirs and of BSE. Our results for carbonaceous chondrites show higher average ¹⁷⁶Lu/¹⁷⁷Hf and ¹⁷⁶Hf/¹⁷⁷Hf than ordinary chondrites, and the mean of carbonaceous chondrites also coincides with replicate analyses of a powder representing a large volume of meteorite, the Allende powder from the Smithsonian Institution. Use of the carbonaceous chondrite mean for BSE Lu-Hf characteristics results in a BSE Hf-Nd point that lies well within the array of terrestrial compositions, and leads to plausible initial ε_Hf values for Precambrian rocks. An improved objective resolution of meteorite data and of meteoritic models for the Earth needs to occur before BSE can be established for Lu-Hf.     

An estimate of the Nd isotopic composition of Iapetus seawater from ca. 490 Ma metalliferous sediments

Well-preserved metalliferous sediments and pillow basalts of Lower Ordovician age (ca. 490 Ma) have been studied in an attempt to specify the Nd isotopic composition of Iapetus seawater. Initial¹⁴³Nd/¹⁴⁴Nd ratios of the pillow basalts are indistinguishable from published initial ratios for the 505-Ma Bay of Islands ophiolite complex and are within the anticipated range for MORB-type basalts 500 Ma ago. Metalliferous sediments occur both interstitial to basalt pillows and as well-developed sedimentary accumulations. The initial¹⁴³Nd/¹⁴⁴Nd ratios for the non-interstitial variety range from 0.511851 to 0.511712 (ε_Nd = ?2.7to?5.4) and are considered to provide an estimate of¹⁴³Nd/¹⁴⁴Nd in Iapetus seawater. The interstitial metalliferous sediments show evidence for a significant basalt-derived Nd component. Although volcanic activity occurred at the margin of Iapetus essentially contemporaneous with the formation of the metalliferous sediments, it is clear that arc-type volcanic material was not a major source of Nd in Iapetus seawater. Rather the source of Nd was from continental regions with a similar average age to those supplying material to the present-day Atlantic Ocean.     

Glacial–interglacial sediment transport to the Meiji Drift,northwest Pacific Ocean: Evidence for timing of Beringian outwashing

A large sediment deposit known as the Meiji Drift, located in the northwestern Pacific Ocean, is thought to have formed from deep water exiting the Bering Sea, although no notable deep water forms there presently. We determine the terrigenous sources since 140 ka to the drift using bulk sediment ⁴⁰Ar–³⁹Ar and Nd isotopic analyses on the silt-sized (20–63 μm) terrigenous fraction from Ocean Drilling Program (ODP) Site 884 to reconstruct paleo-circulation patterns. There are large changes in both isotopic tracers, varying on glacial–interglacial cycles. During glacial intervals, bulk sediment ⁴⁰Ar–³⁹Ar ages range between 40 and 80 Ma, while Nd isotopic values range from ε_Nd = ? 1 to + 2. During interglacial intervals, sediments become much younger and more radiogenic, with bulk sediment ages falling to 2–15 Ma and Nd isotopic values ranging between ε_Nd = + 5 and + 9. These data and quantitative comparison to potential source rocks indicate that the young Kamchatkan and Aleutian Arcs, lying NW and NE of the Meiji Drift, contribute the majority of sediment during interglacials. Conversely, older source rocks, such as those drained by the Yukon River and northeast Russia are the dominant origin of sediments during glacials. Mixing model calculations suggest that as much as 35–45% of the sediment deposited in the Meiji Drift during glacials is from the Bering Sea. It remains unclear whether thermohaline-type circulation or focussing of Bering Sea flow lead to the glacial–interglacial sediment source changes observed here.     

