The isotope composition of Hf in zircon from Paleoarchean plagiogneisses and plagiogranitoids of the Sharyzhalgai uplift (southern Siberian craton): Implications for the continental-crust growth

This paper presents results of U–Pb dating (SHRIMP-II) and Lu–Hf (LA–ICP MS) isotope study of zircon from Paleoarchean plagiogneisses and plagiogranitoids of the Onot and Bulun blocks of the Sharyzhalgai uplift. Magmatic zircons from the Onot plagiogneiss and Bulun gneissic trondhjemite are dated at 3388±11 and 3311±16 Ma, respectively. Magmatic zircons from plagiogneisses and plagiogranitoids of the studied tonalite–trondhjemite–granodiorite (TTG) complexes are characterized mainly by positive values of εHf indicating that felsic melts were generated mainly from juvenile (mafic) sources, which are derived from a depleted mantle reservoir. The variable Hf isotope composition in magmatic zircons and the lower average εHf values in comparison with the depleted mantle values suggest the contributions of both mafic and more ancient crustal sources to magma formation. Metamorphic zircons from the gneissic plagiogranite and migmatized plagiogneiss either inherited the Hf isotope composition from magmatic zircon or are enriched in radiogenic Hf. The more radiogenic Hf isotope composition of metamorphic zircons from the migmatized plagiogneisses is due to their interaction with melt during partial melting. Variations in the Lu–Hf isotope composition of zircon from the Bulun rocks in the period 3.33–3.20 Ga are due to the successive melting of mafic crust or the growing contribution of crustal material to their genesis. Correlation between the Lu–Hf isotope characteristics of zircon and the Sm–Nd parameters of the Onot plagiogneisses points to the contribution of ancient crustal material to their formation. The bimodal distribution of the model Hf ages of zircons reflects two stages of crustal growth in the Paleoarchean: 3.45–3.60 and ~ 3.35 Ga. The isotope characteristics of zircon and rocks of the TTG complexes, pointing to recycling of crustal material, argue for the formation of plagiogneisses and plagiogranitoids as a result of melting of heterogeneous (mafic and more ancient crustal) sources in the thickened crust.     

Calcium isotope constraints on the uptake and sources of Ca in a base-poor forest: A new concept of combining stable (δCa) and radiogenic (εCa) signals

Plant-available reserves of major base cations, Ca²⁺ and Mg²⁺, decreased markedly in soils over the past century, thus posing a potential threat to forest ecosystem health. Trees are thought to obtain dissolved Ca²⁺ ions mainly from an easily accessible soil-water reservoir also termed the ‘exchangeable cation pool’. The status of Ca reserves in this soil pool is sensitive to anthropogenic perturbations such as soil acidification induced by acid rain and/or excessive timber harvesting. Here we show that in a base-poor forest of the northeastern USA (i.e. Wachusett Mountain, Massachusetts) the ‘exchangeable Ca pool’ of deeper mineral soils has a unique isotope signature that is significantly enriched in the radiogenic ⁴⁰Ca, due to the dissolution of K-rich silicate minerals such as biotite. Using a simple isotope mass balance, and assuming that the input of Ca from biotite has a ε_Ca signature of ∼16, the results of our calculation indicate that the weathering of biotite may supply a sizeable fraction, up to 25%, of Ca²⁺ ions into the ‘exchangeable cation pool’ of deeper mineral soils. Importantly, samples of local vegetation (i.e. woody tissues of red oak) show no detectable excess of the radiogenic ⁴⁰Ca, and based on our model the upper limit of a possible biotite-derived Ca contribution in vegetation is estimated at ∼5%. We also found no evidence of the radiogenic ⁴⁰Ca signal in the samples of forest floor and the uppermost organic-rich soils (0-15 cm depth), which in turn suggest that over the long-term development of the forest and its organic matter accumulation, the vegetation growth must have also relied primarily on the non-radiogenic Ca sources. Based on our experimental data, such sources may include (i) wet atmospheric deposition, (ii) the organically-complexed Ca in topsoil horizons, and (iii) chemical weathering and/or fungal-mediated dissolution of apatite and Ca-rich plagioclase. Hence, our stable and radiogenic Ca isotope data indicate that the studied base-poor forest is able to bypass the ‘exchangeable cation pool’ of deeper (i.e. below 15 cm) mineral soils, and still manages to meet its nutritional requirements with respect to Ca. Another important implication of this study is that the organically-complexed Ca in the topsoil horizon (0-15 cm depth) has to be tightly bound to the ion exchange sites, otherwise the large radiogenic ⁴⁰Ca signatures present in the ‘exchangeable cation pool’ of deep mineral soils would be swamped by the downward gravitational flux of non-radiogenic Ca from the decaying organic matter and litterfall. Hence, the limited mobility of the organically-complexed Ca in soils and its tight biological cycling could explain the lack of a significant impact of vegetation on the Ca isotope systematics observed in large rivers.     

