skip to main content


This content will become publicly available on July 1, 2024

Title: Temperature and co-crystallization effects on Zr isotopes
We undertook Zr isotope measurements on zircon, titanite, biotite, amphibole, and whole rocks from the La Posta pluton (Peninsular Ranges, southern California) together with trace element analyses and U-Pb age measurements to understand the controls on Zr isotope fractionation in igneous rocks, including temperature, crystallization sequence, and kinetic effects. We find large (>0.6‰) Zr isotope fractionations (expressed as δ94/90Zr) between titanite and zircon forming at approximately the same temperature. Using equilibrium fractionation factors calculated from ionic and ab initio models, we infer the controls on Zr isotope evolution to include the relative order in which phases appear on the liquidus, with titanite fractionation resulting in isotopically lighter melt and zircon fractionation resulting in isotopically heavier melt. While these models of Zr fractionation can explain δ94/90Zr variations in zircon of up to ∼1.5‰, crystallization order, temperature and presence of co-crystallizing phases do not explain all aspects of the intracrystalline Zr isotopic distribution in zircons in the La Posta pluton or the large range of Zr isotopic values among zircons (>2‰). Without additional constraints, such as knowledge of co-crystallizing phases and a better understand of the true causes of Zr isotope fractionation, Zr isotopes in zircon remains an ambiguous proxy of magmatic evolution.  more » « less
Award ID(s):
2143168
NSF-PAR ID:
10490362
Author(s) / Creator(s):
; ; ; ; ;
Publisher / Repository:
Geochimica et Cosmochimica Acta
Date Published:
Journal Name:
Geochimica et Cosmochimica Acta
Volume:
352
Issue:
C
ISSN:
0016-7037
Page Range / eLocation ID:
69 to 85
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
More Like this
  1. 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. 
    more » « less
  2. null (Ed.)
    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. 
    more » « less
  3. Abstract This study addresses the question of how and where arc magmas obtain their chemical and isotopic characteristics. The Wooley Creek batholith and Slinkard pluton are a tilted, mid- to upper-crustal part of a vertically extensive, late-Jurassic, arc-related magmatic system in the Klamath Mountains, northern California. The main stage of the system is divided into an older lower zone (c. 159 Ma) emplaced as multiple sheet-like bodies, a younger upper zone (c. 158–156 Ma), which is gradationally zoned upward from mafic tonalite to granite, and a complex central zone, which represents the transition between the lower and upper zones. Xenoliths are common and locally abundant in the lower and central zones and preserve a ghost stratigraphy of the three host terranes. Bulk-rock Nd isotope data along with ages and Hf and oxygen isotope data on zircons were used to assess the location and timing of differentiation and assimilation. Xenoliths display a wide range of εNd (whole-rock) and εHf (zircon), ranges that correlate with rocks in the host terranes. Among individual pluton samples, zircon Hf and oxygen isotope data display ranges too large to represent uniform magma compositions, and very few data are consistent with uncontaminated mantle-derived magma. In addition, zoning of Zr and Hf in augite and hornblende indicates that zircon crystallized at temperatures near or below 800 °C; these temperatures are lower than emplacement temperatures. Therefore, the diversity of zircon isotope compositions reflects in situ crystallization from heterogeneous magmas. On the basis of these and published data, the system is interpreted to reflect initial MASH-zone differentiation, which resulted in elevated δ18O and lowered εHf in the magmas prior to zircon crystallization. Further differentiation, and particularly assimilation–fractional crystallization, occurred at the level of emplacement on a piecemeal (local) basis as individual magma batches interacted with partial melts from host-rock xenoliths. This piecemeal assimilation was accompanied by zircon crystallization, resulting in the heterogeneous isotopic signatures. Magmatism ended with late-stage emplacement of isotopically evolved granitic magmas (c. 156 Ma) whose compositions primarily reflect reworking of the deep-crustal MASH environment. 
    more » « less
  4. Zirconium is a commonly used elemental tracer of silicate differentiation, yet its stable isotope systematics remain poorly known. Accessory phases rich in Zr 4+ such as zircon and baddeleyite may preserve a unique record of Zr isotope behavior in magmatic environments, acting both as potential drivers of isotopic fractionation and recorders of melt compositional evolution. To test this potential, we measured the stable Zr isotope composition of 70 single zircon and baddeleyite crystals from a well-characterized gabbroic igneous cumulate. We show that (i) closed-system magmatic crystallization can fractionate Zr stable isotopes at the >0.5% level, and (ii) zircon and baddeleyite are isotopically heavy relative to the melt from which they crystallize, thus driving chemically differentiated liquids toward isotopically light compositions. Because these effects are contrary to first-order expectations based on mineral-melt bonding environment differences, Zr stable isotope fractionation during zircon crystallization may not solely be a result of closed-system thermodynamic equilibrium. 
    more » « less
  5. 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 δ94/90Zr 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 δ94/90Zr value of seawater is much higher than that of Earth’s mantle and continental crust, which has a δ94/90Zr value near zero, indicating the presence of processes in the hydrosphere capable of inducing large mass-dependent fractionation. Furthermore, the seawater δ94/90Zr 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. 
    more » « less