Metamorphic growth and recrystallization of zircons in extremely O-depleted rocks during eclogite-facies metamorphism: Evidence from U-Pb ages, trace elements, and O-Hf isotopes

A combined in situ SIMS and LA-(MC)-ICPMS study of U-Pb ages, trace elements, O and Lu-Hf isotopes was conducted for zircon from eclogite-facies metamorphic rocks in the Sulu orogen. The two microbeam techniques sampled various depths of zircon domains, revealing different element and isotope relationships between residual magmatic cores and new metamorphic rims and thus the geochemical architecture of metamorphic zircons which otherwise cannot be recognized by the single microbeam technique. This enables discrimination of metamorphic growth from different subtypes of metamorphic recrystallization. Magmatic cores with U-Pb ages of 769 ± 9 Ma have positive δ¹⁸O values of 0.1-10.1‰, high Th/U and ¹⁷⁶Lu/¹⁷⁷Hf ratios, high REE contents, and steep MREE-HREE patterns with negative Eu anomalies. They are interpreted as crystallizing from positive δ¹⁸O magmas during protolith emplacement. In contrast, newly grown domains have concordant U-Pb ages of 204 ± 4 to 252 ± 7 Ma and show negative δ¹⁸O values of −10.0‰ to −2.2‰, low Th/U and ¹⁷⁶Lu/¹⁷⁷Hf ratios, low REE contents, and flat HREE patterns with weak to no Eu anomalies. They are interpreted as growing from negative δ¹⁸O fluids that were produced by metamorphic dehydration of high-T glacial-hydrothermally altered rocks during continental subduction-zone metamorphism. Differences in δ¹⁸O between different domains within single grains vary from 0.8‰ to 12.5‰, suggesting different degrees of O isotope exchange between the positive δ¹⁸O magmatic core and the negative δ¹⁸O metamorphic fluid during the metamorphism. The magmatic zircons underwent three subtypes of metamorphic recrystallization, depending on their accessibility to negative δ¹⁸O fluids. The zircons recrystallized in solid-state maintained positive δ¹⁸O values, and REE and Lu-Hf isotopes of protolith zircon, but their U-Pb ages are lowered. The zircons recrystallized through dissolution exhibit negative δ¹⁸O values similar to the metamorphic growths, almost completely reset U-Pb ages, and partially reset REE systems. The zircons recrystallized through replacement show variably negative δ¹⁸O values, and partially reset REE, and U-Pb and Lu-Hf isotopic systems. Therefore, this study places robust constraints on the origin of metamorphic zircons in eclogite-facies rocks and provides a methodological framework for linking the different types of metamorphic zircons to petrological processes during continental collision.     

Extreme oxygen isotope signature of meteoric water in magmatic zircon from metagranite in the Sulu orogen, China: Implications for Neoproterozoic rift magmatism

Unusual ¹⁸O depletion, with δ¹⁸O values as negative as −10‰ to −4‰ relative to VSMOW, was reported in zircons from ultrahigh-pressure eclogite-facies metamorphic rocks in the Dabie-Sulu orogenic belt, China. But it is critical for the negative δ¹⁸O zircons to be distinguished between magmatic and metamorphic origins, because the ¹⁸O depletion can be acquired by high-T eclogite-facies metamorphism of meteoric-hydrothermally altered low δ¹⁸O rocks. While zircon O diffusion kinetics has placed a reasonable constraint on this, zircon trace element compositions can provide a straightforward distinction between the magmatic and metamorphic origins. This paper reports our finding of unusual ¹⁸O depletion in zircon from granitic gneiss in the northeastern end of the Sulu orogen. Zircon δ¹⁸O values vary from −7.8‰ to −3.1‰ along a profile of 50 m length at Zaobuzhen. They are close to extremely low δ¹⁸O values of −9.0‰ to −5.9‰ for metagranite at Qinglongshan and adjacent areas in the southwestern end of the Sulu orogen. CL imaging suggests that the low δ¹⁸O zircons at Zaobuzhen are primarily of magmatic origin, but underwent different degrees of metamorphic modification. Zircon U-Pb dating yields middle Neoproterozoic ages of 751 ± 27 to 779 ± 25 Ma for protolith crystallization and Triassic ages of 214 ± 10 to 241 ± 33 Ma for metamorphic resetting. However, no metamorphic modification occurs in zircon REE patterns that only indicate magmatic recrystallization and hydrothermal alteration, respectively. Thus, the negative δ¹⁸O zircons are interpreted as crystallizing from negative δ¹⁸O magmas due to melting of meteoric-hydrothermally altered negative δ¹⁸O rocks in an active rift setting at about 780 Ma. The variation in zircon δ¹⁸O values indicates considerable O isotope heterogeneity in its granitic protolith. Zircon Lu-Hf isotope analyses give positive ε_Hf(t) values of 1.6-4.1 and Hf model ages of 1.18-1.30 Ga. This suggests that the granitic protolith was derived from the mid-Neoproterozoic reworking of late Mesoproterozoic juvenile crust. The metagranites at Zaobuzhen and Qinglongshan, about 450 km apart, are two known occurrences of the unusually low δ¹⁸O zircons below −6‰ so far reported in the Sulu orogen. They are similar to each other in both protolith and metamorphic ages, so that they share the same nature of both Neoproterozoic protolith and Triassic metamorphism. Therefore, the locally negative δ¹⁸O zircons may register centers of low δ¹⁸O magmatism during the supercontinental rifting.     

