Inter-mineral Fractionation Research Articles

Lower crustal control in the iron isotope systematics of plutonic xenoliths from Adak Island, Central Aleutians, with implications for arc magma geochemistry

We present bulk-rock and mineral Fe isotope data of ultramafic to mafic xenoliths and basaltic to andesitic lavas from Adagdak Volcano (Adak Island, Central Aleutians) to study the effects of early differentiation on the Fe isotopic evolution of island arc basalts and their crystallization products. The Fe isotope composition of ultramafic cumulate xenoliths increases from dunite (δ56Fe = –0.09 to –0.02 ‰) to clinopyroxenite (δ56Fe = +0.06 to +0.09 ‰), consistent with higher modal proportions of clinopyroxene (δ56Fe = –0.05 to +0.11 ‰) relative to olivine (δ56Fe = –0.10 to +0.06 ‰) in the latter. Mid-crustal cumulate amphibole gabbro and hornblendite cumulates also record heavier Fe isotope compositions (δ56Fe = +0.04 to +0.08 ‰) due to the abundance of isotopically heavy amphibole (δ56Fe = +0.07 to +0.09 ‰) and magnetite (δ56Fe = +0.11 to +0.13 ‰) in these rocks. High inter-mineral fractionations observed in spinel-olivine and spinel-clinopyroxene pairs (Δ56Fespl-ol = +0.12 to +0.28 and Δ56Fespl-cpx = +0.06 to +0.19) suggest that spinel is not recording equilibrium crystallization conditions for the ultramafic assemblages, likely due to subsolidus Fe-Mg exchange. Our data also include Fe isotope measurements of one mantle dunite (δ56Fe = +0.03 ± 0.05 ‰). Five Adagdak lavas, spanning from basalts to andesites, yield a narrow range of δ56Fe between +0.03 and +0.06 ‰. Our results highlight the potential of amphibole in driving the Fe isotope depletion trends observed in many erupted arc lavas, as amphibole hosts 28–99 % of the FeOT budget in the amphibole gabbro and hornblendite cumulates. This is also supported by single-crystal synchrotron Mössbauer spectroscopy of two amphibole grains, the first from an amphibole gabbro and the second from a hornblendite, which yield Fe3+/ΣFe ratios of 0.55 ± 0.06 and 0.58 ± 0.02, respectively. Water content and hydrogen isotope compositions determined by secondary-ion mass spectrometry from the same amphibole grains indicate partial dehydrogenation. Using Rayleigh fractionation modeling to account for oxidation during post-crystallization dehydrogenation, we calculate magmatic Fe3+/ΣFe ratios of 0.41 ± 0.04 for the amphibole gabbro and 0.30 ± 0.05 for the hornblendite. These data are then used to estimate an appropriate Fe force constant for Adagdak amphibole and quantitatively evaluate the effects of amphibole fractionation. Through a fractional crystallization model, we show how arc melts may experience periods of increasing δ56Fe during olivine-dominated fractionation, followed by decreasing δ56Fe once magnetite and amphibole saturate as cumulate phases. Notably, this dichotomy between fractionation of isotopically light versus heavy cumulate assemblages and its effects on the Fe isotope evolution of arc magmas is not captured by the Adagdak lava record, highlighting the utility of cumulates in chronicling the early isotopic evolution of magmatic systems.

Zirconium stable isotope fractionation during intra-crustal magmatic differentiation in an active continental arc

Zirconium (Zr) stable isotope variations occur among co-existing Zr-rich accessory phases as well as at the bulk-rock scale, but the petrologic mechanism(s) responsible for Zr isotope fractionation during magmatic differentiation remain unclear. Juvenile magma generation and intra-crustal differentiation in convergent continental margins may play a crucial role in developing Zr isotope variations, and the Northern Volcanic Zone of the Andes is an ideal setting to test this hypothesis. To investigate the influence of these processes on Zr stable isotope compositions, we report δ94/90ZrNIST of whole rock samples from: 1) juvenile arc basalts from the Quaternary Granatifera Tuff, Colombia; 2) lower crust-derived garnet pyroxenites (i.e., arclogites), hornblendites, and gabbroic cumulates found in the same unit; and 3) felsic volcanic products from the Doña Juana Volcanic Complex, a dacitic composite volcano in close proximity to and partially covering the Granatifera Tuff. The basalts have δ94/90ZrNIST values ranging from −0.025 ± 0.018 ‰ to +0.003 ± 0.015 ‰ (n = 8), within the range of mid-ocean ridge basalts. The dacites have δ94/90ZrNIST values ranging from +0.008 ± 0.013 ‰ to +0.043 ± 0.015 ‰ (n = 14), slightly positive relative to the Granatifera and mid-ocean ridge basalts. In contrast, the (ultra)mafic cumulates have highly variable, predominantly positive δ94/90ZrNIST values, ranging from −0.134 ± 0.012 ‰ to +0.428 ± 0.012 ‰ (n = 15). Individual grains and mineral fractions of major rock-forming phases, including garnet (n = 21), amphibole (n = 9), and clinopyroxene (n = 18), were analyzed from 8 (ultra)mafic cumulates. The mineral fractions record highly variable Zr isotopic compositions, with inter-mineral fractionation (Δ94/90Zrgarnet-amphibole) up to 2.067 ‰. Recent ab initio calculations of Zr–O bond force constants in rock-forming phases predict limited inter-mineral Zr isotope fractionation in high-temperature environments, suggesting that the large fractionations we observe are not the product of vibrational equilibrium processes. Instead, we propose a scenario in which large Zr isotopic fractionations develop kinetically, induced by sub-solidus Zr diffusion between coexisting phases via changes in Zr distribution coefficients that arise from changes in temperature. Altogether, Zr isotope variability in this calc-alkaline continental arc setting exhibits no correlation with indices of magmatic differentiation (e.g., Mg#, SiO2), and is not a simple function of fractional crystallization. Furthermore, the garnet clinopyroxenite cumulates studied here represent density-unstable lower arc crust material; consequently, material with isotopically variable δ94/90Zr can be recycled into the mantle as a consequence of lower crustal foundering.

