Search

Zirconium is one of high field strength elements but its isotope behavior during geochemical processes is still uncertain because of the limited database. While Zr isotopes in magmatic rocks are often used to trace the evolution of magmas through fractional crystallization, it is intriguing how highly heterogeneous Zr isotopes were produced by the growth of zircon during crustal anatexis. We address this issue by in-situ zircon Zr isotope analyses of migmatites from two high-temperature metamorphic terranes in the South Lhasa zone and the North Dabie zone, respectively, in China. The results show highly variable δ94Zr values from −0.30‰ to +0.81‰ and from −0.58‰ to +0.49‰, respectively. In addition to the relict zircon of magmatic origin, two types of newly-grown zircons were identified in terms of their occurrences, trace elements and δ94Zr values. The peritectic zircon, mainly occurring in the in-situ leucosomes, exhibits the highest Nb-Ta-Hf-U contents and variably higher δ94Zr values than those of the relict zircon. The anatectic zircon, mainly occurring in the leucocratic veins, shows higher Nb-Ta-Hf-U contents than and similar δ94Zr values to those of the relict zircon. Model calculations demonstrate that the variable Zr isotope compositions of newly-grown zircons would result from decoupled release of Zr from zircon and non-zircon phases. The Zr supply of the peritectic zircon is mainly derived from the decomposition of Zr-bearing minerals in the in-situ anatectic melt (the non-zircon effect), whereas the Zr supply of the anatectic zircon is mainly from the dissolution of pre-existing zircons in the evolved melt (the zircon effect). The significant Zr isotope variations in the migmatites well illustrate the generation, migration and accumulation of the anatectic melts during the partial melting. Therefore, Zr isotopes can be used as a powerful means for distinguishing between the peritectic and anatectic zircons during crustal anatexis. [ABSTRACT FROM AUTHOR]

Mantle metasomatism, which affects the geochemical and lithological properties of the Earth, is crucial to the evolution and modification of the Earth's interior. Variations in chemical proxy of metasomatism, including high‐field strength elements (HFSE, e.g., Zr‐Ti isotopes and isovalent Zr‐Hf), have been commonly utilized as a tool to unravel the processes associated with the evolution of the Earth. However, the impact of mantle metasomatism by diverse agents on the Zr isotopic compositions of metasomatized mantle remains poorly understood. Here we carried out high‐precision double‐spike δ94/90Zr measurements for a suite of basalts, which were derived from the mantle sources metasomatized by typical metasomatic agents of fluid, silicate melt and carbonate melt originating from the deep mantle or recycled crustal materials. Mantle metasomatism results in lithological diversities within the mantle, ranging from hybridized peridotites to pyroxenite/eclogite and carbonated eclogite, which can significantly fractionate the isovalent HFSEs. However, our data show that these basalts have primitive mantle‐like δ94ZrNIST values (−0.033–0.043 ‰), regardless of their superchondritic Zr/Hf. The primitive mantle‐like δ94ZrNIST, irrelevant to any proxy of metasomatism (e.g., Sr‐Nd isotopes, Zr/Hf and La/Sm), indicate that mantle metasomatism and subsequence melting produce no measurable Zr isotopic variations in metasomatized mantle‐derived basalts. The δ94ZrNIST of basalts thus can be representative of the mean metasomatized mantle compositions. Combined with previously reported komatiites and oceanic basalts, we show that the Earth's mantle displays consistent δ94ZrNIST (−0.013 ± 0.053 ‰), even if it has a secular dynamic evolution with the interaction between Earth's exterior and interior. Plain Language Summary: Mantle metasomatism has a significant impact on the geochemical and lithological properties of the Earth's interior. The chemical variations, including the high‐field strength elements (HFSE), caused by this process, could provide key insights into such modification. However, the variation of Zr isotopes during mantle metasomatism remains enigmatic. Here, we analyzed the Zr isotopes of fresh basalts derived from mantle sources metasomatized by diverse metasomatic agents. We find that although mantle metasomatism leads to the substantial fractionation of Zr (Nb) from Hf (Ta), no measurable Zr isotopic variation occurs for metasomatized mantle‐derived melts, as reflected by the homogeneous and primitive mantle‐like Zr isotopic compositions of different samples. Combining our findings with previous data, we conclude that the Earth's mantle, from large‐scale and secular perspectives, maintains a consistent Zr isotopic composition, although the Earth underwent complex and dynamic evolution. Key Points: A first comprehensive investigation of Zr isotopes of mantle metasomatized by diverse agents of fluid, silicate melt and carbonate meltBasalts derived from metasomatized mantle show variable radiogenic isotopes and trace element patterns, but limited Zr isotope variationThe Earth's mantle exhibits consistent δ94Zr, despite its secular dynamic evolution with interaction between Earth's exterior and interior [ABSTRACT FROM AUTHOR]