U-Pb, Hf and O isotope evidence for two episodes of fluid-assisted zircon growth in marble-hosted eclogites from the Dabie orogen

A combined study of internal structure, U-Pb age, and Hf and O isotopes was carried out for metamorphic zircons from ultrahigh-pressure eclogite boudins enclosed in marbles from the Dabie orogen in China. CL imaging identifies two types of zircon that are metamorphically new growth and recrystallized domain, respectively. The metamorphic zircons have low Th and U contents with low Th/U ratios, yielding two groups of ²⁰⁶Pb/²³⁸U age at 245 ± 3 to 240 ± 2 Ma and 226 ± 4 to 223 ± 2 Ma, respectively. Anomalously high δ¹⁸O values were obtained for refractory minerals, with 9.9 to 21.4‰ for garnet and 16.9‰ for zircon. This indicates that eclogite protolith is sedimentary rocks capable of liberating aqueous fluid for zircon growth during continental subduction-zone metamorphism. Most of the zircons are characterized by very low ¹⁷⁶Lu/¹⁷⁷Hf ratios of 0.000001-0.000028, indicating their growth in association with garnet recrystallization. A few of them falling within the older age group have comparatively high ¹⁷⁶Lu/¹⁷⁷Hf ratios of 0.000192-0.000383, suggesting their growth prior to the formation of garnet in the late stage of subduction. The variations in the Lu/Hf ratios for zircons can thus be used to correlate with garnet growth during eclogite-facies metamorphism. In either case, the zircons have variable ε_Hf (t) values for individual samples, suggesting that their protolith is heterogeneous in Hf isotope composition with localized fluid availability in the bulk processes of orogenic cycle. Nevertheless, a positive correlation exists between ²⁰⁶Pb/²³⁸U ages and Lu-Hf isotope ratios for the metamorphically recrystallized zircons, suggesting that eclogite-facies metamorphism in the presence of fluid has the identical effect on zircon Lu-Hf and U-Th-Pb isotopic systems. We conclude that the zircons of the older group grew in the presence of fluid during the subduction prior to the onset of peak ultrahigh-pressure metamorphism, whereas the younger zircons grew in the presence of fluid released during the initial exhumation toward high-pressure eclogite-facies regime.     

In situ U-Pb, O and Hf isotopic compositions of zircon and olivine from Eoarchaean rocks, West Greenland: New insights to making old crust

The sources and petrogenetic processes that generated some of the Earth’s oldest continental crust have been more tightly constrained via an integrated, in situ (U-Pb, O and Hf) isotopic approach. The minerals analysed were representative zircon from four Eoarchaean TTG tonalites and two felsic volcanic rocks, and olivine from one harzburgite/dunite of the Itsaq Gneiss Complex (IGC), southern West Greenland. The samples were carefully chosen from localities with least migmatisation, metasomatism and strain. Zircon was thoroughly characterized prior to analysis using cathodoluminescence, scanning electron, reflected and transmitted light imaging. The zircon from all but one sample showed only minor post-magmatic recrystallisation. ²⁰⁷Pb/²⁰⁶Pb dating of oscillatory-zoned zircon using SHRIMP RG (n = 142) indicates derivation of the felsic igneous rocks from different batches of magma at 3.88, 3.85, 3.81, 3.80 and 3.69 Ga.Analyses of ¹⁸O/¹⁶O compositions of olivine from a harzburgite/dunite (n = 8) using SHRIMP II in multi-collector mode, indicate that the oxygen isotopic composition of this sample of Eoarchaean mantle (δ¹⁸O_Ol = 6.0 ± 0.4‰) was slightly enriched in ¹⁸O, but not significantly different from that of the modern mantle. Zircon δ¹⁸O measurements from the six felsic rocks (n = 93) record mean or weighted mean compositions ranging from 4.9 ± 0.7‰ to 5.1 ± 0.4‰, with recrystallised domains showing no indication of oxygen isotopic exchange during younger tectonothermal events. δ¹⁸O_Zr compositions indicate that the primary magmas were largely in equilibrium with the mantle or mantle-derived melts generated at similar high temperatures, while calculated tonalite δ¹⁸O_WR compositions (6.7-6.9‰) resemble those of modern adakites.LA-MC-ICPMS zircon ¹⁷⁶Hf/¹⁷⁷Hf analyses were obtained from six samples (n = 122). Five samples record weighted mean initial ε_Hf compositions ranging from to 0.5 ± 0.6 to −0.1 ± 0.7 (calculated using λ¹⁷⁶Lu = 1.867 × 10⁻¹¹ yr⁻¹), while one sample records a composition of 1.3 ± 0.7, indicating the magmas were generated from a reservoir with a time averaged, near chondritic Lu/Hf. The derivation of TTG magmas from a chondritic Lu/Hf source implies either that there was not voluminous continental crustal growth nor major mantle differentiation leading to Lu/Hf fractionation during the Hadean or Eoarchaean, or alternatively that rapid recycling of an early formed crust allowed the early mantle to maintain a chondritic Lu/Hf.Previous studies have demonstrated that ancient TTG rocks were mostly produced by dehydration melting of mafic rocks within the stability field of garnet, probably in flatly-subducted or buried oceanic crust. The oxygen isotopic signatures measured here at high spatial resolution allow the source materials to be better defined. Melting of a mixed mafic source consisting of ∼80% unaltered gabbro (δ¹⁸O_WR = 5.5‰) with ∼20% hydrothermally altered gabbro/basalt (δ¹⁸O_WR = 4.0‰) would produce tonalite magmas within the average compositional range observed. ¹⁸O-enriched components such as altered shallow basaltic oceanic crust and pelagic or continental sediments were not present in the sources of these TTG melts. The absence of high ¹⁸O signatures may indicate either the rarity of low temperature altered sediments, or their effective removal from the down-going slab.     