High-temperature inter-mineral potassium isotope fractionation: implications for K-Ca-Ar chronology.

Recent advances in high-precision potassium (K) isotopic analysis have found considerable isotopic variation in rock samples of the Earth's continental and oceanic crusts; however, it is still uncertain whether there is any resolvable inter-mineral and mineral-melt K isotopic fractionation during igneous and metamorphic processes. Here, we report K isotope compositions of mineral separates from three extremely well preserved igneous rocks (intrusive/extrusive and mafic/intermediate/felsic) in order to investigate possible inter-mineral and mineral-melt K isotopic fractionation at magmatic temperatures. For the first time, we found large inter-mineral fractionation of K isotopes in natural samples (up to 1.072‰), where plagioclase displays a significant enrichment of heavier K isotopes compared to potassium feldspar and biotite in a granite. In addition, we also observed smaller but measurable K isotope fractionation (0.280‰±0.030‰) between ternary feldspar phenocrysts and matrix in a trachyandesite, as well as a comparable isotope fractionation (0.331‰±0.010‰) between plagioclase and the bulk in a gabbroic intrusive rock. We also evaluated such results by comparing the theoretically calculated equilibrium K isotope fractionation factors between relevant igneous minerals in literature and this study. In general, the measured inter-mineral fractionations are consistent with the theoretical calculations (i.e., plagioclase is enriched in heavier isotopes compared to potassium feldspar). Specifically, the measured K isotope fractionation between phenocryst rim and matrix in the trachyandesite agrees well with the calculated equilibrium isotope fractionation. However, the measured K isotope fractionations between phenocryst core and matrix as well as between plagioclase and K-feldspar are significantly larger (by a factor of ~2-3) than the calculated isotope fractionations, which suggest isotopic disequilibrium due to kinetic processes. Using a range of plagioclase-melt isotope fractionation factors inferred from the theoretical calculations in this study, we modeled the K isotopic fractionation during the formation of lunar anorthositic crust, and the result shows a negligible effect on the K isotopic compositions in both lunar crust and mantle. The K isotopic difference between Earth and Moon, therefore, cannot be the result of Lunar Magma Ocean differentiation. Finally, we evaluate the effect of observed inter-mineral fractionations on K-Ar and 40Ar-39Ar dating. This study indicates the variation of 40K/K ratio would contribute a maximum 0.08% error to the K-Ar and 40Ar-39Ar age uncertainties. We propose a refined 40K/total K ratio as 0.00011664±0.00000011 (116.64±0.11ppm) instead of the conventional value, 0.0001167(2) for the present Earth. Because some minerals fractionate K isotopes, ultrahigh precision age dating with the K-Ca-Ar dating systems must measure the K isotope fractionation in the same mineral fractions used for age dating.

Potassium distribution and isotope composition in the lithospheric mantle in relation to global Earth’s reservoirs

Recent analytical advances have provided means to measure potassium (K) isotopes in various terrestrial materials, but little is known about K distribution and stable isotope composition in the lithospheric mantle because of: (a) common low K abundances, (b) potential contamination and alteration, (c) diversity of mantle rocks and minerals hosting K in different tectonic settings. We report K abundances and δ41K values for well-studied whole-rock (WR) mantle xenoliths (spinel and garnet peridotites and pyroxenites) from mobile belts, a craton, a subduction zone, as well as for K-rich phases (mica, amphibole, silicate glass) and xenolith-bearing volcanic materials (67 samples). The xenolith materials show extremely broad ranges of K content (7 μg/g to 6.6 wt.%) and δ41K (−2.77‰ to 0.62‰). They contrast with the narrow δ41K range for host volcanic materials (−0.53‰ to −0.27‰) and literature data on oceanic basalts (melting products of upwelling asthenosphere: −0.43 ± 0.17‰, 2sd). Amphibole-bearing subduction zone peridotites show the highest WR δ41K values (0.40–0.62‰) likely inherited from fluids released into the mantle wedge from subducted oceanic crust. All other WR samples yield negative δ41K: −0.06‰ to −2.77‰ for peridotites and −0.17‰ to −0.52‰ for pyroxenites. The δ41K in K-rich mantle phases range from positive values (0.16–0.57‰) for phlogopite in strongly metasomatized peridotites to negative values (−0.27 to −0.94‰) for phlogopite, amphibole and glass pockets from other samples, which cannot be explained by equilibrium inter-mineral fractionation inferred from ab initio calculations. We attribute the broad δ41K variations to (a) isotope fractionation during fluid-rock interaction in the mantle, and (b) distinct sources of K-bearing fluids. Kinetic isotope fractionation during fluid percolation and diffusion is inferred for composite xenoliths (phlogopite and pyroxenite veins in peridotites) that have lower δ41K in the hosts than in the veins due to slower migration of 41K than 39K from the veins (former fluid channels) to host mantle. Overall, the K isotope fractionation in the lithospheric mantle appears to be greater than for magmatic fractionation in the crust. The average δ41K of normal off-craton continental lithospheric mantle calculated from the least altered fertile and lightly metasomatized lherzolites is −0.57 ± 0.28‰ (2sd). This value is within error (though a little lower) of estimates for both continental crust and MORB and OIB mantle sources indicating that these major silicate Earth reservoirs have similar bulk δ41K values, apparently due to low or negligible K isotopic fractionation during their formation by magmatic differentiation and melting. By contrast, K isotopes in modern and fossil subduction zones are fractionated via fluid-related equilibrium and kinetic processes.