Early Paleozoic subduction of the Paleo-Asian Ocean: Geochronological and geochemical evidence from the Dashizhai basalts,Inner Mongolia

Zircon U-Pb results of basalt from the Dashizhai Town in Inner Mongolia, NE China, shows that the basaltic lava was erupted at 439±3 Ma, much older than the “Permian basalts” as previously thought. These rocks show arc-type trace element patterns (i.e., Nb-Ta depletion and light REE and large ion lithophile element enrichment) and unradiogenic Sr and highly radiogenic Nd and Hf isotope compositions. They can be subdivided into two petrogenetic groups: Group 1 basalts have relatively high TiO₂, MgO and compatible elements and low Sr and Th, characterized by mid-oceanic ridge basalt (MORB)-type Sr-Nd-Hf isotope compositions (⁸⁷Sr/⁸⁶Sr(i)=0.7028−0.7032, ε_Nd(t)=+9.8−+11.2, ε_Hf(t)=+16.1−+18.4). Group 2 has lower TiO₂, MgO and compatible elements and higher Sr and Th, and relatively evolved Sr-Nd-Hf isotope compositions (⁸⁷Sr/⁸⁶Sr(i)=0.7037−0.7038, ε_Nd(t)=+5.7−+7.3, ε_Hf(t)=+12.6−+13.0). Both groups were interpreted as melts derived from a metasomatized mantle wedge formed during the subduction of Paleo-Asian Ocean. The mantle source for Group 1 was probably a highly isotopically depleted oceanic mantle modified by predominant slab fluids; whereas subducted sediments had an important contribution to the melting source for Group 2. The petrogenesis of the Dashizhai basalts provides clear evidence for early Paleozoic subduction of the Paleo-Asian Ocean, and the highly radiogenic Nd and Hf compositions in these rocks suggest that these lavas and their possible intrusive counterparts were one of the important components for Phanerozoic crustal growth. Our and previous studies on the “Dashizhai Formation” volcanic rocks yield an unrealistic eruption range of 440-270 Ma for different rock types, we thus advise to disassemble the previously defined “Dashizhai Formation” into multiple lithologic units and to reinterpret the spatial and temporal distributions of different volcano-sedimentary associations. Supported by National Basic Research Program of China (Grant No. 2006CB403504)     

Metamorphic effect on zircon Lu-Hf and U-Pb isotope systems in ultrahigh-pressure eclogite-facies metagranite and metabasite

The Hf isotope composition of original igneous or detrital zircons in high-grade metamorphic rocks can be used to trace protolith origin, but metamorphic effect on the Hf isotope composition of newly grown domains remains to evaluate. We report a detailed in situ combined study of intragrain U-Pb and Lu-Hf isotopes in zircons from granitic gneiss and eclogite in the Dabie orogen of China that experienced ultrahigh-pressure eclogite-facies metamorphism. The results show correlations in ²⁰⁶Pb / ²³⁸U age, initial Hf isotope composition, and Th / U and Lu / Hf ratios between the domains of different origins. The metamorphic domains are characterized by low Th / U and Lu / Hf ratios but high ?_Hf(t) values relative to the igneous core and mantle of pre-metamorphic ages. Positive correlations are observed between Th / U and Lu / Hf ratios, pointing to the similar effect of metamorphism on both U-Th-Pb and Lu-Hf isotope systems. Thus the metamorphic domains are distinguished from the igneous core and mantle by their low Lu / Hf ratios that are less than 0.001 for the granitic gneiss and less than 0.0001 for the eclogite. Despite differences in both protolith age and geochemical source between granitic gneiss and eclogite, rim ?_Hf(t) values are variably 3.1 to 13.5 greater than core ?_Hf(t) values when calculated at timing of protolith formation. This indicates that the zircon overgrowth was associated with a metamorphic medium that has high ¹⁷⁶Hf / ¹⁷⁷Hf but low ¹⁷⁶Lu / ¹⁷⁷Hf ratios. While the metamorphic domains contain more radiogenic Hf isotopes than the original igneous core and mantle, their Lu / Hf ratios are significantly lower than those of core and mantle. Therefore, the metamorphic zircons acquired their initial Hf isotope ratios from metamorphic fluids that have high ¹⁷⁶Hf / ¹⁷⁷Hf ratios but low Lu / Hf ratios with sound variability depending on the Lu-Hf isotope compositions of pre-existing and co-precipitating phases.     