Correlated microanalysis of zircon: Trace element, δO, and U-Th-Pb isotopic constraints on the igneous origin of complex >3900 Ma detrital grains

The origins of >3900 Ma detrital zircons from Western Australia are controversial, in part due to their complexity and long geologic histories. Conflicting interpretations for the genesis of these zircons propose magmatic, hydrothermal, or metamorphic origins. To test the hypothesis that these zircons preserve magmatic compositions, trace elements [rare earth elements (REE), Y, P, Th, U] were analyzed by ion microprobe from a suite of >3900 Ma zircons from Jack Hills, Western Australia, and include some of the oldest detrital zircons known (4400-4300 Ma). The same ∼20 μm domains previously characterized for U/Pb age, oxygen isotope composition (δ¹⁸O), and cathodoluminescence (CL) zoning were specifically targeted for analysis. The zircons are classified into two types based on the light-REE (LREE) composition of the domain analyzed. Zircons with Type 1 domains form the largest group (37 of 42), consisting of grains that preserve evolved REE compositions typical of igneous zircon from crustal rocks. Grains with Type 1 domains display a wide range of CL zoning patterns, yield nearly concordant U/Pb ages from 4400 to 3900 Ma, and preserve a narrow range of δ¹⁸O values from 4.7‰ to 7.3‰ that overlap or are slightly elevated relative to mantle oxygen isotope composition. Type 1 domains are interpreted to preserve magmatic compositions. Type 2 domains occur in six zircons that contain spots with enriched light-REE (LREE) compositions, here defined as having chondrite normalized values of La_N > 1 and Pr_N > 10. A subset of analyses in Type 2 domains appear to result from incorporation of sub-surface mineral inclusions in the analysis volume, as evidenced by positively correlated secondary ion beam intensities for LREE, P, and Y, which are anti-correlated to Si, although not all Type 2 analyses show these features. The LREE enrichment also occurs in areas with discordant U/Pb ages and/or high Th/U ratios, and is apparently associated with past or present radiation damage. The enrichment is not attributed to hydrothermal alteration, however, as oxygen isotope ratios in Type 2 domains overlap with magmatic values of Type 1 domains, and do not appear re-set as might be expected from dissolution or ion-exchange processes operating at variable temperatures. Thus, REE compositions in Type 2 domains where mineral inclusions are not suspected are best interpreted to result from localized enrichment of LREE in areas with past or present radiation damage, and with a very low fluid/rock ratio. Correlated in situ analyses allow magmatic compositions in these complex zircons to be distinguished from the effects of secondary processes. These results are additional evidence for preservation of magmatic compositions in Jack Hills zircons, and demonstrate the benefits of detailed imaging in studies of complicated detrital zircons of unknown origin. The data reported here support previous interpretations that the majority of >3900 Ma zircons from the Jack Hills have an origin in evolved granitic melts, and are evidence for the existence of continental crust very early in Earth’s history.     