Metallogeny and lead isotopic composition of base metal sulfide deposits in the Rappen area,northern Sweden

Early Proterozoic volcanic and sedimentary rocks of the Rappen district in northern Sweden were deposited at a destructive plate margin to the south of the Archaean craton of the western Baltic Shield. The volcano-sedimentary suite was intruded by two generations of early Proterozoic granites at ca. 1.89–1.85 Ga and ca.1.82–1.78 Ga, respectively, and metamorphosed at upper amphibolite facies conditions. Small stratabound iron, copper, and zinc deposits occur in felsic to mafic tuffs and arkosic sediments. Small deposits of molybdenum, tungsten, and uranium formed during the emplacement of the younger granites. The lead isotopic compositions of sulfide trace lead from the various deposits are highly heterogeneous. In the ²⁰⁶Pb/²⁰⁴Pb–²⁰⁷Pb/²⁰⁴Pb diagram they fall on mixing arrays between little evolved early Proterozoic lead and highly radiogenic Caledonian lead. The least radiogenic lead isotopic compositions from the various deposits have a wide range of ²⁰⁷Pb/²⁰⁴Pb ratios and thus indicate variable involvement of Archaean crustal lead in the Proterozoic deposits. Deposits hosted by siliciclastic rocks have higher ²⁰⁷Pb/²⁰⁴Pb ratios than deposits hosted in mafic to felsic tuffites. The lead isotopic heterogeneity suggests that the lead in the various deposits was locally derived and, furthermore, that the sedimentary rocks in part originated from the Archaean craton to the north. Lead mixing arrays in the ²⁰⁶Pb/²⁰⁴Pb–²⁰⁷Pb/²⁰⁴Pb diagram demonstrate that in Paleozoic time radiogenic lead was mobilized and transported in the basement. Source ages calculated from the mixing arrays (ca.1.9 Ga and ca.1.8 Ga) correspond to the age of the Early Proterozoic volcanism and metamorphism respectively. One group of deposits includes lead from at least three sources and illustrates that radiogenic lead was multiply mobilized and transported in the Proterozoic basement. It occurs in deposits that occur in zones that became permeable during the reactivations of the basement.     

Mass‐Independent and Mass‐Dependent Ca Isotopic Compositions of Thirteen Geological Reference Materials Measured by Thermal Ionisation Mass Spectrometry

We report mass‐independent and mass‐dependent Ca isotopic compositions for thirteen geological reference materials, including carbonates (NIST SRM 915a and 915b), Atlantic seawater as well as ten rock reference materials ranging from peridotite to sandstone, using traditional ε and δ values relative to NIST SRM 915a, respectively. Isotope ratio determinations were conducted by independent unspiked and ⁴³Ca‐⁴⁸Ca double‐spiked measurements using a customised Triton Plus TIMS. The mean of twelve measurement results gave ε^40/44Ca values within ± 1.1, except for GSP‐2 that had ε^40/44Ca = 4.04 ± 0.15 (2SE). Significant radiogenic ⁴⁰Ca enrichment was evident in some high K/Ca samples. At an uncertainty level of ± 0.6, all reference materials had the same ε^43/44Ca and ε^48/44Ca values. We suggest the use of δ^44/42Ca to report mass‐dependent Ca isotopic compositions. The precision under intermediate measurement conditions for δ^44/42Ca over eight months in our laboratory was ± 0.03‰ (with n ≥ 8 repeat measurements). Measured igneous reference materials gave δ^44/42Ca values ranging from 0.27‰ to 0.54‰. Significant Ca isotope fractionation may occur during magmatic and metasomatism processes. Studied reference materials with higher (Dy_n/Yb_n) tend to have lower δ^44/42Ca, implying a potential role of garnet in producing magmas with low δ^44/42Ca. Sandstone GBW07106 had a δ^44/42Ca value of 0.22‰, lower than all igneous rocks studied so far.     

Evolution of the depleted mantle: Hf isotope evidence from juvenile rocks through time

The covariant behavior of Lu-Hf and Sm-Nd isotopes during most magmatic processes has long been recognized, but the details of this behavior in the depleted mantle reservoir have not been adequately examined. We report new whole-rock Hf and Nd isotope data for 1) juvenile, mantle-derived rocks, mid-Archean to Mesozoic in age, and 2) early Archean gneisses from West Greenland. Hf and Nd isotopic compositions of the juvenile rocks are well correlated, with the best fit corresponding to the equation ε_Hf = 1.40 ε_Nd + 2.1, and is similar to the collective Hf-Nd correlation for terrestrial samples of ε_Hf = 1.36 ε_Nd + 3.0. The early Archean Greenland gneisses, in contrast, have an extreme range in ε_Nd values (⁻4.4 to ⁺4.2; Bennett et al., 1993) that is not mirrored by the Hf isotopic system. The ε_Hf values for these rocks are consistently positive and have much less variation (0 to ⁺3.4) than their ε_Nd counterparts.The information from the Hf isotopic compositions of the West Greenland gneisses portrays an early Archean mantle that is relatively isotopically homogeneous at 3.8 to 3.6 Ga and moderately depleted in incompatible elements. There is no evidence that any of these gneisses have been derived from an enriched reservoir. The Hf isotopic data are in stark contrast to the Nd isotopic record and strongly imply that the picture of extreme initial isotopic heterogeneity indicated by Nd isotopes is not a real feature of the West Greenland gneisses but is rather an artifact produced by disturbances in the Sm-Nd isotope system of these rocks.Although Hf and Nd isotopic data do not uniquely constrain either the nature of the earliest crust or the timing of crustal growth, the most probable candidate for the enriched reservoir complementary to the depleted mantle in the pre-4.0 Ga Earth is a mafic, oceanic-type crust. In order to explain the predominantly positive ε_Hf and ε_Nd values for the early Archean rocks, this crust must have had a short residence time at the surface of the Earth before returning to the mantle where it was isolated from mixing with the depleted mantle for several hundred million years. The following period from 3.5 to 2.7 Ga may mark a transition during which this early formed mafic crust was mixed progressively back into the depleted mantle reservoir. While a present-day volume of continental crust at 4.0 Ga cannot be excluded on isotopic grounds, we find such a scenario unlikely based on the lack of direct isotopic and physical evidence for its existence. An important aspect of crustal growth and evolution, therefore, may be the transformation of the enriched reservoir from being predominantly mafic in the early Earth to becoming progressively more sialic through time.     