Geochemical component relationships in MORB from the Mid-Atlantic Ridge, 22–35°N

New trace element and Hf, Nd, and Pb isotope data are reported for 22 basalts collected between 22°N and 35°N on the Mid-Atlantic Ridge. (La / Sm)_N ratios identify the presence of enriched (E)-MORB in the northernmost part of this area and normal (N)-MORB elsewhere. A negative correlation is observed when ¹⁴³Nd / ¹⁴⁴Nd is plotted against ²⁰⁶Pb / ²⁰⁴Pb, ²⁰⁷Pb / ²⁰⁴Pb, and ²⁰⁸Pb / ²⁰⁴Pb, whereas ¹⁷⁶Hf / ¹⁷⁷Hf appears not to correlate with any of the other isotopic ratios. The E-MORB samples are characterized by high ²⁰⁶Pb / ²⁰⁴Pb, ²⁰⁷Pb / ²⁰⁴Pb, ²⁰⁸Pb / ²⁰⁴Pb, and low ¹⁴³Nd / ¹⁴⁴Nd. Principal Component Analysis (PCA) of Pb isotopes alone identifies three, and only three, significant geochemical end-members (‘components’). Including Nd and Hf isotopic data in the PCA produces spurious components, partly because of curved mixing relationships, and partly because of fractionation during melting. Our preferred interpretation of why ¹⁷⁶Hf / ¹⁷⁷Hf is decoupled from the other isotopic ratios is, as inferred from recent experimental data, that the Hf isotopic compositions of the melt and the residue fail to equilibrate during melting. A strong correlation between (Sr / Nd)_N and (Eu / Eu*)_N indicates that plagioclase is a residual phase of N-MORB, but not of E-MORB melting. The three end-members identified in this study are the depleted mantle, a common-type component, and an enriched plume-type end-member. The common, or ‘C’-type, end-member is characteristic of E-MORB and may itself be a mixture containing recycled oceanic crust (the MORB suite, terrigenous sediments, and/or oceanic plateaus). The plume-type end-member is likely to represent the lower mantle and may involve some primordial material. It is shown that mantle isochrons in general and the Pb–Pb isochron in particular do not characterize a specific geodynamic process acting to create mantle heterogeneities.     

A Sr,Nd, Hf,and Pb isotope perspective on the genesis and long-term evolution of alkaline magmas from Erebus volcano,Antarctica

We report new Nd, Hf, Sr, and high-precision Pb isotopic data for 44 lava and tephra samples from Erebus volcano. The samples cover the entire compositional range from basanite to phonolite and trachyte, and represent all three phases of the volcanic evolution from 1.3 Ma to the present. Isotopic analyses of 7 samples from Mt. Morning and the Dry Valley Drilling Project (DVDP) are given for comparison. The Erebus volcano samples have radiogenic ²⁰⁶Pb/²⁰⁴Pb, unradiogenic ⁸⁷Sr/⁸⁶Sr, and intermediate ¹⁴³Nd/¹⁴⁴Nd and ¹⁷⁶Hf/¹⁷⁷Hf, and lie along a mixing trajectory between the two end-member mantle components DMM and HIMU. The Erebus time series data show a marked distinction between the early-phase basanites and phonotephrites, whose Nd, Hf, Sr, and Pb isotope compositions are variable (particularly Pb), and the current ‘phase-three’ evolved phonolitic lavas and bombs, whose Nd, Hf, Sr, and Pb isotope compositions are essentially invariant. Magma mixing is inferred to play a fundamental role in establishing the isotopic and compositional uniformity in the evolved phase-three phonolites. In-situ analyses of Pb isotopes in melt inclusions hosted in an anorthoclase crystal from a 1984 Erebus phonolite bomb and in an olivine from a DVDP basanite are uniform and identical to the host lavas within analytical uncertainties. We suggest that, in both cases, the magma was well mixed at the time melt inclusions were incorporated into the different mineral phases.     