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 δ 94/90Zr NIST 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 δ 94/90Zr NIST 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 δ 94/90Zr NIST 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 δ 94/90Zr NIST 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 (Δ94/90Zr garnet-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#, SiO 2), 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 δ 94/90Zr can be recycled into the mantle as a consequence of lower crustal foundering. [ABSTRACT FROM AUTHOR]

Zirconium (Zr) stable isotopes recently emerged as potential tracers of magmatic processes and, as a result, their behavior in high-temperature environments have been the focus of extensive characterization. In contrast, few studies have focused on Zr behavior and isotopic fractionation in low temperature or aqueous environments. Here, we describe a new analytical routine for highly precise and accurate analysis of Zr isotopes of water samples, using a combination of double-spike and iron co-precipitation methods. To assess the impact of potential systematic biases a series of experiments were conducted on natural and synthetic water samples. Our results show that the spike-to-sample ratio, matrix composition, and high field-strength element (HFSE) concentration have negligible effects on measured seawater Zr isotopic compositions, and that the Fe co-precipitation method used yields accurate and precise Zr isotope data. We thus apply this method to natural seawater samples collected from a water column profile in the Pacific Ocean off the coast of California, with depths ranging from 5 to 711 m. We find that the natural seawater samples are highly fractionated relative to solid-Earth values and display marked variability in δ 94/90Zr as a function of depth, ranging from ∼ +0.650 ‰ near the surface, to + 1.530 ‰ near the profile bottom, with an analytical uncertainty of ± ∼0.045 ‰ (2 SE, external reproducibility). The δ 94/90Zr value of seawater is much higher than that of Earth's mantle and continental crust, which has a δ 94/90Zr value near zero, indicating the presence of processes in the hydrosphere capable of inducing large mass-dependent fractionation. Furthermore, the seawater δ 94/90Zr value exhibits systematic variations with respect to water depth and salinity, suggesting that Zr isotopic compositions may be sensitive to seawater chemical properties and source highlighting its potential utility as a tracer of biogeochemical processes within the ocean. [ABSTRACT FROM AUTHOR]