Sm-Nd, Lu-Hf and Pb-Pb signatures of gneisses and granitoids from the La Grande belt: extent of late Archean crustal recycling in the northeastern Superior Province, Canada

Sm-Nd, Lu-Hf and Pb-Pb isotopic signatures were determined for gneisses and felsic plutons of the La Grande granite-greenstone and the Nemiscau metasedimentary belts of Canada. The northern part of the La Grande belt exposes gneisses of the Langelier complex formed between ca. 2.8 and 2.9 Ga. The gneisses yielded εNd_(T) values between −2 and +1, εHf_(T) between −1 and +3, initial ²⁰⁷Pb/²⁰⁴Pb ratios of ∼14.9, higher than the value of 14.6 derived from the Stacey-Kramers growth curve, and crustal extraction ages ≥3.0 Ga. Modeling shows that the syn- to late-tectonic intrusions of granitoid rocks record at least 20%, and up to 40%, recycling of this gneissic basement. The southern part of the La Grande belt, where no basement gneisses are exposed, records lower proportions (5-20%) of this crustal end-member. In both parts of the La Grande belt, the post-tectonic plutons record the largest proportion of recycled crust, likely related to southeastward thrusting events in the Superior craton, crustal thickening and concomitant partial melting.The La Grande plutons have isotopic signatures more radiogenic than those of similar intrusions that formed concurrently, to the south, in the Abitibi greenstone belt. This reflects an ancient crust environment for the former vs. an oceanic setting for the latter. Mantle reservoirs with a protracted history of incompatible element depletion were present beneath the whole eastern Superior Province, in the late Archean.     

Highly depleted Hadean mantle reservoirs in the sources of early Archean arc-like rocks, Isua supracrustal belt, southern West Greenland

Growing evidence from the accessible geological record reveals that crust-mantle differentiation on Earth started as early as 4.4 Ga. In order to assess the extent of early Archean mantle depletion, we obtained ¹⁷⁶Lu-¹⁷⁶Hf, ¹⁴⁷Sm-¹⁴³Nd, and high field strength element (HFSE) concentration data for the least altered, well characterized boninite-like metabasalts and associated metasedimentary rocks from the Isua supracrustal belt (southern West Greenland). The metasediments exhibit initial εHf₍₃₇₂₀₎ values from −0.7 to +1.5 and initial εNd₍₃₇₂₀₎ values from +1.6 to +2.1. Initial εHf₍₃₇₂₀₎ values of the least altered boninite-like metabasalts span a range from +3.5 to +12.9 and initial εNd₍₃₇₂₀₎ values from −0.3 to +3.2. These initial Hf-isotope ratios display coherent trends with SiO₂, Al₂O₃/TiO₂ and other relatively immobile elements, indicating contamination via assimilation of enriched components, most likely sediments derived from the earliest crust in the region. This model is also consistent with previously reported initial γOs₍₃₇₂₀₎ values for some of the samples. In addition to the positive εHf₍₃₇₂₀₎ values, the least disturbed samples exhibit positive εNd₍₃₇₂₀₎ values and a co-variation of εHf₍₃₇₂₀₎ and εΝd₍₃₇₂₀₎ values. Based on these observations, it is argued, that the most depleted samples with initial εHf₍₃₇₂₀₎ values of up to +12.9 and high ¹⁷⁶Lu/¹⁷⁷Hf of ∼0.05 to ∼0.09 tap a highly depleted mantle source with a long term depletion history in the garnet stability field. High precision high field strength element (HFSE) data obtained for the Isua samples confirm the contamination trend. Even the most primitive samples display negative Nb-Ta anomalies and elevated Nb/Ta, indicating a subduction zone setting and overprint of the depleted mantle sources by felsic melts generated by partial melting of eclogite. Collectively, the data for boninite-like metabasalts support the presence of strongly depleted mantle reservoirs as previously inferred from Hf isotope data for Hadean zircons and combined ¹⁴²Nd-¹⁴³Nd isotope data for early Archean rocks.     