Rate of growth of the preserved North American continental crust: Evidence from Hf and O isotopes in Mississippi detrital zircons

Detrital zircons from the Mississippi River have been analyzed for U-Th-Pb, Lu-Hf and O isotopes to constrain the rate of growth of the preserved North American continental crust. One hundred and forty two concordant zircon U/Pb dates on grains mounted in epoxy, obtained by Excimer laser ablation ICP-MS method, resolved six major periods of zircon crystallization: 0-0.25, 0.3-0.6, 0.95-1.25, 1.3-1.5, 1.65-1.95 and 2.5-3.0 Ga. These age ranges match the ages of the recognized lithotectonic units of the North American continent in the hinterland of the Mississippi River. Ninety-six zircons mounted on tape, which show no age zonation and were within 7.5% of concordance, were selected to represent the six U/Pb age time intervals and analyzed for Lu-Hf and O isotope by laser ablation MC-ICP-MS and SHRIMP II, respectively. The δ¹⁸O values of the zircons show a small step increase in the maximum δ¹⁸O values at the Archean-Proterozoic boundary from 7.5‰ in the Archean to 9.5‰, and rarely 13‰, in the Proterozoic and Phanerozoic. However, the average value of δ¹⁸O in zircons changes little with time, showing that the increase in the maximum δ¹⁸O values between 2.5 and 2.0 Ga, which can be attributed to an increase in the sediment content of the source regions of younger granitoids, is largely balanced by an increase in zircons with anomalously low δ¹⁸O, which can be attributed to hydrothermally altered crust in the granitoid source region.εHf_i values for the zircons range from 13.1 to −26.9. Zircons derived from juvenile crust, which we define as having mantle δ¹⁸O (4.5-6.5‰) and lying within error of the Hf depleted mantle growth curve, are rare or absent in the Mississippi basin. The overwhelming majority of zircons crystallized from melted pre-existing continental crust, or mantle-derived magmas that were contaminated by continental crust. The average time difference between primitive crust formation and remelting for each of the recognized lithotectonic time intervals, which is defined as crustal incubation time in this study, is 890 ± 460 Myr. There is also a suggestion that the crustal incubation time increases with decreasing age in the Mississippi basin, which is consistent with the declining role of radioactive heat production in the lower crust with time.The average Hf model age (1.94 Ga), weighted by fraction of zircons in the river load is in reasonable agreement with the Nd model age (1.7 Ga) for the Mississippi River. However, if the zircons are weighted by the area of North America covered by the six recognized periods of zircon crystallization the average model age is 2.35 Ga, which compares favorably with an area weighted Nd model age of 2.36 Ga. Our preferred approach is to use the measured O isotope values to constrain variations in the ¹⁷⁶Lu/¹⁷⁷Hf ratio of the granitic source region from which the zircons crystallized, making the assumption that zircons with mantle-like O isotopic ratios have higher ¹⁷⁶Lu/¹⁷⁷Hf than zircons with higher O isotope values. This method gives an average Hf model age of 2.53 Ga, which is 180 Myr older than the constant ¹⁷⁶Lu/¹⁷⁷Hf calculation.The area weighted zircon Hf model ages show two distinct periods of crust formation for the North American continent, 1.6-2.2 and 2.9-3.4 Ga. At least 50% of the preserved North American continental crust was extracted from the mantle by 2.9 Ga and 90% by 1.6 Ga. Two similar periods of crustal growth are also recognized in Gondwana (Hawkesworth C. J. and Kemp A. I. S. (2006) Using hafnium and oxygen isotopes in zircons to unravel the record of crustal evolution. Chem. Geol.226, 144-162.), suggesting that these may be periods of global continental crustal growth. However, we stress that more data from other continents are required before the hypothesis of episodic global continental growth can be accepted with confidence.     

Rare earth and trace element distribution in zircons from miaskite lamproites of the Panozero complex,Central Karelia

Ion microprobe study of rare-earth and trace element composition of zircons from miaskite lamproites of the Panozero sanukitoid complex in Central Karelia made it possible to divide them into weakly altered and metasomatically altered zircons. The latter differ in elevated contents of LREE, Ca, Al, Fe, Ti, Sr, Ba, and Th, a flat REE distribution pattern, and a reduced Ce anomaly. Zircons show moderate to strong degrees of alteration, which are recorded in their geochemical features. The metasomatic alteration was caused by fluid related to the mantle alkaline magmatism. At the final stage, this fluid caused the crystallization of zircon domain with extremely high contents of REE (55000 ppm), Ti, Ba, Sr, and Th. The use of a Ti thermometer for unaltered zircons from the miaskite lamproites yields strongly underestimated temperatures, which require additional explanation or revision of the thermometer. For strongly altered zircons with sharply elevated Ti content, the use of this thermometer seems to be impossible.     