The isotopic composition of the detrital sediment record harbours a valuable proxy for estimating the composition of the erodible upper crust since the Archaean. Refractory elements such as titanium (Ti) and zirconium (Zr) can display systematic variations in their isotopic composition as a result of magmatic differentiation. Hence, the isotopic composition of such elements in detrital sediments could potentially be used to infer the average composition (e.g., SiO 2 content) of their source region, even when elemental systematics are obfuscated by weathering and diagenetic processes. A key premise of this approach is that the isotopic composition of sediments remains unbiased relative to their protolith. To what extent isotopic fractionation can occur during sedimentary processes, notably the hydrodynamic sorting of heavy mineral assemblages with contrasting isotopic compositions, remains poorly understood. We investigate the effects of such processes on the Ti and Zr isotope composition of a suite of detrital sediments from the Eastern Mediterranean Sea (EMS). These sediments are binary mixtures of two main provenance components, Saharan dust and Nile sediment, with strongly contrasting mineralogical and geochemical signatures. The EMS sediments display clear evidence for hydrodynamic sorting of zircon, expressed as a large variation in Zr/Al 2 O 3 and deviation of εHf relative to the terrestrial εNd-εHf array. Our new data, however, do not show pronounced Zr isotope variation resulting from either hydrodynamic sorting of zircon or sediment provenance. Although this agrees with theoretical models that predict negligible equilibrium zircon-melt Zr isotope fractionation, it contrasts with recent observations suggesting that kinetic Zr isotope fractionation might be a common feature in igneous rocks. For the EMS sediments, the negligible shift in Zr isotope composition through hydrodynamic sorting means that fine-grained samples accurately reflect the composition of their source. The nearly overlapping Zr isotope compositions of Sahara- and Nile-derived sediment, however, mean that Zr isotopes, in this case, have insufficient resolution to be a useful provenance proxy. Titanium behaves differently. A small but resolvable, systematic difference in Ti isotope composition is observed between the Sahara and Nile provenance components. Samples with a strong Saharan dust signature show some Ti isotope evidence for hydrodynamic sorting of oxides in tandem with zircon, but a much stronger effect is inferred for Nile sediment. Regression of the EMS sediment samples shows that the Ti isotope composition of the Nile-derived component is strongly fractionated compared to its protolith, the Ethiopian flood basalts. Whereas Ti in Nile sediment is carried in essentially unmodified concentration, and by inference isotope composition, from its sources to the delta, large-scale hydrodynamic sorting of Fe-Ti oxides occurs in the littoral cell. This process causes a decrease in TiO 2 /Al 2 O 3 of the residual fine-grained sediment fraction and shifts its Ti isotope composition to heavier compositions. The potential of such an "oxide effect" in detrital sediments has implications for crustal evolution models that use Ti isotopes as a proxy for the proportion of felsic crust and can account for the observed scatter in the shale record. [ABSTRACT FROM AUTHOR]

The niobium-92-zirconium-92 (92Nb-92Zr) decay system with a half-life of 37 Ma has great potential to date the evolution of planetary materials in the early Solar System. Moreover, the initial abundance of the p-process isotope 92Nb in the Solar System is important for quantifying the contribution of p-process nucleosynthesis in astrophysical models. Current estimates of the initial 92Nb/93Nb ratios have large uncertainties compromising the use of the 92Nb-92Zr cosmochronometer and leaving nucleosynthetic models poorly constrained. Here, the initial 92Nb abundance is determined to high precision by combining the 92Nb-92Zr systematics of cogenetic rutiles and zircons from mesosiderites with U-Pb dating of the same zircons. The mineral pair indicates that the 92Nb/93Nb ratio of the Solar System started with (1.66 ± 0.10) × 10-5, and their 92Zr/90Zr ratios can be explained by a three-stage Nb-Zr evolution on the mesosiderite parent body. Because of the improvement by a factor of 6 of the precision of the initial Solar System 92Nb/93Nb, we can show that the presence of 92Nb in the early Solar System provides further evidence that both type Ia supernovae and core-collapse supernovae contributed to the light p-process nuclei. [ABSTRACT FROM AUTHOR]

Conflicting results exist regarding the mechanisms, direction, and magnitude of Zr isotope fractionation in igneous systems. To better understand the origin of the fractionations observed in magmatic Zr-bearing minerals and bulk rocks, we theoretically investigated the main potential driving processes: thermodynamic equilibrium effects driven by either (i) vibrational energy or (ii) nuclear volume, and (iii) diffusion-driven kinetic effects. Vibrational equilibrium fractionation properties were estimated for zircon (VIIIZrSiO 4), baddeleyite (VIIZrO 2), gittinsite (VIZrCaSi 2 O 7), sabinaite (Na 4 VIIIZr 2 TiC 4 O 16), and vlasovite (Na 2 VIZrSi 4 O 11). These properties show dependency on Zr coordination, as well as the presence of strong covalent bonds (C O, Si O by order of decreasing effect) in the material. More importantly, despite the large variety of structures investigated, the predicted mass-dependent equilibrium fractionations (Δ94/90Zr ∼±0.05‰ relative to zircon at 800 °C) are systematically one order of magnitude smaller than required to explain the natural variability observed to date in natural settings (δ94/90Zr from ∼+1 to −5‰). Likewise, careful evaluation of expected nuclear field shift (NFS) effects predict a magnitude of fractionation of ∼0.08‰ (at 800 °C), further supporting the conclusion that equilibrium effects cannot be invoked to explain extreme δ94/90Zr zircon values. Furthermore, the mass-dependency of all Zr isotope ratios reported in zircon crystals precludes a contribution of NFS effects larger than ∼0.01‰ on δ94/90Zr. On the other hand, we show that diffusion, and in particular the development of Zr diffusive boundary layers in silicate magmas during fractional crystallization, provides a viable and most likely mechanism to produce permil-level, mass-dependent isotope fractionations similar to those observed in natural systems. We propose testable scenarii to explain the large and contrasting Zr isotopes signatures in different magmatic zircons, which underline the importance of magmatic composition, Zr diffusivity, and crystallization timescales. [ABSTRACT FROM AUTHOR]