Calcium isotope record of Phanerozoic oceans: Implications for chemical evolution of seawater and its causative mechanisms

A total of 280 brachiopods of Ordovician to Cretaceous age, complemented by published data from belemnites and planktonic foraminifera, are used to reconstruct the evolution of calcium isotope composition of seawater (δ^44/40Ca_SW) over the Phanerozoic. The compiled δ^44/40Ca_SW record shows a general increase from ∼1.3‰ (NIST SRM 915a) at the beginning of the Ordovician to ∼2‰ at present. Superimposed on this trend is a major long-term positive excursion from the Early Carboniferous to Early Permian as well as several short-term, mostly negative, oscillations.A numerical model of the global cycles of calcium, carbon, magnesium and strontium was used to estimate whether the recorded δ^44/40Ca_SW variations can be explained by varying magnitudes of input and output fluxes of calcium to the oceans. The model uses the record of marine ⁸⁷Sr/⁸⁶Sr ratios as proxy for seafloor spreading rates, a record of oceanic Mg/Ca ratios to estimate rates of dolomite formation, and reconstructed atmospheric CO₂, discharge and erosion rates to estimate continental weathering fluxes.The model results indicate that varying magnitudes of the calcium input and output fluxes cannot explain the observed δ^44/40Ca_SW trends, suggesting that the isotope signatures of these fluxes must also have changed. As a possible mechanism we suggest variable isotope fractionation in the sedimentary output flux controlled by the dominant mineralogy in marine carbonate deposits, i.e. the oscillating ‘calcite-aragonite seas’. The ultimate control of the calcium isotope budget of the Phanerozoic oceans appears to have been tectonic processes, specifically variable rates of oceanic crust production that modulated the hydrothermal calcium flux and the oceanic Mg/Ca ratio, which in turn controlled the dominant mineralogy of marine carbonates, hence the δ^44/40Ca_SW. As to the causes of the short-term oscillations recorded in the secular δ^44/40Ca_SW trend, we tentatively propose that these are related to variable rates of dolomite formation and/or to changing chemical composition of the riverine flux, in particular and ratios, induced by variable proportions of silicate vs. carbonate weathering rates on the continents.     

The origin of shoshonites: new insights from the Tertiary high-potassium intrusions of eastern Tibet

The shoshonitic intrusions of eastern Tibet, which range in age from 33 to 41 Ma and in composition from ultramafic (SiO₂ = 42 %) to felsic (SiO₂ = 74 %), were produced during the collision of India with Eurasia. The mafic and ultramafic members of the suite are characterized by phenocrysts of phlogopite, olivine and clinopyroxene, low SiO₂, high MgO and Mg/Fe ratios, and olivine forsterite contents of Fo₈₇ to Fo₉₃, indicative of equilibrium with mantle olivine and orthopyroxene. Direct melting of the mantle, on the other hand, could not have produced the felsic members. They have a phenocryst assemblage of plagioclase, amphibole and quartz, high SiO₂ and low MgO, with Mg/Fe ratios well below the values expected for a melt in equilibrium with the mantle. Furthermore, the lack of decrease in Cr with increasing SiO₂ and decreasing MgO from ultramafic to felsic rocks precludes the possibility that the felsic members were derived by fractional crystallization from the mafic members. Similarly, magma mixing, crustal contamination and crystal accumulation can be excluded as important processes. Yet all members of the suite share similar incompatible element and radiogenic isotope ratios, which suggests a common origin and source. We propose that melting for all members of the shoshonite suite was initiated in continental crust that was thrust into the upper mantle at various points along the transpressional Red River-Ailao Shan-Batang-Lijiang fault system. The melt formed by high-degree, fluid-absent melting reactions at high-T and high-P and at the expense of biotite and phengite. The melts acquired their high concentrations of incompatible elements as a consequence of the complete dissolution of pre-existing accessory minerals. The melts produced were quartz-saturated and reacted with the overlying mantle to produce garnet and pyroxene during their ascent. The felsic magmas reacted little with the adjacent mantle and preserved the essential features of their original chemistry, including their high SiO₂, low Ni, Cr and MgO contents, and low Mg/Fe ratio, whereas the mafic and ultramafic magmas are the result of extensive reaction with the mantle. Although the mafic magmas preserved the incompatible element and radiogenic isotope ratios of their crustal source, buffering by olivine and orthopyroxene extensively modified their MgO, Ni, Cr, SiO₂ contents and Mg/Fe ratio to values dictated by equilibrium with the mantle.     

Calcium isotope (δCa) fractionation along hydrothermal pathways, Logatchev field (Mid-Atlantic Ridge, 14°45′N)