Oxygen and iron isotope constraints on near-surface fractionation effects and the composition of lunar mare basalt source regions

Oxygen and iron isotope analyses of low-Ti and high-Ti mare basalts are presented to constrain their petrogenesis and to assess stable isotope variations within lunar mantle sources. An internally-consistent dataset of oxygen isotope compositions of mare basalts encompasses five types of low-Ti basalts from the Apollo 12 and 15 missions and eight types of high-Ti basalts from the Apollo 11 and 17 missions. High-precision whole-rock δ¹⁸O values (referenced to VSMOW) of low-Ti and high-Ti basalts correlate with major-element compositions (Mg#, TiO₂, Al₂O₃). The observed oxygen isotope variations within low-Ti and high-Ti basalts are consistent with crystal fractionation and match the results of mass-balance models assuming equilibrium crystallization. Whole-rock δ⁵⁶Fe values (referenced to IRMM-014) of high-Ti and low-Ti basalts range from 0.134‰ to 0.217‰ and 0.038‰ to 0.104‰, respectively. Iron isotope compositions of both low-Ti and high-Ti basalts do not correlate with indices of crystal fractionation, possibly owing to small mineral-melt iron fractionation factors anticipated under lunar reducing conditions.The δ¹⁸O and δ⁵⁶Fe values of low-Ti and the least differentiated high-Ti mare basalts are negatively correlated, which reflects their different mantle source characteristics (e.g., the presence or absence of ilmenite). The average δ⁵⁶Fe values of low-Ti basalts (0.073 ± 0.018‰, n = 8) and high-Ti basalts (0.191 ± 0.020‰, n = 7) may directly record that of their parent mantle sources. Oxygen isotope compositions of mantle sources of low-Ti and high-Ti basalts are calculated using existing models of lunar magma ocean crystallization and mixing, the estimated equilibrium mantle olivine δ¹⁸O value, and equilibrium oxygen-fractionation between olivine and other mineral phases. The differences between the calculated whole-rock δ¹⁸O values for source regions, 5.57‰ for low-Ti and 5.30‰ for high-Ti mare basalt mantle source regions, are solely a function of the assumed source mineralogy. The oxygen and iron isotope compositions of lunar upper mantle can be approximated using these mantle source values. The δ¹⁸O and δ⁵⁶Fe values of the lunar upper mantle are estimated to be 5.5 ± 0.2‰ (2σ) and 0.085 ± 0.040‰ (2σ), respectively. The oxygen isotope composition of lunar upper mantle is identical to the current estimate of Earth’s upper mantle (5.5 ± 0.2‰), and the iron isotope composition of the lunar upper mantle overlaps within uncertainty of estimates for the terrestrial upper mantle (0.044 ± 0.030‰).     

Growth rate of the preserved continental crust: II. Constraints from Hf and O isotopes in detrital zircons from Greater Russian Rivers

Detrital zircons from the Ob, Yenisey, Lena, Amur, Volga, Dnieper, Don and Pechora rivers have been analyzed for U-Th-Pb, O and Lu-Hf isotopes to constrain the growth rate of the preserved continental crust in Greater Russia. Four major periods of zircon crystallization, 0.1-0.55, 0.95-1.3, 1.45-2.0 and 2.5-2.9 Ga, were resolved from a compilation of 1366 zircon U/Pb ages. The Archean zircons have δ¹⁸O values lying between 4.53‰ and 7.33‰, whereas Proterozoic and Phanerozoic zircons have a larger range of δ¹⁸O values in each of the recognized U/Pb time intervals with maximum δ¹⁸O values up to 12‰. We interpret the zircons with δ¹⁸O between 4.5‰ and 6.5‰ to have been derived from a magmatic precursor that contains little or no sedimentary component. The variable δ¹⁸O values of the zircons were used to constrain the ¹⁷⁶Lu/¹⁷⁷Hf ratios of the crustal source region of the zircons, which, in turn, were used to calculate Hf model ages (T_DM^V). The crustal incubation time, the time difference between primitive crust formation (dated by T_DM^V) and crustal melting (dated by zircon U/Pb age), varies between 300 to 1000 Myr for the majority of analyzed zircon grains, but can be up to 2500 Myr. The average T_DM^V Hf model age weighted by the fraction of zircons in the river load is 2.12 Ga, which is in reasonable agreement with the area-weighted average of 2.25 Ga. The T_DM^V Hf model age crustal growth curve for zircons with mantle-like δ¹⁸O values (4.5-6.5‰), weighted by area, shows that growth of the Great Russian continental crust started at 4.2 Ga, and that there are two principal periods of crustal growth, 3.6-3.3 Ga and 0.8-0.6 Ga, which are separated by an interval of low but more or less continuous growth. An alternative interpretation, in which the average ¹⁷⁶Lu/¹⁷⁷Hf ratio (0.0115) of the continental crust is used for the Paleoproterozoic zircons from the Lena River, lowers the average T_DM^V age of these grains by about 500 Myr and delays the onset of significant crustal growth to 3.5 Ga.The two principal growth periods recognized in Greater Russia differ from those identified from the Gondwana and the Mississippi river basin, which show peaks at 1.7-1.9 and 2.9-3.1 Ga (Hawkesworth and Kemp, 2006a) and 1.6-2.2 and 2.9-3.4 Ga (Wang et al., 2009), respectively. The older 3.6-3.3 Ga or 3.5-3.3 Ga peak for Greater Russia is slightly older than the older Gondwana-Mississippi peaks, whereas the younger 0.8-0.6 Ga peak is distinctly younger than the youngest peak in either Gondwana or the Mississippi river basin. This suggests that the two major peaks of crustal growth identified in Gondwana and the Mississippi river basin may not be global periods of enhanced continental growth and that the major periods of crustal growth may differ from continent to continent.     