Zircons widely occur in magmatic rocks and often display internal zonation finely recording the magmatic history. Here, we presented in situ high-precision (2SD <0.15 for d94Zr) and high-spatial-resolution (20 µm) stable Zr isotope compositions of magmatic zircons in a suite of calc-alkaline plutonic rocks from the juvenile part of the Gangdese arc, southern Tibet. These zircon grains are internally zoned with Zr isotopically light cores and increasingly heavier rims. Our data suggest the preferential incorporation of lighter Zr isotopes in zircon from the melt, which would drive the residual melt to heavier values. The Rayleigh distillation model can well explain the observed internal zoning in single zircon grains, and the best-fit models gave average zircon-melt fractionation factors for each sample ranging from 0.99955 to 0.99988. The average fractionation factors are positively correlated with the median Ti-in-zircon temperatures, indicating a strong temperature dependence of Zr isotopic fractionation. The results demonstrate that in situ Zr isotope analyses would be another powerful contribution to the geochemical toolbox related to zircon. The findings of this study solve the fundamental issue on how zircon fractionates Zr isotopes in calc-alkaline magmas, the major type of magmas that led to forming continental crust over time. The results also show the great potential of stable Zr isotopes in tracing magmatic thermal and chemical evolution and thus possibly continental crustal differentiation. [ABSTRACT FROM AUTHOR]

We present a detailed analysis of spectra and other observables for the entire chain of Zr isotopes, from neutron number 52 to 70, in the framework of the interacting boson model with configuration mixing. The results suggest a remarkable interplay of multiple quantum phase transitions (QPTs). One type of QPT involves an abrupt crossing of normal and intruder configurations, superimposed on a second type of QPT involving gradual shape-changes within each configuration. [ABSTRACT FROM AUTHOR]

The effects of the tensor force on the ground properties of Zr isotopes are studied in the framework of the Skyrme–Hartree–Fock approach. It is found that the tensor force strongly affects the ground state energies and the geometric symmetry properties, in particular for those isotopes near N=60 region. The effects are attributed to the fact that the tensor force enlarges the spin and pseudospin symmetry breaking and therefore results in a ∼2 MeV sub-shell gap between d3/2 and s1/2 single-particle levels.

High spin structure of Zr isotopes, in particular, around A = 8 0 has been studied in yrast and nonyrast regions. Spin dependence of shapes for the yrast levels are investigated by employing Cranked Hartree–Fock–Bogoliubov (CHFB) theory using a pairing + quadrupole + hexadecapole model interaction and the calculations are in good accord with the experimental data. The nonyrast states are treated by incorporating temperature degree of freedom using the statistical theory (ST). Highly deformed prolate shapes dominate the nonrotating proton rich region at low temperatures (T) with coexisting oblate and prolate shapes in 8 0 Zr. Hot rotating nuclei show highest deformation around A = 8 0 among all the other Zr isotopes even at high temperatures. 8 4 Zr exhibits interesting structural transitions, hence studied in detail in yrast and non yrast regions. Triaxiality predominates in both yrast and nearly yrast (low temperature) regions at low spins with transition to elongated shapes at mid spin values 30–38 ℏ to highly deformed oblate shapes at higher spins. CHFB predicts a strong backbending effect at 32 ℏ and 40 ℏ. A shape coexistence between the rare shape phase of noncollective prolate and oblate is reported in 8 4 Zr at low temperature and spin = 3 6 – 3 8 ℏ. Prolate shape phase disappears with increasing temperature and spin but the nucleus remains highly deformed (with β ≈ 0. 4 at spin ≥ 40 ℏ) even at high temperatures of the order of 3–3.5 MeV, hence a very promising candidate for GDR probes of nuclear shapes. [ABSTRACT FROM AUTHOR]