Hafnium/rare earth element fractionation in the sedimentary system and crustal recycling into the Earth's mantle

Among long-lived radioactive parent-daughter element pairs, the ratio Lu/Hf is strongly fractionated relative to constant Sm/Nd in the Earth's sedimentary system. This is caused by high resistance to chemical weathering of the mineral zircon (Zr,Hf)SiO₄. Zircon-bearing sandy sediments on and near continents have very low Lu/Hf, while deep-sea clays have up to three times the chondritic Lu/Hf ratio. Turbidity currents mechanically carry the low-Lu/Hf sandy material onto the ocean floor. The results are important for the crust-to-mantle recycling discussion, where most recycled materials would be subducted oceanic sediments. Such sediment should be capable of explaining the HfNd mantle isotopic variation by mixing with peridotite, but in fact any average pelagic sediment has Nd/Hf and Lu/Hf too high to allow mixing curves to pass through the Hf/Nd isotopic array. The array could only be reproduced by subduction of turbidite sandstone with pelagic sediment in the approximate ratio 1.2 to 1, and by maintaining a good mixture between the two components. At least today, turbidites are available for subduction only at locations quite different and distant from those where pelagic sediments may be recycled; furthermore, mantle isotopic variation shows that the mantle often cannot mix itself well enough to homogenize these widely-separated sedimentary components to the degree required. The Lu/Hf fractionations place a severe restriction on the ability of recycled sediments to explain mantle isotopic patterns.     

Zircon Hf isotope composition of metamorphic eclogite from Xindian,Dabie Terrain

Hf isotope measurement has been carried out for UHP metamorphic eclogite from Xindian by using LA-MC-ICP-MS technique. The result indicates that metamorphic growth zircon has high 176Hf/177Hf (0.282544―0.282612) and low 176Lu/177Hf (0.000004―0.000211) ratio,inherited and recrystallized proto-lith zircon has low 176Hf/177Hf (0.282266―0.282466) and high 176Lu/177Hf (0.000090―0.002144) composi-tions. The low 176Lu/177Hf of growth zircon comes from its decreasing of Lu and increasing of Hf during UHP process. The high 176Hf/177Hf deduced from high radiogenic 176Hf,which was produced from long-term evolution of high Lu/Hf ratio minerals. Partial recrystallization of protolith zircon would not cause reworking of Lu/Hf isotope in zircon. Compared to U-Pb,zircon Lu-Hf system has better stability. The initial Hf isotope composition of metamorphic growth zircon may represent the Hf isotope compo-sition of whole rock system at the same time. The initial εHf of 3.0 for metamorphic precursor formation of Xindian eclogite indicates that the source material mainly derived from weak depleted mantle or mixing of depleted mantle with old crust.     

Petrogenesis of the concealed Daqiling intrusion in Guangxi and its tectonic significance: Constraints from geochemistry,zircon U-Pb dating and Nd-Hf isotopic compositions

The samples from the hidden Daqiling muscovite monzonite granite, which has recently been recognized within the Limu Sn-polymetallic ore field, have been analyzed for zircon U-Pb ages and whole rock geochemical and Nd-Hf isotopic compositions to discuss its genesis, source, and tectonic setting. LA-ICP-MS zircon U-Pb dating indicates that the granite crystallized in the late Indosinian (224.8±1.6 Ma). The granite is enriched in SiO₂ and K₂O and low in CaO and Na₂O. It is strongly peraluminous with the A/CNK values of 1.09–1.20 and 1.4 vol%–2.7 vol% normal corundum. Chondrite-normalized REE patterns show slightly right-dipping shape with strongly negative Eu anomalies (δEu =0.08–0.17). All samples show enrichment of LILEs (Cs, Rb and K) and HFSEs (U, Pb, Ce and Hf), but have relatively low contents of Ba, Sr and Ti. The zircon saturation temperatures (T _zr) are from 711 to 740°C, which are slightly lower than the average value of typical S-type granite (764°C). The granite has negative ? _Nd(t) and ? _Hf(t) values, which change from ?9.1 to ?10.1 with the peak values of ?9.2 to ?9.0 and from ?3.7 to ?12.6 with the peak values of ?6 to ?5, respectively. The T _DM ^C (Nd) and T _DM ^C (Hf) values are 1.74–1.82 Ga with the peak values of 1.73–1.75 Ga and 1.49–2.04 Ga with the peak values of 1.5–1.6 Ga, respectively. These characteristics reveal that the source region of the granite is dominantly late Paleoproterozoic to early Mesoproterozoic crustal materials. Seven inherited magmatic zircons are dated at the age of 248.6±4.3 Ma, which suggests the existence of the early Indosinian granite in Limu area. These zircons have the ? _Hf(t) values of ?6.7–?2.3, similar to those of the Daqiling granite, implying the involvement of the early Indosinian granite during the formation of the Daqiling granite. Inherited zircon of 945±11 Ma has the ? _Hf(t) and T _DM(Hf) values of 8.7 and 1.14 Ga, respectively, compatible with those of the Neoproterozoic arc magmatic rocks in the eastern Jiangnan orogenic belt. Therefore we inferred that Neoproterozoic arc magma might have been involved in the formation of the Daqiling granite, and that the Neoproterozoic arc magma belt and continent-arc collision belt between the Yangtze and Cathaysia Blocks might have extended westsouthward to Limu region. It is proposed that the underplating of mantle materials triggered by crustal extension and thinning resulted in partial melting of crustal materials to form the Daqiling granite in the late Indosinian under post-collisional tectonic setting.     