Magnesium and iron isotopic evidence of inter-mineral diffusion in ultramafic cumulates of the Peridotite Zone, Stillwater Complex

To better understand the role and extent of inter-mineral diffusion during subsolidus processes, we investigated the iron and magnesium isotopic compositions of olivine, orthopyroxene, and chromite separates from the Peridotite Zone of the Stillwater Complex. Olivine and orthopyroxene show limited Mg isotopic variations, with δ26Mg values ranging from −0.40 to −0.26‰ and from −0.29 to −0.22‰, respectively. In contrast, chromite displays extremely large Mg isotopic variations, with δ26Mg values ranging from −0.05 to +0.84‰. The δ56Fe values of olivine and orthopyroxene range from 0.00 to +0.17‰ and −0.04 to +0.06‰, respectively, whereas those of chromite range from −0.09 to +0.13‰. Most olivine-orthopyroxene pairs in our samples show no clear Fe-Mg isotopic differences, whereas silicate and coexisting chromite pairs plot away from theoretically predicted equilibrium lines, indicating disequilibrium inter-mineral fractionation. Higher δ56Fe values in silicates than in chromite and significantly higher δ26Mg values in chromite than in silicates indicate that subsolidus re-equilibration is responsible for the observed disequilibrium Fe-Mg isotope fractionation. We develop a quantitative model based on the investigated olivine and chromite to reproduce the observed kinetic Fe-Mg isotope fractionations. Our model results indicate a systematic difference between the Fe and Mg isotope fractionation factors, β, of olivine (βFe ≈ 0.27 and βMg ≈ 0.16) and chromite (0.03 < βFe < 0.08 and 0.05 < βMg < 0.16). This study demonstrates that combined investigations of the Fe-Mg isotopic compositions of cumulus minerals provide more recognizable and more reliable information on inter-mineral diffusion among igneous minerals in magma chambers than elemental analyses alone.

Heterogeneous nickel isotopic compositions in the terrestrial mantle – Part 1: Ultramafic lithologies

High precision nickel stable isotopic compositions (δ60/58Ni) are reported for 22 peridotite xenoliths from the USA (Kilbourne Hole, New Mexico), Tanzania, and Cameroon. For a subset of these, δ60/58Ni is also reported for their constituent mineral separates (olivine, orthopyroxene, clinopyroxene, and spinel). Bulk peridotites show significant heterogeneity in Ni isotopic composition, ranging from +0.02‰ to +0.26‰. Unmetasomatised fertile peridotites from three localities, define an average δ60/58Ni of +0.19±0.09‰ (n = 18). This value is comparable to previous estimates for the δ60/58Ni of the bulk silicate earth (BSE), but is unlikely to be representative, given observed heterogeneity, presented here and elsewhere. Samples with reaction rims and interstitial glass (interpreted as petrographic indications of minor metasomatism) were excluded from this average; their Ni isotopic compositions extend to lighter values, spanning nearly the entire range observed in peridotite worldwide. Dunites (n = 2) are lighter in δ60/58Ni than lherzolites and harzburgites from the same location, and pyroxenites (n = 5) range from +0.16‰ to as light as −0.38‰.The δ60/58Ni in the Kilbourne Hole xenoliths correlate negatively with bulk-rock Fe concentration and positively with 143Nd/144Nd, providing evidence that light δ60/58Ni is associated with mantle fertility and enrichment. The trend between δ60/58Ni and Fe concentration in bulk rocks appears to be global, replicated across the peridotites in this work from other localities, and in literature data.The inter-mineral fractionations are small; the maximum difference between heaviest and lightest phase is 0.12‰. This provides evidence that bulk rock δ60/58Ni variation does not result from differences in modal mineralogy, fractional crystallization or degrees of partial melting. The δ60/58Ni fractionation appears to be an equilibrium effect and usually is in the decreasing order spinel > olivine = orthopyroxene > clinopyroxene. However, the fractionation between clinopyroxene and orthopyroxene varies in magnitude and sign, and is correlated with pyroxene Si/Fe positively, and Fe/Mg negatively. The magnitude of inter-pyroxene fractionation also correlates with other pyroxene compositional ratios (e.g. La/Smclinopyroxene); as well as bulk rock δ60/58Ni, and [U]. These data provide evidence that Ni isotopes fractionate at the bulk rock and mineral scale in response to mantle enrichment processes, possibly related to recycling of isotopically light subducted components.

Origin of Rodingite Forming Fluids Constrained by Calcium and Strontium Isotope Ratios in the Leka Ophiolite Complex

Alteration of oceanic lithosphere plays an important role in the global element cycling due to its dominant abundance on the Earth's surface. The formation of rodingites, a Ca rich lithology that occurs intimately associated with Ca depleted serpentinite complexes, is a widespread process during strong alteration of ocean-floor lithologies and may represent a key process that influences the global Ca cycle. Stable Ca and radiogenic Sr isotope compositions of rodingites and associated lithologies from the Leka ophiolite complex, Norway, preserve mantle signatures and thus provide evidence that the Ca and Sr sources for rodingitisation are dominantly mantle derived, with no detectable seawater input. The difference of ~0.7‰ in δ44/40Ca of different phases found in the rocks is overall consistent with inter-mineral fractionation at high temperatures related to the CaO bonding environment, but there are also indications for isotopic disequilibria between non-cogenetic mineral phases.While the water required for rodingite formation may originate from seawater, the dissolved Ca and Sr involved in the mineral reactions during rodingitisation (Plg + Ca - > Gros + Clz + Al) can be balanced at a local scale, being derived from the serpentinisation of mantle peridotites (Cpx1 + H2O + Al = Srp + Chlorite + Ca + Cpx2). Consequently, rodingites do not act as a sink for oceanic Ca. Instead, they are a sink for Ca released during serpentinisation of the oceanic lithospheric mantle.