Zircon megacrysts from kimberlite: oxygen isotope variability among mantle melts

The oxygen isotope ratios of Phanerozoic zircons from kimberlite pipes in the Kaapvaal Craton of southern Africa and the Siberian Platform vary from 4.7 to 5.9‰ VSMOW. High precision, accurate analyses by laser reveal subtle pipe-to-pipe differences not previously suspected. These zircons have distinctive chemical and physical characteristics identifying them as mantle-derived megacrysts similar to zircons found associated with diamond, coesite, MARID xenoliths, Cr-diopside, K-richterite, or Mg-rich ilmenite. Several lines of evidence indicate that these ¹⁸O values are unaltered by kimberlite magmas during eruption and represent compositions preserved since crystallization in the mantle, including: U/Pb age, large crystal size, and the slow rate of oxygen exchange in non-metamict zircon. The average ¹⁸O of mantle zircons is 5.3‰, ∼0.1 higher and in equilibrium with values for olivine in peridotite xenoliths and oceanic basalts. Zircon megacrysts from within 250 km of Kimberley, South Africa have average ¹⁸O=5.32±0.17 (n=28). Small, but significant, differences among other kimberlite pipes or groups of pipes may indicate isotopically distinct reservoirs in the sub-continental lithosphere or asthenosphere, some of which are anomalous with respect to normal mantle values of 5.3±0.3. Precambrian zircons (2.1–2.7 Ga) from Jwaneng, Botswana have the lowest values yet measured in a mantle zircon, ¹⁸O=3.4 to 4.7‰. These zircon megacrysts originally crystallized in mafic or ultramafic rocks either through melting and metasomatism associated with kimberlite magmatism or during metamorphism. The low ¹⁸O zircons are best explained by subduction of late Archean ocean crust that exchanged with heated seawater prior to underplating as eclogite and to associated metasomatism of the mantle wedge. Smaller differences among other pipes and districts may result from variable temperatures of equilibration, mafic versus ultramafic hosts, or variable underplating. The narrow range in zircon compositions found in most pipes suggests magmatic homogenization. If this is correct, these zircons document the existence of significant quantities of magma in the sub-continental mantle that was regionally variable in ¹⁸O and this information restricts theories about the nature of ancient subduction. Received: 8 August 1997 / Accepted: 6 May 1998     

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. δ⁵⁶Fe 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‰. δ²⁶Mg 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 δ⁵⁶Fe; ±0.10‰ for δ²⁶Mg, 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: Δ⁵⁶Fe_ol-cpx = −0.10 ± 0.12‰ (2SD, n = 18); Δ⁵⁶Fe_ol-opx = −0.05 ± 0.11‰; Δ²⁶Mg_ol-opx = −0.09 ± 0.12‰; Δ²⁶Mg_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 δ⁵⁶Fe 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 δ²⁶Mg is −0.30 ± 0.09‰, indistinguishable from chondrites, MORB, and OIB. Our data support the conclusion that the bulk silicate Earth (BSE) has chondritic δ⁵⁶Fe and δ²⁶Mg.The origin of inter-mineral fractionations of Fe and Mg isotopic ratios remains debated. δ⁵⁶Fe 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 δ⁵⁶Fe, the larger deviations from average δ⁵⁶Fe for three samples likely indicate changes due to metasomatic processes. Two samples show heavy δ⁵⁶Fe 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 δ⁵⁶Fe and slightly heavy δ²⁶Mg, which may reflect Fe-Mg inter-diffusion between peridotite and percolating melt.     

Lithium isotopes in Guatemalan and Franciscan HP-LT rocks: Insights into the role of sediment-derived fluids during subduction