Pb,Hf and Nd isotope compositions of the two Réunion volcanoes (Indian Ocean): A tale of two small-scale mantle “blobs”?

Pb, Hf, Nd and Sr isotopes of basaltic lavas from the two Réunion Island volcanoes are reported in order to examine the origin of the sources feeding these volcanoes and to detect possible changes through time. Samples, chosen to cover the whole lifetime of the two volcanoes (from 2 Ma to present), yield a chemically restricted (compared to OIB lavas) but complex distribution. Réunion plume isotopic characteristics have been defined on the basis of the composition of uncontaminated shield-building lavas from the Piton de la Fournaise volcano. The average ?_Nd, ?_Hf, ⁸⁷Sr/⁸⁶Sr and ²⁰⁶Pb/²⁰⁴Pb, ²⁰⁷Pb/²⁰⁴Pb, and ²⁰⁸Pb/²⁰⁴Pb isotope ratios calculated for this component are + 4.4, + 9.1, 0.70411, 18.97, 15.59 and 39.03, respectively. In Pb–Pb isotope space, each volcano defines a distinct linear trend but slight variations are also detected within the various volcanic sequences. The Piton des Neiges volcano yields a distinct and significantly more scattered isotopic distribution than Piton de la Fournaise for both Pb, Hf and Nd isotope tracers. A principal component analysis of the Pb isotope data from Piton de la Fournaise reveals a major contribution of the C and EM-1 components (with a clear Dupal flavor) as main components for the modern Réunion plume. The same components have been identified for Piton des Neiges but with a stronger participation of a depleted mantle component and a weaker EM-1 contribution. The compositional change of the lavas erupted by the Piton des Neiges and Piton de la Fournaise volcanoes is attributed to the impingement of two small-scale blobs of plume material at the base of the Réunion lithosphere. Compared to other hot-spots worldwide, in particular Hawaii and Kerguelen, magmas beneath Réunion are generated from a considerably more homogeneous, compositionally more primitive plume higher in ²⁰⁶Pb. Although shallow-level contamination processes have been locally detected they did not alter significantly the composition of the plume magmas. This is tentatively attributed to mantle dynamics producing small, high-velocity blobs that ascend rapidly through the lithosphere, and to the lack of a well-developed magma chamber at depth in the lithosphere.     