Diffusion-driven extreme Mg and Fe isotope fractionation in Panzhihua ilmenite: Implications for the origin of mafic intrusion

To investigate the petrogenesis of Fe-Ti oxide ore deposits, we report Mg and Fe isotopic compositions for coexisting olivine, clinopyroxene and ilmenite in Fe-Ti oxide ores, magnetite-bearing gabbros and gabbros from the Panzhihua Fe-Ti-oxide-bearing layered mafic intrusion, Southwest China. Olivine and clinopyroxene have δ26Mg values ranging from −0.47 to −0.32‰ and −0.40 to −0.18‰, and δ57Fe values from −0.21 to +0.23‰ and −0.16 to +0.20‰, respectively. Most of these mineral pairs display disequilibrium inter-mineral fractionation as they fall off the theoretically predicted equilibrium fractionation lines. Ilmenites from oxide ores and magnetite-bearing gabbros (Group 1) have mantle-like or lower δ26Mg values of −0.80 to −0.13‰ and δ57Fe values of −0.33 to −0.23‰, and those from gabbros (Group 2) display slightly to extremely higher δ26Mg values of +0.48 to +23.10‰ and much lower δ57Fe values of −0.59 to −0.33‰. The δ26Mg negatively correlates with δ57Fe in all ilmenites, which cannot be explained by simple extensive fractional crystallization or Soret diffusion. Instead, the negative correlations between δ26Mg and δ57Fe and between MgO and FeO in ilmenites result from Mg-Fe inter-diffusion among ilmenite, silicate minerals and high-Ti basaltic melts. The extremely large isotopic variations were produced by the large Mg activity gradient between different types of ilmenites and melts, which was enhanced by interstitial liquid immiscibility process. Our study therefore demonstrates that combined Mg-Fe isotopes can be used to trace the genesis of Fe-Ti-oxide-bearing ore.

Mg isotope systematics during magmatic processes: Inter-mineral fractionation in mafic to ultramafic Hawaiian xenoliths

Observed differences in Mg isotope ratios between bulk magmatic rocks are small, often on a sub per mill level. Inter–mineral differences in the 26Mg/24Mg ratio (expressed as δ26Mg) in plutonic rocks are on a similar scale, and have mostly been attributed to equilibrium isotope fractionation at magmatic temperatures. Here we report Mg isotope data on minerals in spinel peridotite and garnet pyroxenite xenoliths from the rejuvenated stage of volcanism on Oahu and Kauai, Hawaii. The new data are compared to literature data and to theoretical predictions to investigate the processes responsible for inter–mineral Mg isotope fractionation at magmatic temperatures. Theory predicts up to per mill level differences in δ26Mg between olivine and spinel at magmatic temperatures and a general decrease in Δ26Mgolivine-spinel (=δ26Mgolivine – δ26Mgspinel) with increasing temperature, but also with increasing Cr# in spinel. For peridotites with a simple petrogenetic history by melt depletion, where increasing depletion relates to increasing melting temperatures, Δ26Mgolivine-spinel should thus systematically decrease with increasing Cr# in spinel. However, most natural peridotites, including the Hawaiian spinel peridotites investigated in this study, are overprinted by variable extents of melt-rock reaction, which disturb the systematic primary temperature and compositionally related olivine–spinel Mg isotope systematics. Diffusion, subsolidus re-equilibration, or surface alteration may further affect the observed olivine–spinel Mg isotope fractionation in peridotites, making Δ26Mgolivine-spinel in peridotites a difficult–to–apply geothermometer. The available Mg isotope data on clinopyroxene and garnet suggest that this mineral pair is a more promising geothermometer, but its application is restricted to garnet–bearing igneous (garnet pyroxenites) and metamorphic rocks (eclogites). Although the observed δ26Mg variation is on a sub per mill range in bulk magmatic rocks, the clearly resolvable inter–mineral Mg isotope differences imply that crystallization or preferential melting of isotopically distinct minerals such garnet, spinel, and clinopyroxene should cause Mg isotope fractionation between bulk melt and residue. Calculated Mg isotope variations during partial mantle melting indeed predict differences between melt and residue, but these are analytically resolvable only for melting of mafic lithologies, that is, garnet pyroxenites. Contributions from garnet pyroxenite melts may thus account for some of the isotopically light δ26Mg observed in ocean island basalts and trace lithological mantle heterogeneity. Consequently, applications for high-temperature Mg isotope fractionations are promising and diverse, and recent advances in analytical precision may allow the full petrogenetic potential inherent in the sub per mill variations in δ26Mg in magmatic rocks to be exploited.