We investigate the Logatchev Hydrothermal Field at the Mid-Atlantic Ridge, 14°45′N to constrain the calcium isotope hydrothermal flux into the ocean. During the transformation of seawater to a hydrothermal solution, the Ca concentration of pristine seawater ([Ca]_SW) increases from about 10 mM to about 32 mM in the hydrothermal fluid endmember ([Ca]_HydEnd) and thereby adopts a δ^44/40Ca_HydEnd of −0.95 ± 0.07‰ relative to seawater (SW) and a ⁸⁷Sr/⁸⁶Sr isotope ratio of 0.7034(4). We demonstrate that δ^44/40Ca_HydEnd is higher than that of the bedrock at the Logatchev field. From mass balance calculations, we deduce a δ^44/40Ca of −1.17 ± 0.04‰ (SW) for the host-rocks in the reaction zone and −1.45 ± 0.05‰ (SW) for the isotopic composition of the entire hydrothermal cell of the Logatchev field. The values are isotopically lighter than the currently assumed δ^44/40Ca for Bulk Earth of −0.92 ± 0.18‰ (SW) [Skulan J., DePaolo D. J. and Owens T. L. (1997) Biological control of calcium isotopic abundances in the global calcium cycle. Geochim. Cosmochim. Acta61,(12) 2505-2510] and challenge previous assumptions of no Ca isotope fractionation between hydrothermal fluid and the oceanic crust [Zhu P. and Macdougall J. D. (1998) Calcium isotopes in the marine environment and the oceanic calcium cycle. Geochim. Cosmochim. Acta62,(10) 1691-1698; Schmitt A. -D., Chabeaux F. and Stille P. (2003) The calcium riverine and hydrothermal isotopic fluxes and the oceanic calcium mass balance. Earth Planet. Sci. Lett. 6731, 1-16]. Here we propose that Ca isotope fractionation along the fluid flow pathway of the Logatchev field occurs during the precipitation of anhydrite. Two anhydrite samples from the Logatchev Hydrothermal Field show an average fractionation of about Δ^44/40Ca = −0.5‰ relative to their assumed parental solutions. Ca isotope ratios in aragonites from carbonate veins from ODP drill cores indicate aragonite precipitation directly from seawater at low temperatures with an average δ^44/40Ca of −1.54 ± 0.08‰ (SW). The relatively large fractionation between the aragonite precipitates and seawater in combination with their frequent abundance in weathered mafic and ultramafic rocks suggest a reconsideration of the marine Ca isotope budget, in particular with regard to ocean crust alteration.     

Calcium Isotope Ratio (δ44/40Ca) Measurements of Ca‐Dominated Minerals and Rocks without Column Chemistry Using the Double‐Spike Technique and Thermal Ionisation Mass Spectrometry

In this study, to evaluate whether bias free Ca isotope ratios can be properly achieved by thermal ionisation mass spectrometry (TIMS) using the ⁴²Ca–⁴³Ca double‐spike technique without chemical purification, a series of comparable experiments (with or without column chemistry) were made on Ca‐dominated minerals and rocks. Minerals, including fluorite, calcite, titanite and apatite, displayed similar Ca isotope ratios with Δ^44/40Ca_{with‐without} ranging from ?0.02 to +0.07‰. For Ca‐rich rocks, we mainly focused on the carbonates since they are the main repositories of Ca at the surface of the Earth. Coral, stalagmite, carbonatite, dolomite, marble and limestone are studied here. Interestingly, δ^44/40Ca_{SRM 915a} of these minerals and rocks without chemical purification displayed little drift compared with that of rocks with chemical purification, with Δ^44/40Ca_{with‐without} merely spanning from ?0.04 to +0.04‰. This implies that Ca isotope ratios can be achieved without column chemistry, possibly due to a property of TIMS in which Ca ions are only ionised at a target temperature and with a specific activator without ionising other ions. Therefore, for Ca‐dominated minerals or rocks, we suggest that column chemistry is unnecessary if they are totally dissolved and mixed in proper proportion with the ⁴²Ca–⁴³Ca double spike for TIMS measurement.     

Effects of basement composition and age on silicic magmas across an accreted terrane-Precambrian crust boundary,Sierra Madre Occidental,Mexico

Trace element and isotopic compositions of mid-Tertiary siliceous magma sequences from two localities of the Sierra Madre Occidental, northern Mexico, display differences that reflect the composition and age of the basement through which they erupted. The crust beneath the section at San Buenaventura is thicker and more evolved and forms part of the North American basement, while that under El Divisadero consists of allochthonous terranes of island arc/oceanic? crust accreted during the Mesozoic.The volcanics are highly differentiated and range in composition from basalt to rhyolite (SiO₂=50–76%). Those erupted through the accreted terranes display a small range of isotope ratios and have lowest initial (age-corrected) Sr isotope ratios (>0.7044) and the highest Nd (<0.5126) and Pb isotope ratios (²⁰⁶Pb/²⁰⁴Pb ∼18.9). Isotope ratios of the continental suite are more variable and form an array which trends away from that of the accreted terrane suite toward compositions more typical of old crust (to ⁸⁷Sr/⁸⁶Sr ∼0.710 and ¹⁴³Nd/¹⁴⁴Nd ∼0.5123). The volcanics in the continental zone are relatively more enriched in moderately incompatible elements compared with those within the accreted terranes (Ce/Yb=25–45 vs. 13–33, respectively), but are depleted in some highly incompatible elements such as U and Rb (e.g., Th/U=3.8–7.5 vs. 2.5–4.0, respectively). Those higher in the stratigraphic sections have higher ⁸⁷Sr/⁸⁶Sr, ²⁰⁸Pb/²⁰⁴Pb, and Th/U ratios, and lower ¹⁴³Nd/¹⁴⁴Nd ratios than those lower in the sections.The data have implications for the nature of the sources and the petrogenesis of these volcanics. The isotope ratios of both suites fall between those of mafic magma compositions from the Sierra Madre Occidental, and intermediate and felsic lower crustal xenoliths in northern Mexico and the southwestern USA. The relationship between the isotope ratios of the sequences and the age of the basement, combined with the fact that the overall data set forms well-defined isotopic arrays, demonstrates the strong effects of the crust on the chemistry of the silicic magmas. In the continental suite, isotope ratios covary with Th/Pb and U/Pb ratios, approaching the compositions found in the intermediate and felsic granulite facies xenoliths, strongly indicating that they are not anatectic melts of the lower crust but rather reflect interaction between mantle-derived basaltic parental magmas and the crust. Crustal contributions appear to be large, on the order of 20–70%. The small range of isotope ratios in the accreted terrane suite appears to reflect interaction of the basaltic parent with relatively juvenile crust whose isotopic composition is similar to the mantle-derived magmas. High Th/U and Th/Rb ratios indicate that the crustal contamination occurs in the lower crust. Moreover, the less radiogenic ²⁰⁶Pb/²⁰⁴Pb and ²⁰⁷Pb/²⁰⁴Pb ratios in the continental suite indicate that the depletion in highly incompatible elements in the continental lower crust is an old feature. The secular changes in the isotope ratios within the stratigraphic sections indicate increasingly shallow crustal contributions with time, initially by predominantly mafic deep lower crust and later by more felsic middle crust. Using lavas from outside of the two heavily sampled stratigraphic sections, the differences in the isotopic compositions between volcanics erupted through the accreted terranes and the continental basement help to delineate the location of the boundary.     