REE and <Emphasis Type="Italic">ε</Emphasis><Subscript>Nd</Subscript> of clay fractions in sediments from the eastern Pacific Ocean: Evidence for clay sources

Clay fractions in the non-calcareous surface sediments from the eastern Pacific were analyzed for clay minerals, REE and ¹⁴³Nd/¹⁴⁴Nd. Montmorillonite/illite ratio (M/I ratio), total REE contents (ΣREE), LREE/HREE ratio and cerium anomaly (δCe) may effectively indicate the genesis of clay minerals. Clay fractions with M/I ratio <1, δCe >0.85, ΣREE <400 μg/g, LREE/HREE ratio ≈4, and REE patterns similar to those of pelagic sediments are terrigenous and autogenetic mixed clay fractions and contain more autogenetic montmorillonite. Clay fractions with M/I ratio >1, δCe=0.86 to 1.5, ΣREE=200 to 350 μg/g, LREE/HREE ratio ≈6 and REE distribution patterns similar to that of China loess are identified as terrigenous clay fraction. The ¹⁴³Nd/¹⁴⁴Nd ratios or _ɛNd values of clay fractions inherit the features of terrigenous sources of clay minerals. Clay fractions are divided into 4 types according to _ɛNd values. Terrigenous clay minerals of type I with the _ɛNd values of ™8 to ™6 originate mainly from North American fluvial deposits. Those of type II with the ε Nd values of ™9 to ™7 are mainly from the East Asia and North American fluvial deposits. Those of type III with ε Nd values of ™6 to ™3 could come from the central and eastern Pacific volcanic islands. Those of type IV with ε Nd values of ™13 to ™12 may be from East Asia eolian. The terrigenous and autogenetic mixed clay fractions show patchy distributions, indicating that there are volcanic or hot-spot activities in the eastern Pacific plate, while the terrigenous clay fractions cover a large part of the study area, proving that the terrigenous clay minerals are dominant in the eastern Pacific.     

A multi-isotopic and trace element investigation of the Cretaceous-Tertiary boundary layer at Stevns Klint, Denmark - inferences for the origin and nature of siderophile and lithophile element geochemical anomalies

Os, Sr, Nd and Pb isotope data were collected from a profile across the Cretaceous-Tertiary (K-T) boundary layer at Stevns Klint, Denmark. ?_Nd [T=65 Ma] values from within the boundary layer (Fish Clay) are lower by ∼1 ? unit than those of the underlying Maastrichtian limestone and the overlying Danian chalk sequences. Systematic profile-upward changes of Pb, Sr and Os isotopic compositions and concentrations in the boundary layer cannot be accounted for by in situ growth of daughter products since the sedimentation of the Fish Clay. While Os, Nd and Pb isotopes indicate the admixing of less radiogenic components to the Fish Clay, Sr isotopes show elevated radiogenic values in the boundary layer, relative to the carbonate sequences beneath and above it. The sudden change in lithophile (e.g., Sr, Pb and Nd) isotope compositions at the base of the Fish Clay and profile-upward trends of ⁸⁷Sr/⁸⁶Sr and ²⁰⁶Pb/²⁰⁴Pb ratios towards those of the overlying Danian chalk are interpreted to reflect recovery from enhanced, acid rain-induced continental (local?) weathering input to the seawater. However, a continental crustal source is invalid for the siderophile element Os. In the light of evidence from chromium isotopes for a cosmic origin of the platinum group elements (PGEs) and certain moderately siderophile elements (Cr, Ni, Co, V) in K-T boundary sediments, including Stevns Klint [Shukolyukov and Lugmair, Science 282 (1998) 927-929], and supported by the finding of projectile debris [Bauluz et al., Earth Planet. Sci. Lett. 182 (2000) 127-136] and the occurrence of abundant Ni-rich spinel at many K-T sites [Robin et al., Nature 363 (1993) 615-617; Kyte, Nature 396 (1998) 237-239], we favor to explain the sudden drop of ¹⁸⁷Os/¹⁸⁸Os ratios from 0.210 to 0.160 at the K-T boundary to derive from global fall-out of extraterrestrial matter. The present ¹⁸⁶Os/¹⁸⁸Os ratio of 0.119836±0.000004 measured in the basal layer of the Fish Clay is within the uncertainty a chondritic value. We therefore exclude the possibility of a major contribution of PGEs to the sediment from iron meteorites. Chondrite-normalized (Ru/Ir)_N ratios of ∼0.95±0.14 and (Os/Ir)_N ratios of ∼0.93±0.14 in the Fish Clay cannot distinguish between abundance ratios of different types of chondrites, and strongly sub-chondritic (Pt/Ir)_N ratios of ∼0.62±0.09 (2σ) suggest differential PGE remobilization through the sedimentary column (and consequently the alteration of inter-element ratios). PGEs and the moderately siderophile elements Cr, Ni, V, and Co form an elemental association with systematically upward-decreasing concentrations in the Fish Clay. Low Co/Ni ratios of ∼0.12 in the Fish Clay relative to values of ∼0.35 in the over- and underlying carbonate sequences support mixing of meteorite-derived (Co/Ni ∼0.05) and terrestrial upper mantle/crustal (Co/Ni >∼0.3) sources. While lithophile element isotope data indicate an increased continental crustal input to the Fish Clay at the K-T transition, the uncertainty with respect to possible post-depositional alteration of abundance patterns of siderophile and moderately siderophile elements - though not affecting the chondritic isotopic composition of Os - does not allow confirmation of indications from chromium isotopes for a carbonaceous (CV-type) meteorite as the preferred K-T impactor type by Shukolyukov and Lugmair [Science 282 (1998) 927-929].     