Magnesium isotopic evidence for chemical disequilibrium among cumulus minerals in layered mafic intrusion

Magnesium isotopic compositions of olivine, clinopyroxene, and ilmenite from the Baima intrusion, SW China, for the first time, are investigated to constrain the magnitude and mechanisms of Mg isotope fractionation among cumulus minerals in layered mafic intrusions and to evaluate their geological implications. Olivine and clinopyroxene have limited Mg isotope variations, with δ26Mg ranging from −0.33 to +0.05‰ and from −0.29 to −0.13‰, respectively, similar to those of mantle xenolithic peridotites. By contrast, ilmenites display extremely large Mg isotopic variation, with δ26Mg ranging from −0.50 to +1.90‰. The large inter-mineral fractionations of Mg isotopes between ilmenite and silicates may reflect both equilibrium and kinetic processes. A few ilmenites have lighter Mg isotopic compositions than coexisting silicates and contain high MgO contents without compositional zoning, indicating equilibrium fractionation. The implication is that the light Mg isotopic compositions of lunar high-Ti basalts may result from an isotopically light source enriched in cumulate ilmenites. On the other hand, most ilmenites have heavy Mg isotopic compositions, coupled with high MgO concentration and chemical zoning, which can be quantitatively modeled by kinetic Mg isotope fractionations induced by subsolidus Mg–Fe exchange between ilmenite and ferromagnesian silicates during the cooling of the Baima intrusion. The extensive occurrence of kinetic Mg isotope fractionation in ilmenites implies the possibility of widespread compositional disequilibrium among igneous minerals in magma chambers. Consequently, disequilibrium effects need to be considered in studies of basaltic magma evolution, magma chamber processes, and magmatic Fe–Ti oxide ore genesis.

Chromite-induced magnesium isotope fractionation during mafic magma differentiation

To better understand the mechanism of Mg isotopic variation in magma systems, here we report high precision Mg isotopic data of 17 bulk rock samples including dunite, clinopyroxenite, hornblendite and gabbro and 10 pairs of dunite-hosted olivine and chromite separates from the well-characterized Alaskan-type Xiadong intrusion in NW China, which formed by continuous and high degree of lithological differentiation from mafic magmas. Chromite separates have highly variable δ26Mg values from −0.10‰ to 0.40‰, and are consistently heavier than coexisting olivine separates (−0.39‰ to −0.15‰). Both mineral δ26Mg values and the degrees of inter-mineral fractionation are well correlated with geochemical indicators of magma differentiation, indicating that these inter-sample and inter-mineral Mg isotope fractionations are caused by magma evolution. The δ26Mg values range from −0.20‰ to −0.02‰ in the dunite, −0.43‰ in the clinopyroxenite, −0.43‰ to −0.28‰ in the hornblendite, 0.18‰ in the chromite-bearing hornblendite, and −0.56‰ to −0.16‰ in the gabbro. The Mg isotopic variations in different types of rocks are closely related to fractional crystallization and accumulation of different proportions of oxides vs. silicates. Chromite crystallization and accumulation is the most important factor in controlling Mg isotope fractionation during the formation of the Xiadong intrusion. Compared to basaltic and granitic magmas, differentiation of the Alaskan-type intrusions occurs at a relatively high oxygen fugacity, which favors chromite crystallization and consequently significant Mg isotope fractionations at both mineral and whole-rock scales. Therefore, Mg isotope systematics can be used to trace the degree of magma differentiation and related-mineralization.

Mineral composition control on inter-mineral iron isotopic fractionation in granitoids

This study reports elemental and iron isotopic compositions of feldspar and its coexisting minerals from four Dabie I-type granitoids to evaluate the factors that control inter-mineral Fe isotopic fractionation in granitoids. The order of heavy iron isotope enrichment is feldspar>pyrite>magnetite>biotite≈hornblende. Feldspar has heavier iron isotopic compositions than its co-existing magnetite (Δ56Feplagioclase–magnetite=+0.376‰ to +1.084‰, Δ56Fealkali-feldspar–magnetite=+0.516‰ to +0.846‰), which can be attributed to its high Fe3+/Fetot ratio and low coordination number (tetrahedrally-coordinated) of Fe3+. Δ56Femagnetite–biotite of coexisting magnetite and biotite ranges from 0.090‰ to 0.246‰. Based on homogeneous major and iron isotopic compositions of mineral replicates, the inter-mineral fractionation in this study should reflect equilibrium fractionation. The large variations of inter-mineral fractionation among feldspar, magnetite and biotite cannot be simply explained by temperature variation, but strongly depend on mineral compositions. The Δ56Feplagioclase–magnetite and Δ56Fealkali-feldspar–magnetite are positively correlated with albite mode in plagioclase and orthoclase mode in alkali-feldspar, respectively. This could be explained by different Fe–O bond strength in feldspar due to different Fe3+/∑Fe or different crystal parameters. The Δ56Femagnetite–biotite increases with decreasing Fe3+/∑Febiotite and increasing mole (Na+K)/Mgbiotite, indicating a decrease of β factor in low Fe3+/∑Fe and high (Na+K)/Mg biotite.High-silica leucosomes from Dabie migmatites with a feldspar accumulation petrogenesis have higher δ56Fe values (δ56Fe=0.42–0.567‰) than leucosome that represents pristine partial melt (δ56Fe=0.117±0.016‰), indicating that accumulation of feldspar could account for high δ56Fe values of these rocks. High δ56Fe values are also predicted for other igneous rocks that are mainly composed of cumulate feldspar crystals, e.g., anorthosites. Feldspar accumulation, however, cannot explain high δ56Fe values of most high-silica granitoids reported in the literature, based on their low Sr, Ba contents and negative Eu anomalies.