High-pressure, low-temperature (HP-LT) rocks from a Cretaceous age subduction complex occur as tectonic blocks in serpentinite mélange along the Motagua Fault (MF) in central Guatemala. Eclogite and jadeitite among these are characterized by trace element patterns with enrichments in fluid mobile elements, similar to arc lavas. Eclogite is recrystallized from MORB-like altered oceanic crust, presumably at the boundary between the down-going plate and overlying mantle wedge. Eclogite geochemistry, mineralogy and petrography suggest a two step petrogenesis of (1) dehydration during prograde metamorphism at low temperatures (<500 °C) followed by (2) partial rehydration/fertilization at even lower T during exhumation. In contrast, Guatemalan jadeitites are crystallized directly from low-T aqueous fluid as veins in serpentinizing mantle during both subduction and exhumation. The overall chemistry and mineralogy of Guatemalan eclogites are similar to those from the Franciscan Complex, California, implying similar P-T-x paths.Li concentrations (?90 ppm) in mineral separates and whole rocks (WR) from Guatemalan and Franciscan HP-LT rocks are significantly higher than MORB (4-6 ppm), but similar to HP-LT rocks globally. Li isotopic compositions range from −5‰ to +5‰ for Guatemalan HP-LT rocks, and −4‰ to +1‰ for Franciscan eclogites, overlapping previous findings for other HP-LT suites. The combination of Li concentrations greater than MORB, and Li isotopic values lighter than MORB are inconsistent with a simple dehydration model. We prefer a model in which Li systematics in Guatemalan and Franciscan eclogites reflect reequilibration with subduction fluids during exhumation. Roughly 5-10% of the Li in these fluids is derived from sediments.Model results predict that the dehydrated bulk ocean crust is isotopically lighter (δ⁷Li ? +1 ± 3‰) than the depleted mantle (∼+3.5 ± 0.5‰), while the mantle wedge beneath the arc is the isotopic complement of the bulk crust. A subduction fluid with an AOC-GLOSS composition over the full range of model temperatures (50-600 °C) gives an average fluid δ⁷Li (∼+7 ± 5‰ 1σ) that is isotopically heavier than the depleted mantle. If the lowest temperature steps are excluded (50-260 °C) as too cold to participate in circulation of the mantle wedge, then the average subduction fluid (δ⁷Li = +4 ± 2.3‰ 1σ, is indistinguishable from depleted mantle. Because of the relatively compatible nature of Li in metamorphic minerals, the most altered part of the crust (uppermost extrusives), may retain a Li isotopic signature (∼+5 ± 3‰) heavier than the bulk crust. The range of Li isotopic values for OIB, IAB and MORB overlap, making it is difficult to resolve which of these components may contribute to the recycled component in the mantle using δ⁷Li alone.     

Quantification and isotopic analysis of nitrogen in rocks at the ppm level using sealed tube combustion technique: A prelude to the study of altered oceanic crust

The present paper reports recent improvements in sealed tube combustion technique used for the determination of N isotopic composition in various rocks characterized by low N contents (i.e. few ppm). Nitrogen is extracted from samples by combustion in quartz tubes sealed under vacuum. The nitrogen gas purified using Cu, CuO and CaO, is quantified as dinitrogen N₂ by capacitance manometry in ultra-high vacuum line. Nitrogen isotopic analysis is performed on a triple-collector static vacuum mass spectrometer, allowing measurement of nanomole quantity of N₂. Nitrogen amount and isotopic composition of the analytical blanks are low and describe Gaussian distribution with mean values of 0.65 ± 0.30 nmol N and − 3.7‰ ± 2.7‰, respectively (2σ). Systematic analyses of international and internal standards demonstrate that this technique provides accurate and precise results. The precision on N content and isotopic composition are better than ± 8% and ± 0.5‰ respectively, even for samples containing less than 2 ppm N. The sealed tube combustion technique is shown to apply successfully to rocks of various lithologies such as metagabbros, metaperidotites and altered basalts. It is thus suitable for studying oceanic crust in a perspective to better constrain N exchanges between Earth mantle and surface reservoirs. The investigation can also be extended to analysis of small size samples, particularly when little sample exists and when high spatial resolution is required.     

Central Antarctic provenance of Permian sandstones in Dronning Maud Land and the Karoo Basin: Integration of U-Pb and TDM ages and host-rock affinity from detrital zircons

In conjugate SE Africa and Antarctica, Early Permian sandstones of the Swartrant Formation of the Ellisras Basin, Vryheid Formation of the Karoo Basin, and Amelang Plateau Formation of Dronning Maud Land (DML) were deposited after Gondwanan glaciation on a westward paleoslope. We analysed detrital zircons for U-Pb ages by a laser ablation microprobe-inductively coupled plasma mass spectrometer (LAM-ICPMS) and attached age significance only to clusters of three or more overlapping analyses. We analysed Hf-isotope compositions by a multi-collector spectrometer (LAM-MC-ICPMS) and trace elements by electron microprobe (EMP) and ICPMS. These analyses indicate the rock type and source (whether crustal or juvenile mantle) of the host magma, and a “crustal” model age (T_DM^C). The integrated analysis gives a more distinctive, and more easily interpreted, picture of crustal evolution in the provenance area than age data alone.Zircons from the Ellisras Basin are aged 2700-2540 Ma with minor populations about 2815 Ma and 2040 Ma, which correspond with the ages of the upslope parts of the proximal Kaapvaal Craton and Limpopo Belt. Mafic rock is the dominant host rock, and it reflects the Archean granite-greenstone terrane of the Kaapvaal Craton.The three Karoo Basin samples and the two DML samples have zircons with these common properties: (1) 1160-880 Ma, host magma mafic granitoid (< 65% SiO₂) derived from juvenile depleted mantle sources (ε_Hf positive) at 1.65 Ga and 1.35 Ga, with T_DM^C of 2.0-0.9 Ga; (2) 760 to 480 Ma, host magma granitoid and low-heavy rare earth element rock (?alkaline rock-carbonatite), derived from mixed crustal and juvenile depleted mantle sources (ε_Hf positive and negative) at 1.50 Ga and 1.35 Ga, with T_DM^C of 2.0-0.9 Ga.Together with similar detrital zircons in Triassic sandstone of SE Australia, these properties reflect those in upslope central Antarctica, indicating a provenance of ∼ 1000 Ma (Grenville) cratons embedded in 700-500 Ma (Pan-Gondwanaland) fold belts. Detrital zircons in Cambrian sediments of the Ellsworth-Whitmore Mountains block and Cambrian metasediments of the Welch Mountains with comparable properties suggest that the central Antarctic provenance operated also in the ∼ 500 Ma Cambrian.     