Trace element and isotopic effects of combined wallrock assimilation and fractional crystallization

Equations describing trace element and isotopic evolution in a magma chamber affected simultaneously by fractional crystallization and wallrock assimilation are presented for a model where the mass assimilation rate(?_a) is an arbitrary fraction(r) of the fractional crystallization rate(?_c). The equations also apply to recharge of a crystallizing magma. Relatively simple analytical expressions are obtained for both radiogenic isotope variations (Nd, Sr, Pb) and stable isotopes (O, H) including the effects of mass-dependent fractionation. Forr = 1 a modified zone refining equation is obtained for trace element concentrations, but forr < 1 behavior is a combination of zone refining and fractional crystallization. Asr → ∞, simple binary mixing is approached. The isotopic and trace element “mixing” trends generated can be much different from binary mixing, especially forr < 1. The model provides the basis for a more general approach to the problem of wallrock assimilation, and shows that binary mixing models are insufficient to rule out crustal assimilation as a cause of some of the isotopic variations observed in igneous rocks, including cases where clustering of isotopic values occurs partway between presumed endmember values. The coupled assimilation-fractional crystallization model provides an explanation for certain trace element and isotopic properties of continental margin orogenic magmas (e.g. Sr concentration versus⁸⁷Sr/⁸⁶Sr) which had previously been interpreted as evidence against assimilation. So-called “pseudoisochrons” can be understood as artifacts of contamination using this model. A significant correlation exists between country rock age and low¹⁴³Nd/¹⁴⁴Nd ratios in continental igneous rocks, clearly suggestive that crustal contamination is generally important.     

Os–Hf–Sr–Nd isotope and PGE systematics of spinel peridotite xenoliths from Tok,SE Siberian craton: Effects of pervasive metasomatism in shallow refractory mantle