Zinc isotope fractionation during mantle melting and constraints on the Zn isotope composition of Earth’s upper mantle

The zinc (Zn) stable isotope system has great potential for tracing planetary formation and differentiation processes due to its chalcophile, lithophile and moderately volatile character. As an initial approach, the terrestrial mantle, and by inference, the bulk silicate Earth (BSE), have previously been suggested to have an average δ66Zn value of ∼+0.28‰ (relative to JMC 3-0749L) primarily based on oceanic basalts. Nevertheless, data for mantle peridotites are relatively scarce and it remains unclear whether Zn isotopes are fractionated during mantle melting. To address this issue, we report high-precision (±0.04‰; 2SD) Zn isotope data for well-characterized peridotites (n=47) from cratonic and orogenic settings, as well as their mineral separates. Basalts including mid-ocean ridge basalts (MORB) and ocean island basalts (OIB) were also measured to avoid inter-laboratory bias. The MORB analyzed have homogeneous δ66Zn values of +0.28±0.03‰ (here and throughout the text, errors are given as 2SD), similar to those of OIB obtained in this study and in the literature (+0.31±0.09‰). Excluding the metasomatized peridotites that exhibit a wide δ66Zn range of −0.44‰ to +0.42‰, the non-metasomatized peridotites have relatively uniform δ66Zn value of +0.18±0.06‰, which is lighter than both MORB and OIB. This difference suggests a small but detectable Zn isotope fractionation (∼0.1‰) during mantle partial melting. The magnitude of inter-mineral fractionation between olivine and pyroxene is, on average, close to zero, but spinels are always isotopically heavier than coexisting olivines (Δ66ZnSpl-Ol=+0.12±0.07‰) due to the stiffer Zn-O bonds in spinel than silicate minerals (Ol, Opx and Cpx). Zinc concentrations in spinels are 11–88 times higher than those in silicate minerals, and our modelling suggests that spinel consumption during mantle melting plays a key role in generating high Zn concentrations and heavy Zn isotopic compositions of MORB. Therefore, preferential melting of spinel in the peridotites may account for the Zn isotopic difference between spinel peridotites and basalts. By contrast, the absence of Zn isotope fractionation between silicate minerals suggests that Zn isotopes are not significantly fractionated during partial melting of spinel-free garnet-facies mantle. If the studied non-metasomatized peridotites represent the refractory upper mantle, mass balance calculation shows that the depleted MORB mantle (DMM) has a δ66Zn value of +0.20±0.05‰ (2SD), which is lighter than the primitive upper mantle (PUM) estimated in previous studies (+0.28±0.05‰, 2SD, Chen et al., 2013b; +0.30±0.07‰, 2SD, Doucet et al., 2016). This indicates that the Earth’s upper mantle has a heterogeneous Zn isotopic composition vertically, which is probably due to shallow mantle melting processes.

In-situ Fe isotope ratio determination in Fe–Ti oxides and sulfides from drilled gabbros and basalt from the IODP Hole 1256D in the eastern equatorial Pacific

In-situ Fe isotope measurements have been carried out to estimate the impact of the hydrothermal metamorphic overprint on the Fe isotopic composition of Fe–Ti-oxides and Fe-sulfides of the different lithologies of the drilled rocks from IODP Hole 1256D (eastern equatorial Pacific; 15Ma crust formed at the East Pacific Rise). Most igneous rocks normally have a very restricted range in their 56Fe/54Fe ratio. In contrast, Fe isotope compositions of hot fluids (>300°C) from mid-ocean-ridge spreading centers define a narrow range that is shifted to lower δ56Fe values by 0.2‰–0.5‰ as compared to igneous rocks. Therefore, it is expected that mineral phases that contain large amounts of Fe are especially affected by the interaction with a fluid that fractionates Fe isotopes during exsolution/precipitation of those minerals.We have used a femtosecond UV-Laser ablation system to determine mineral 56Fe/54Fe ratios of selected samples with a precision of <0.1‰ (2σ level) at micrometer-scale. We have found significant variations of the δ56FeIRMM-014 values in the minerals between different samples as well as within samples and mineral grains. The overall observed scale of δ56Femagnetite in 1256D rocks ranges from −0.12 to +0.64‰, and of δ56Feilmenite from −0.77 to +0.01‰. Pyrite in the lowermost sheeted dike section is clearly distinguishable from the other investigated lithological units, having positive δ56Fe values between +0.29 and +0.56‰, whereas pyrite in the other samples has generally negative δ56Fe values from −1.10 to −0.59‰.One key observation is that the temperature dependent inter-mineral fractionations of Fe isotopes between magnetite and ilmenite are systematically shifted towards higher values when compared to theoretically expected values, while synthesized, well equilibrated magnetite–ilmenite pairs are compatible with the theoretical predictions. Theoretical considerations including β-factors of different aqueous Fe-chlorides and Rayleigh-type fractionations in the presence of a hydrous, chlorine-bearing fluid can explain this observation. The disagreement between observed and theoretical equilibrium fractionation, the fact that magnetite, in contrast to ilmenite shows a slight downhole trend in the δ56Fe values, and the observation of small scale heterogeneities within single mineral grains imply that a general re-equilibration of the magnetite–ilmenite pairs is overprinted by kinetic fractionation effects, caused by the interaction of magnetite/ilmenite with hydrothermal fluids penetrating the upper oceanic crust during cooling, or incomplete re-equilibration at low temperatures.Furthermore, the observation of significant small-scale variations in the 56Fe/54Fe ratios of single minerals in this study highlights the importance of high spatial-resolution-analyses of stable isotope ratios for further investigations.