Model for kinetic effects on calcium isotope fractionation (δCa) in inorganic aragonite and cultured planktonic foraminifera

The calcium isotope ratios (δ⁴⁴Ca = [(⁴⁴Ca/⁴⁰Ca)_sample/(⁴⁴Ca/⁴⁰Ca)_standard −1] · 1000) of Orbulina universa and of inorganically precipitated aragonite are positively correlated to temperature. The slopes of 0.019 and 0.015‰ °C⁻¹, respectively, are a factor of 13 and 16 times smaller than the previously determined fractionation from a second foraminifera, Globigerinoides sacculifer, having a slope of about 0.24‰ °C⁻¹. The observation that δ⁴⁴Ca is positively correlated to temperature is opposite in sign to the oxygen isotopic fractionation (δ¹⁸O) in calcium carbonate (CaCO₃). These observations are explained by a model which considers that Ca²⁺-ions forming ionic bonds are affected by kinetic fractionation only, whereas covalently bound atoms like oxygen are affected by kinetic and equilibrium fractionation. From thermodynamic consideration of kinetic isotope fractionation, it can be shown that the slope of the enrichment factor α(T) is mass-dependent. However, for O. universa and the inorganic precipitates, the calculated mass of about 520 ± 60 and 640 ± 70 amu (atomic mass units) is not compatible with the expected ion mass for ⁴⁰Ca and ⁴⁴Ca. To reconcile this discrepancy, we propose that Ca diffusion and δ⁴⁴Ca isotope fractionation at liquid/solid transitions involves Ca²⁺-aquocomplexes (Ca[H₂O]_n²⁺ · mH₂O) rather than pure Ca²⁺-ion diffusion. From our measurements we calculate that such a hypothesized Ca²⁺-aquocomplex correlates to a hydration number of up to 25 water molecules (490 amu). For O. universa we propose that their biologically mediated Ca isotope fractionation resembles fractionation during inorganic precipitation of CaCO₃ in seawater. To explain the different Ca isotope fractionation in O. universa and in G. sacculifer, we suggest that the latter species actively dehydrates the Ca²⁺-aquocomplex before calcification takes place. The very different temperature response of Ca isotopes in the two species suggests that the use of δ⁴⁴Ca as a temperature proxy will require careful study of species effects.     

Charnockitic magmatism in southern India

Large charnockite massifs cover a substantial portion of the southern Indian granulite terrain. The older (late Archaean to early Proterozoic) charnockites occur in the northern part and the younger (late Proterozoic) charnockites occur in the southern part of this high-grade terrain. Among these, the older Biligirirangan hill, Shevroy hill and Nilgiri hill massifs are intermediate charnockites, with Pallavaram massif consisting dominantly of felsic charnockites. The charnockite massifs from northern Kerala and Cardamom hill show spatial association of intermediate and felsic charnockites, with the youngest Nagercoil massif consisting of felsic charnockites. Their igneous parentage is evident from a combination of features including field relations, mineralogy, petrography, thermobarometry, as well as distinct chemical features. The southern Indian charnockite massifs show similarity with high-Ba-Sr granitoids, with the tonalitic intermediate charnockites showing similarity with high-Ba-Sr granitoids with low K₂O/Na₂O ratios, and the felsic charnockites showing similarity with high-Ba-Sr granitoids with high K₂O/Na₂O ratios. A two-stage model is suggested for the formation of these charnockites. During the first stage there was a period of basalt underplating, with the ponding of alkaline mafic magmas. Partial melting of this mafic lower crust formed the charnockitic magmas. Here emplacement of basalt with low water content would lead to dehydration melting of the lower crust forming intermediate charnockites. Conversely, emplacement of hydrous basalt would result in melting at higher {ie565-01} favoring production of more siliceous felsic charnockites. This model is correlated with two crustal thickening phases in southern India, one related to the accretion of the older crustal blocks on to the Archaean craton to the north and the other probably related to the collision between crustal fragments of East and West Gondwana in a supercontinent framework.     