Highlights • First comprehensive study of Zr stable isotopes in terrestrial basalts and their igneous differentiates. • Undifferentiated basaltic samples display limited Zr isotope compositions, suggesting limited Zr isotope heterogeneity within the terrestrial mantle. • N-MORBs that sample depleted MORB mantle have variable Zr isotope compositions relative to OIB or T- and E-MORB. • Significant Zr isotope variation in differentiated igneous rocks (i.e., >65 wt% SiO 2) interpreted to reflect crystallisation of isotopically light zircon. • Estimated primitive mantle δ94/90Zr IPGP-Zr is 0.048 ± 0.032‰; 2 sd, n = 48. Abstract High-precision double-spike Zr stable isotope measurements (expressed as δ94/90Zr IPGP-Zr , the permil deviation of the 94Zr/90Zr ratio from the IPGP-Zr standard) are presented for a range of ocean island basalts (OIB) and mid-ocean ridge basalts (MORB) to examine mass-dependent isotopic variations of zirconium in Earth. Ocean island basalt samples, spanning a range of radiogenic isotopic flavours (HIMU, EM) show a limited range in δ94/90Zr IPGP-Zr (0.046 ± 0.037‰; 2sd, n = 13). Similarly, MORB samples with chondrite-normalized La/Sm of >0.7 show a limited range in δ94/90Zr IPGP-Zr (0.053 ± 0.040‰; 2sd, n = 8). In contrast, basaltic lavas from mantle sources that have undergone significant melt depletion, such as depleted normal MORB (N-MORB) show resolvable variations in δ94/90Zr IPGP-Zr , from −0.045 ± 0.018 to 0.074 ± 0.023‰. Highly evolved igneous differentiates (>65 wt% SiO 2) from Hekla volcano in Iceland are isotopically heavier than less evolved igneous rocks, up to 0.53‰. These results suggest that both mantle melt depletion and extreme magmatic differentiation leads to resolvable mass-dependent Zr isotope fractionation. We find that this isotopic fractionation is most likely driven by incorporation of light isotopes of Zr within the 8-fold coordinated sites of zircons, driving residual melts, with a lower coordination chemistry, towards heavier values. Using a Rayleigh fractionation model, we suggest a α zircon-melt of 0.9995 based on the whole rock δ94/90Zr IPGP-Zr values of the samples from Hekla volcano (Iceland). Zirconium isotopic fractionation during melt-depletion of the mantle is less well-constrained, but may result from incongruent melting and incorporation of isotopically light Zr in the 8-fold coordinated M2 site of orthopyroxene. Based on these observations lavas originating from the effect of melt extraction from a depleted mantle source (N-MORB) or that underwent zircon saturation (SiO 2 > 65 wt%) are removed from the dataset to give an estimate of the primitive mantle Zr isotope composition of 0.048 ± 0.032‰; 2sd, n = 48. These data show that major controls on Zr fractionation in the Earth result from partial melt extraction in the mantle and by zircon fractionation in differentiated melts. Conversely, fertile mantle is homogenous with respect to Zr isotopes. Zirconium mass-dependent fractionation effects can therefore be used to trace large-scale mantle melt depletion events and the effects of felsic crust formation. [ABSTRACT FROM AUTHOR]