Large magnesium isotope fractionation in peridotite xenoliths from eastern North China craton: Product of melt–rock interaction

To investigate the effects of melt–rock interaction on Mg isotope fractionation and mantle Mg isotopic heterogeneity, we report high-precision Mg isotopic data of olivine (Ol), orthopyroxene (Opx), clinopyroxene (Cpx) and spinel (Spl) for 25 peridotite xenoliths from the eastern North China craton. These xenoliths range from lherzolites, Cpx-rich lherzolites to wehrlites, and are variably metasomatised. The lherzolites have Ol with Fo contents from 89 to 90 and have a homogeneous Mg isotopic composition (δ26Mg=−0.26 to −0.20), similar to the typical mantle value. By contrast, Cpx-rich lherzolites and wehrlites have lower Ol with Fo contents (78–88) and exhibit larger Mg isotopic variations, with δ26Mg ranging from −0.39 to +0.09. The δ26Mg values of minerals in these xenoliths are also variable and range from −0.45 to −0.03 in Ol, from −0.26 to −0.01 in Opx, from −0.34 to +0.22 in Cpx and from −0.16 to +0.25 in Spl. Inter-mineral fractionations between coexisting pyroxene and Ol in lherzolites and most isotopically light wehrlites (Δ26MgOpx–Ol=−0.04 to +0.09‰; Δ26MgCpx–Ol= +0.02 to +0.25‰) vary as a function of temperature and are consistent with equilibrium inter-mineral isotope fractionations. By contrast, large disequilibrium Mg isotope fractionation occurs between coexisting pyroxene and Ol in the majority of Cpx-rich lherzolites (Δ26MgOpx–Ol=+0.16 to +0.32‰; Δ26MgCpx–Ol=+0.04 to +0.34‰). Both types of isotope fractionations also occur between Spl and Ol, with Spl being consistently heavier than Ol (Δ26MgSpl–Ol=+0.15 to +0.55‰). Overall, the isotopically equilibrated but light wehrlites may result from mantle metasomatism by isotopically light melt, whereas large disequilibrium isotope fractionations in Cpx-rich peridotites likely reflect kinetic isotope fractionation during melt–peridotite interaction. Both processes result in the heterogeneous Mg isotopic composition of the lithospheric mantle beneath the eastern North China craton.

Iron and magnesium isotopic compositions of peridotite xenoliths from Eastern China

We present high-precision measurements of Mg and Fe isotopic compositions of olivine, orthopyroxene (opx), and clinopyroxene (cpx) for 18 lherzolite xenoliths from east central China and provide the first combined Fe and Mg isotopic study of the upper mantle. δ 56Fe in olivines varies from 0.18‰ to −0.22‰ with an average of −0.01 ± 0.18‰ (2SD, n = 18), opx from 0.24‰ to −0.22‰ with an average of 0.04 ± 0.20‰, and cpx from 0.24‰ to −0.16‰ with an average of 0.10 ± 0.19‰. δ 26Mg of olivines varies from −0.25‰ to −0.42‰ with an average of −0.34 ± 0.10‰ (2SD, n = 18), opx from −0.19‰ to −0.34‰ with an average of −0.25 ± 0.10‰, and cpx from −0.09‰ to −0.43‰ with an average of −0.24 ± 0.18‰. Although current precision (∼±0.06‰ for δ 56Fe; ±0.10‰ for δ 26Mg, 2SD) limits the ability to analytically distinguish inter-mineral isotopic fractionations, systematic behavior of inter-mineral fractionation for both Fe and Mg is statistically observed: Δ 56Fe ol–cpx = −0.10 ± 0.12‰ (2SD, n = 18); Δ 56Fe ol–opx = −0.05 ± 0.11‰; Δ 26Mg ol–opx = −0.09 ± 0.12‰; Δ 26Mg ol–cpx = −0.10 ± 0.15‰. Fe and Mg isotopic composition of bulk rocks were calculated based on the modes of olivine, opx, and cpx. The average δ 56Fe of peridotites in this study is 0.01 ± 0.17‰ (2SD, n = 18), similar to the values of chondrites but slightly lower than mid-ocean ridge basalts (MORB) and oceanic island basalts (OIB). The average δ 26Mg is −0.30 ± 0.09‰, indistinguishable from chondrites, MORB, and OIB. Our data support the conclusion that the bulk silicate Earth (BSE) has chondritic δ 56Fe and δ 26Mg. The origin of inter-mineral fractionations of Fe and Mg isotopic ratios remains debated. δ 56Fe between the main peridotite minerals shows positive linear correlations with slopes within error of unity, strongly suggesting intra-sample mineral–mineral Fe and Mg isotopic equilibrium. Because inter-mineral isotopic equilibrium should be reached earlier than major element equilibrium via chemical diffusion at mantle temperatures, Fe and Mg isotope ratios of coexisting minerals could be useful tools for justifying mineral thermometry and barometry on the basis of chemical equilibrium between minerals. Although most peridotites in this study exhibit a narrow range in δ 56Fe, the larger deviations from average δ 56Fe for three samples likely indicate changes due to metasomatic processes. Two samples show heavy δ 56Fe relative to the average and they also have high La/Yb and total Fe content, consistent with metasomatic reaction between peridotite and Fe-rich and isotopically heavy melt. The other sample has light δ 56Fe and slightly heavy δ 26Mg, which may reflect Fe–Mg inter-diffusion between peridotite and percolating melt.

First-principles estimates of equilibrium magnesium isotope fractionation in silicate, oxide, carbonate and hexaaquamagnesium(2+) crystals

Equilibrium mass-dependent magnesium isotope fractionation factors are estimated for a range of crystalline compounds including oxides, silicates, carbonates, and salts containing the Mg ( H 2 O ) 6 2 + solvation complex. Fractionation factors for the gas-phase species Mg and MgO are also presented. Fractionation factors are calculated with density functional perturbation theory (DFPT), using norm-conserving pseudopotentials. The results suggest that there will be substantial inter-mineral fractionation, particularly between tetrahedrally coordinated Mg 2+ in spinel (MgAl 2O 4) and the more common octahedrally coordinated Mg 2+-sites in silicate and carbonate minerals. Isotope fractionations calculated for Mg 2+ in hexaaquamagnesium(2+) salts are in good agreement with previous fractionation models of Mg aq 2 + based on large molecular clusters ( Black et al., 2007), but show possibly more significant disagreement with a more recent study ( Rustad et al., 2010). These models further suggest that solvated Mg aq 2 + , in the form of Mg ( H 2 O ) 6 2 + , will have higher 26Mg/ 24Mg than coexisting magnesite and dolomite. Calculated fractionations are consistent with Mg-isotope fractionations observed in peridotite mineral separates and inorganic carbonate precipitates. Predicted large, temperature-sensitive spinel-silicate fractionations, in particular, may find use in determining equilibration temperatures of peridotites and other high-temperature rock types.