Phanerozoic magma underplating and crustal growth beneath the North China Craton

Evidence for post‐Archaean crustal growth via magma underplating is largely based on U–Pb dating of zircons from granulite‐facies xenoliths. However, whether the young zircons from such xenoliths are genetically related to magma underplating or to anatexis remains controversial. The lower‐crustal xenoliths carried by igneous rocks in the Chifeng and Ningcheng (North China Craton) have low SiO₂ and high MgO, indicating that parental melts of their protoliths were of unambiguous mantle origin. The xenoliths contain abundant magmatic zircons with late‐Palaeozoic ages, and have more radiogenic zircon Hf‐isotope compositions and hence younger model ages than ancient crustal magmas and the “reworking array” of the basement rocks. Our data suggest that the granulites represent episodic magmatic underplating to the lower crust of this craton in Phanerozoic time. Considering the observation that regional lowermost crust (~5 km) is mafic and characterized by Phanerozoic zircons, this work reports an example of post‐Archaean crustal growth via magma underplating.     

Non-biological fractionation of stable Ca isotopes in soils of the Atacama Desert, Chile

We measured Ca stable isotope ratios (δ^44/40Ca) in an ancient (2 My), hyperarid soil where the primary source of mobile Ca is atmospheric deposition. Most of the Ca in the upper meter of this soil (3.5 kmol m⁻²) is present as sulfates (2.5 kmol m⁻²), and to a lesser extent carbonates (0.4 kmol m⁻²). In aqueous extracts of variably hydrated calcium sulfate minerals, δ^44/40Ca_E values (vs. bulk Earth) increase with depth (1.4 m) from a minimum of −1.91‰ to a maximum of +0.59‰. The trend in carbonate-δ^44/40Ca in the top six horizons resembles that of sulfate-δ^44/40Ca, but with values 0.1-0.6‰ higher. The range of observed Ca isotope values in this soil is about half that of δ^44/40Ca values observed on Earth. Linear correlation among δ^44/40Ca, δ³⁴S and δ¹⁸O values indicates either (a) a simultaneous change in atmospheric input values for all three elements over time, or (b) isotopic fractionation of all three elements during downward transport. We present evidence that the latter is the primary cause of the isotopic variation that we observe. Sulfate-δ³⁴S values are positively correlated with sulfate-δ¹⁸O values (R² = 0.78) and negatively correlated with sulfate δ^44/40Ca_E values (R² = 0.70). If constant fractionation and conservation of mass with downward transport are assumed, these relationships indicate a δ^44/40Ca fractionation factor of −0.4‰ in CaSO₄. The overall depth trend in Ca isotopes is reproduced by a model of isotopic fractionation during downward Ca transport that considers small and infrequent but regularly recurring rainfall events. Near surface low Ca isotope values are reproduced by a Rayleigh model derived from measured Ca concentrations and the Ca fractionation factor predicted by the relationship with S isotopes. This indicates that the primary mechanism of stable isotope fractionation in CaSO₄ is incremental and effectively irreversible removal of an isotopically enriched dissolved phase by downward transport during small rainfall events.     

Mantle and crustal sources of Archean anorthosite: a combined in situ isotopic study of Pb–Pb in plagioclase and Lu–Hf in zircon

Isotopic analyses of ancient mantle-derived magmatic rocks are used to trace the geochemical evolution of the Earth’s mantle, but it is often difficult to determine their primary, initial isotope ratios due to the detrimental effects of metamorphism and secondary alteration. We present in situ analyses by LA-MC-ICPMS for the Pb isotopic compositions of igneous plagioclase (An_75–89) megacrysts and the Hf isotopic compositions of BSE-imaged domains of zircon grains from two mantle-derived anorthosite complexes from south West Greenland, Fiskenæsset and Nunataarsuk, which represent two of the best-preserved Archean anorthosites in the world. In situ LA-ICPMS U–Pb geochronology of the zircon grains suggests that the minimum crystallization age of the Fiskenæsset complex is 2,936 ± 13 Ma (2σ, MSWD = 1.5) and the Nunataarsuk complex is 2,914 ± 6.9 Ma (2σ, MSWD = 2.0). Initial Hf isotopic compositions of zircon grains from both anorthosite complexes fall between depleted mantle and a less radiogenic crustal source with a total range up to 5 ε_Hf units. In terms of Pb isotopic compositions of plagioclase, both anorthosite complexes share a depleted mantle end member yet their Pb isotopic compositions diverge in opposite directions from this point: Fiskenæsset toward a high-μ, more radiogenic Pb, crustal composition and Nunataarsuk toward low-μ, less radiogenic Pb, crustal composition. By using Hf isotopes in zircon in conjunction with Pb isotopes in plagioclase, we are able to constrain both the timing of mantle extraction of the crustal end member and its composition. At Fiskenæsset, the depleted mantle melt interacted with an Eoarchean (~3,700 Ma) mafic crust with a maximum ¹⁷⁶Lu/¹⁷⁷Hf ~0.028. At Nunataarsuk, the depleted mantle melt interacted with a Hadean (~4,200 Ma) mafic crust with a maximum ¹⁷⁶Lu/¹⁷⁷Hf ~0.0315. Evidence from both anorthosite complexes provides support for the long-term survival of ancient mafic crusts that, although unidentified at the surface to date, could still be present within the Fiskenæsset and Nunataarsuk regions.     