Os–Hf–Sr–Nd isotopes and PGE were determined in peridotite xenoliths carried to the surface by Quaternary alkali basaltic magmas in the Tokinsky Stanovik Range on the Aldan shield. These data constrain the timing and nature of partial melting and metasomatism in the lithospheric mantle beneath SE Siberian craton. The xenoliths range from the rare fertile spinel lherzolites to the more abundant, strongly metasomatised olivine-rich (70–84%) rocks. Hf–Sr–Nd isotope compositions of the xenoliths are mainly within the fields of oceanic basalts. Most metasomatised xenoliths have lower ¹⁴³Nd / ¹⁴⁴Nd and ¹⁷⁶Hf / ¹⁷⁷Hf and higher ⁸⁷Sr / ⁸⁶Sr than the host basalts indicating that the metasomatism is older and has distinct sources. A few xenoliths have elevated ¹⁷⁶Hf / ¹⁷⁷Hf (up to 0.2838) and plot above the Hf–Nd mantle array defined by oceanic basalts.¹⁸⁷Os / ¹⁸⁸Os in the poorly metasomatised, fertile to moderately refractory (Al₂O₃ ≥ 1.6%) Tok peridotites range from 0.1156 to 0.1282, with oldest rhenium depletion ages being about 2 Ga. The ¹⁸⁷Os / ¹⁸⁸Os in these rocks show good correlations with partial melting indices (e.g. Al₂O₃, modal cpx); the intercept of the Al–¹⁸⁷Os / ¹⁸⁸Os correlation with lowest Al₂O₃ estimates for melting residues (∼0.3–0.5%) has a ¹⁸⁷Os / ¹⁸⁸Os of ∼0.109 suggesting that these peridotites may have experienced melt extraction as early as 2.8 Gy ago. ¹⁸⁷Os / ¹⁸⁸Os in the strongly metasomatised, olivine-rich xenoliths (0.6–1.3% Al₂O₃) ranges from 0.1164 to 0.1275 and shows no apparent links to modal or chemical compositions. Convex-upward REE patterns and high abundances of heavy to middle REE in these refractory rocks indicate equilibration with evolved silicate melts at high melt / rock ratios, which may have also variably elevated their ¹⁸⁷Os / ¹⁸⁸Os. This inference is supported by enrichments in Pd and Pt on chondrite-normalised PGE abundance patterns in some of the rocks. The melt extraction ages for the Tok suite of 2.0 to 2.8 Ga are younger than oldest Os ages reported for central Siberian craton, but they must be considered minimum estimates because of the extensive metasomatism of the most refractory Tok peridotites. This metasomatism could have occurred in the late Mesozoic to early Cenozoic when the Tok region was close to the subduction-related Pacific margin of Siberia and experienced large-scale tectonic and magmatic activity. This study indicates that metasomatic effects on the Re–Os system in the shallow lithospheric mantle can be dramatic.     

Possible early Neoproterozoic magmatism associated with slab window in the Pingshui segment of the Jiangshan-Shaoxing suture zone: Evidence from zircon LA-ICP-MS U-Pb geochronology and geochemistry

We report here geochemical data, U-Pb zircon ages, and Hf isotopes for the high-Mg diorites (HMDs), Nb-enriched basaltic porphyrys (NEBPs) and plagiogranites (PLAGs) in the Pingshui segment of the Jiangshan-Shaoxing suture zone. The HMDs are characterized by high Mg^# (>60), high Na and LREE contents, depletion of HREE and HFSE, and pronounced positive ε_Nd(t) values of 7.0 to 7.7, similar to some adakitic high-Mg andesites. The NEBPs are relatively Na-rich (Na₂O/K₂O>6) and display high abundances of P₂O₅ (∼1.00%), TiO₂ (∼3.08%) and HFSE (e.g., Nb=9.53–10.27 ppm). Their Nd isotopic compositions (ε_Nd(t)=6.8–8.0) are comparable to those of the HMDs. The PLAGs are metaluminous (A/CNK=0.84–0.89) and sodic (Na₂O/K₂O>10). Their depletion in HFSE (e.g., Nb, Ta) is consistent with “SSZ-type” plagiogranite. Zircon LA-ICP-MS U-Pb dating yields an age of 932±7 Ma for the HMD, 916±6 Ma for the NEBP, and 902±5 Ma for the PLAG, respectively, indicating that they were products of early Neoproterozoic magmatism. The PLAGs exhibit relatively high zircon Hf isotopes and positive ε_Hf(t) values of 11.0 to 16.2, consistent with their Nd isotopic data (ε_Nd(t)=7.5–8.4). Such features are similar to those of oceanic plagiogranites in ophiolites and distinct from those of crust-derived granites. The PLAGs were most likely derived from partial melting of subducted oceanic crust in an active continental margin. Considering these results in the context of the regional geology, we suggest that a slab window in the subducting oceanic crust between the Yangtze Block and Cathaysia Block was possibly the principal cause for the unique arc magmatism in the area. The upwelling asthenosphere below the slab window may have provided significant thermodynamic conditions. Supported by China Geological Survey (Grant No. 1212010610611) and the Ministry of Land and Resources (Grant No. 200811015)