Zirconium, as a high field strength element, has been widely used to trace the differentiation of terrestrial planets. It is also a major constituent in zircon, an important accessory mineral providing constraints on the history of the Earth. Recently, stable Zr isotopes have shown potential in tracing magma differentiation. To fuel the applications of stable Zr isotopes in tracing igneous processes, we review (1) the geochemical behaviors of Zr in igneous systems, which are fundamental for understanding Zr isotopes, and (2) mass-dependent Zr isotope fractionation in igneous rocks and zircons regarding its isotopic variability, mechanisms, geological implications, and potential applications. At the bulk rock scale, igneous rocks with SiO 2 > 65 wt% show large Zr isotopic variations, which have been proposed to result from the segregation of isotopically light zircon from the melt. At the mineral scale, igneous zircons show Zr isotopic variations from homogeneous to highly heterogeneous. Zircon–melt equilibrium isotope fractionation (EIF) is likely small, with the preference of zircon for light Zr isotopes from the melt. In comparison, diffusive effects in melt can lead to larger isotope fractionation between zircon and melt, if zircon growth is limited by Zr diffusion in melt. On the other hand, in a diffusion-controlled regime, the growth of Zr-poor mineral may produce local Zr saturated and isotopically heavy melt areas; zircons crystallized from such areas can be isotopically heavier than the initial melt. Although the Zr isotope variability and fractionation mechanisms are complex, current studies suggest that (1) bulk-rock Zr isotopes can be used to trace the differentiation of felsic magmas, and that (2) zircon Zr isotopes have the potential to reveal zircon crystallization kinetics and magma dynamics. Integrated with other geochemical and isotopic tools, stable Zr isotopes may provide new insight into the dynamic history of diverse igneous systems through time. • Both equilibrium and kinetic isotope fractionation contribute to Zr isotopic variations. • Isotope fractionation in felsic magmas is mainly driven by zircon–melt segregation. • Different Zr isotope fractionation mechanisms contributed to isotopic variations in zircon. • Diffusion-limited zircon crystallization is mainly controlled by supersaturation. • Supersaturation links zircon Zr isotopes to crystallization kinetics and magma dynamics. [ABSTRACT FROM AUTHOR]

The effects of the tensor force on the ground properties of Zr isotopes are studied in the framework of the Skyrme–Hartree–Fock approach. It is found that the tensor force strongly affects the ground state energies and the geometric symmetry properties, in particular for those isotopes near N = 60 region. The effects are attributed to the fact that the tensor force enlarges the spin and pseudospin symmetry breaking and therefore results in a ∼2 MeV sub-shell gap between d 3 / 2 and s 1 / 2 single-particle levels. [ABSTRACT FROM AUTHOR]

Zircons widely occur in magmatic rocks and often display internal zonation finely recording the magmatic history. Here, we presented in situ high-precision (2SD <0.15‰ for δ 94 Zr) and high-spatial-resolution (20 µm) stable Zr isotope compositions of magmatic zircons in a suite of calc-alkaline plutonic rocks from the juvenile part of the Gangdese arc, southern Tibet. These zircon grains are internally zoned with Zr isotopically light cores and increasingly heavier rims. Our data suggest the preferential incorporation of lighter Zr isotopes in zircon from the melt, which would drive the residual melt to heavier values. The Rayleigh distillation model can well explain the observed internal zoning in single zircon grains, and the best-fit models gave average zircon-melt fractionation factors for each sample ranging from 0.99955 to 0.99988. The average fractionation factors are positively correlated with the median Ti-in-zircon temperatures, indicating a strong temperature dependence of Zr isotopic fractionation. The results demonstrate that in situ Zr isotope analyses would be another powerful contribution to the geochemical toolbox related to zircon. The findings of this study solve the fundamental issue on how zircon fractionates Zr isotopes in calc-alkaline magmas, the major type of magmas that led to forming continental crust over time. The results also show the great potential of stable Zr isotopes in tracing magmatic thermal and chemical evolution and thus possibly continental crustal differentiation., Competing Interests: The authors declare no competing interest., (Copyright © 2020 the Author(s). Published by PNAS.)