Investigation of magnesium isotope fractionation during granite differentiation: Implication for Mg isotopic composition of the continental crust

High-precision Mg isotopic analysis was performed on a suite of well-characterized I-type granitoids and associated hornblende and biotite minerals from the Dabie Orogen in central China, to address the behavior of Mg isotopes during granite differentiation. Although these granitoids formed through different degrees of partial melting and fractional crystallization, with large variations in elemental and mineral compositions, their δ 26Mg values vary from −0.26 to −0.14 and are indistinguishable within our analytical precision (± 0.07‰; 2 SD). Coexisting hornblendes and biotites in these granitoids display similar Mg isotopic composition, with δ 26Mg ranging from −0.31 to −0.14 in hornblendes and −0.23 to −0.12 in biotites. The inter-mineral fractionation factors (Δ 26Mg Hbl-Bt = δ 26Mg Hbl − δ 26Mg Bt) vary from −0.10 to −0.02, with an average = −0.06 ± 0.08 (2 SD). The limited inter-mineral fractionation agrees with the theoretic prediction that Mg cations in both hornblende and biotite are octahedrally coordinated with oxygen, which restricts the magnitude of equilibrium isotope fractionation. Overall, data from both bulk granitoids and associated mineral separates suggest that Mg isotope fractionation during I-type granite differentiation is limited. Collectively, granitoids studied here have Mg isotopic composition similar to that of terrestrial basalts and peridotites ( δ 26Mg = −0.21 ± 0.07 vs. −0.25 ± 0.07; 2 SD), confirming that magmatic processes do not significantly fractionate Mg isotopes. The continental crust in the Dabie Orogen, as sampled by these I-type granitoids, has a mantle-like Mg isotopic composition. Given that significant Mg isotope fractionation occurs during chemical weathering processes, Mg isotopes may potentially be used for tracing granite genesis, in particular, if sedimentary materials are involved in granite sources.

Calcium isotopic fractionation between clinopyroxene and orthopyroxene from mantle peridotites

We report the first observation of Ca isotopic fractionation between co-existing clinopyroxene and orthopyroxene from Kilbourne Hole and San Carlos mantle peridotites. The 44Ca/ 40Ca in orthopyroxenes is 0.36 to 0.75‰ heavier than that in the co-existing clinopyroxenes. Using these isotopic constraints and the relative proportions of major Ca-bearing minerals in the upper mantle, the estimated 44Ca/ 40Ca of the upper mantle is 1.05 ± 0.04‰ heavier relative to NIST SRM 915a. This is slightly higher than our average for basalts (0.97 ± 0.04‰ heavier relative to NIST SRM 915a). Combined with published 44Ca/ 40Ca data on low temperature Ca-bearing minerals (calcite, aragonite and barite), we infer that the inter-mineral fractionation of Ca isotopes at both low- and high temperatures is primarily controlled by the strength of Ca–O bond. Accordingly, the mineral with a shorter Ca–O bond and a smaller Ca coordination number (i.e., stronger Ca–O bond) yields a heavier Ca isotopic ratio (i.e., higher 44Ca/ 40Ca). Since stable isotopes of major elements, such as Ca and Mg, exhibit small fractionations during igneous processes, the estimate of stable isotopic compositions of the bulk differentiated planetary bodies, including the Earth and the Moon, needs to take into account the relative proportions of major rock-forming minerals and their respective isotopic signatures.

Spinel–olivine magnesium isotope thermometry in the mantle and implications for the Mg isotopic composition of Earth

The magnesium isotopic composition of Earth is not yet well constrained despite significant advances in methods for measuring Mg isotope ratios in rocks. One impediment to establishing 25Mg/ 24Mg and 26Mg/ 24Mg of Earth is the lack of constraints on inter-mineral Mg isotope fractionations at high temperatures. Advances in computational chemistry afford the capacity to predict quantitatively Mg isotope fractionations among high-temperature minerals. High-precision MC-ICPMS measurements in turn provide the opportunity to test these predictions in well-characterized samples. Toward this end, we present new high-precision 25Mg/ 24Mg and 26Mg/ 24Mg measurements of mantle minerals and compare these ratios with predictions for temperature-dependent inter-mineral fractionations. Our results for two San Carlos volcanic field xenoliths show that there is measurable and systematic fractionation in Mg isotope ratios between constituent minerals that are consistent with theoretical predictions. The observed order from highest to lowest 25Mg/ 24Mg is spinel > clinopyroxene > orthopyroxene > olivine. The fractionation between spinel and olivine suggests an equilibration temperature of 814° +/− 60 °C based on the temperature dependence obtained from ab initio calculations. This temperature is consistent with independent T indicators involving spinel, suggesting that spinel and olivine are in Mg isotopic equilibrium in these mantle rocks, and lending credence to the accuracy of the results. Pyroxene, on the other hand, is apparently not in Mg isotopic equilibrium with spinel and olivine if the predicted temperature-dependent fractionations are correct. Consideration of the influences of modal abundances and inter-mineral fractionations on the Mg isotopic compositions of mantle minerals, and comparisons to new meteorite data reported herein, strengthen previous suggestions that the Earth may be different from carbonaceous chondrites in 25Mg/ 24Mg.