Chemistry of rainwater in the Massif Central (France): a strontium isotope and major element study

Atmospheric aerosols (sea salt, crustal dust, and biogenic aerosols) are the primary source of dissolved species in rainwater as well as one of the sources of dissolved species in river water. Chemical weathering studies require quantification of this atmospheric input. The crustal component of atmospheric input can have various origins, both distant and local. The proportions of the various inputs (marine, distant or local) are determined in this study.Strontium isotope ratios and Ca, Na, K, Mg, Al, Cl, SO₄, NO₃ and Sr concentrations were measured in rainwater samples collected in the Massif Central (France) over a period of one year. Each sample, collected automatically, represents a monthly series of rain events. Chemical composition of the rainwater samples varied considerably and the ⁸⁷Sr/⁸⁶Sr ratios ranged between 0.709198 and 0.713143.Using Na as an indicator of marine origin, and Al for the crustal input in rain samples, the proportion of marine and crustal elements was estimated from elemental ratios. A marine origin of 4 to 100% of Cl, of 0.6 to 20% of the SO₄, of <1 to 10% of Ca, <1 to 40% of K, 4 to 100% of Mg and 1 to 44% of Sr was determined.Strontium isotopes were used to characterize the crustal sources. The ⁸⁷Sr/⁸⁶Sr ratios of the crustal sources varied considerably from 0.7092 to 0.71625 and indicate the occurrence of multiple sources for the crustal component in the analysed rainwaters.     

U-Pb zircon dating of mafic dykes and its application to the Proterozoic geological history of the Vestfold Hills,East Antarctica

The Vestfold Hills, one of several Archaean cratonic blocks within the East Antarctic Shield, comprises a high-grade metamorphic basement complex intruded by at least nine generations of Early to Middle Proterozoic mafic dykes. Extensive U-Pb ion microprobe (SHRIMP) analyses of zircons, derived predominantly from late-stage felsic differentiates of the mafic dykes, provide precise crystallisation ages for several dyke generations. These new ages enable constraints to be placed on both the history of mafic magmatism in the Vestfold Hills and the timing of the various interspersed Proterozoic deformation events. In addition to demonstrating the utility of zircons derived from felsic late-stage differentiates for the dating of co-genetic mafic dykes, this study also places doubt on previous wholerock Rb-Sr dating of mafic dyke suites in this and other areas of East Antarctica. The ²⁰⁷Pb/²⁰⁶Pb zircon ages of 2241±4 Ma and 2238±7 Ma for the Homogeneous and Mottled Norites, respectively, provide a younger emplacement age for associated group 2 High-Mg tholeiite dykes than the whole-rock Rb-Sr date (2424±72 Ma) originally interpreted as the age of all high-Mg intrusives in the Vestfold Hills. Zircon ages of 1754±16 Ma and 1832±72 Ma confirm the previously defined Rb-Sr age of the group 2 Fe-rich tholeiites. Two later dyke generations, the group 3 and 4 Fe-rich tholeiites, are distinguished on the basis of field orientations and cross-cutting relationships, and yield zircon emplacement ages of 1380±7 Ma and 1241±5 Ma which also define minimum ages for two suites of lamprophyre dykes. Xenocrystic zircons within both felsic segregations and mafic dykes yield zircon ages of 2478±5 Ma to 2740 Ma, indicating the presence of Archaean crustal source rocks of this antiquity beneath the Vestfold Hills.     

Magma sources for Mesozoic anorogenic granites of the White Mountain magma series,New England,USA

The magma sources for granitic intrusions related to the Mesozoic White Mountain magma series in northern New England, USA, are addressed relying principally upon Nd isotopes. Many of these anorogenic complexes lack significant volumes of exposed mafic lithologies and have been suspected of representing crustal melts. Sm–Nd and Rb–Sr isotope systematics are used to evaluate magma sources for 18 felsic plutons with ages ranging from about 120 to 230 Ma. The possibility of crustal sources is further examined with analyses of representative older crust including Paleozoic granitoids which serve as probes of the lower crust in the region. Multiple samples from two representative intrusions are used to address intrapluton initial isotopic heterogeneities and document significant yet restricted variations (<1 in _Nd). Overall, Mesozoic granite plutons range in _Nd [T] from +4.2 to -2.3, with most +2 to 0, and in initial ⁸⁷Sr/⁸⁶Sr from 0.7031 to 0.709. The isotopic variations are roughly inversely correlated but are not obviously related to geologic, geographic, or age differences. Older igneous and metamorphic crust of the region has much lower Nd isotope ratios with the most radiogenic Paleozoic granitoid at _Nd [180 Ma] of -2.8. These data suggest mid-Proterozoic separation of the crust in central northern New England. Moreover, the bulk of the Mesozoic granites cannot be explained as crustal melts but must have large mantle components. The ranges of Nd and Sr isotopes are attributed to incorporation of crust by magmas derived from midly depleted mantle sources. Crustal input may reflect either magma mixing of crustal and mantle melts or crustal assimilation which is the favored interpretation. The results indicate production of anorogenic granites from mantle-derived mafic magmas.