Paleogene crustal anatexis and metamorphism in Lhasa terrane, eastern Himalayan syntaxis: Evidence from U-Pb zircon ages and Hf isotopic compositions of the Nyingchi Complex

In the eastern Himalayan syntaxis, the southern Lhasa terrane is dominated by middle- to high-grade metamorphic rocks (Nyingchi Complex), which are intruded by felsic melts. U-Pb zircon dating and zircon Hf isotopic composition of these metamorphic and magmatic rocks provide important constraints on the tectono-thermal evolution of the Lhasa terrane during convergent process between Indian and Asian continents. U-Pb zircon data for an orthogneiss intruding the Nyingchi Complex yield a protolith magma crystallization age of 83.4 ± 1.2 Ma, with metamorphic ages of 65-46 Ma. This orthogneiss is characterized by positive ε_Hf (t) values of + 8.3 and young Hf model ages of ~ 0.6 Ga, indicating a derivation primarily from a depleted-mantle or juvenile crustal source. Zircons from a quartz diorite yield a magma crystallization age of 63.1 ± 0.6 Ma, with ε_Hf (t) values of − 8.2 to − 2.7, suggesting that this magma was sourced from partial melting of older crustal materials. Zircon cores from a foliated biotite granite show ages ranging from 347 to 2690 Ma, with age peaks at 347-403 Ma, 461-648 Ma and 1013-1183 Ma; their zircon ε_Hf (t) values range from − 30.6 to + 6.9. Both the U-Pb ages and Hf isotopic composition of the zircon cores are similar to those of detrital zircons from the Nyingchi Complex paragneiss, implying that the granite was derived from anatexis of the Nyingchi Complex metasediments. The zircon rims from the granite indicate crustal anatexis at 64.4 ± 0.7 Ma and subsequent metamorphism at 55.1 ± 1.3 and 41.4 ± 2.3 Ma. Our results suggest that the late Cretaceous magmatism in the southern Lhasa terrane resulted from Neo-Tethys oceanic slab subduction and we infer that Paleocene crustal anatexis and metamorphism were related to the thermal perturbation caused by rollback of the northward subducted Neo-Tethyan oceanic slab.     

SHRIMP U-Pb dating, trace elements and the Lu-Hf isotope system of coesite-bearing zircon from amphibolite in the SW Sulu UHP terrane, eastern China

In this study, we link mineral inclusion data, trace element analyses, U-Pb age and Hf isotope composition obtained from distinct zircon domains of complex zircon to unravel the origin and multi-stage metamorphic evolution of amphibolites from the Sulu ultrahigh-pressure (UHP) terrane, eastern China. Zircon grains separated from amphibolites from the CCSD-MH drill hole (G12) and Niushan outcrop (G13) were subdivided into two main types based on cathodoluminescence (CL) and Laser Raman spectroscopy: big dusty zircons with inherited cores and UHP metamorphic rims and small clear zircons. Weakly zoned, grey-white luminescent inherited cores preserve mineral inclusions of Cpx + Pl + Ap ± Qtz indicative of a mafic igneous protolith. Dark grey luminescent overgrowth rims contain the coesite eclogite-facies mineral inclusion assemblage Coe + Grt + Omp + Phe + Ap, and formed at T = 732-839 °C and P = 3.0-4.0 GPa. In contrast, white luminescent small clear zircons preserve mineral inclusions formed during retrograde HP quartz eclogite to LP amphibolite-facies metamorphism (T = 612-698 °C and P = 0.70-1.05 GPa). Inherited zircons from both samples yield SHRIMP ²⁰⁶Pb/²³⁸U ages of 695-520 Ma with an upper intercept age of 800 ± 31 Ma. The UHP rims yield consistent Triassic ages around 236-225 and 239-225 Ma for G12 and G13 with weighted means of 229 ± 3 and 231 ± 3 Ma, respectively. Small clear zircons from both samples give ²⁰⁶Pb/²³⁸U ages around 219-210 Ma with a weighted mean of 214 ± 3 Ma, interpreted as the age of retrograde quartz eclogite-facies metamorphism. Matrix amphibole from both samples indicate Ar-Ar ages of 209 ± 0.7 and 207 ± 0.7 Ma, respectively, probably dating late amphibolite-facies retrogression. The data suggest subduction of Neoproterozoic mafic igneous rocks to UHP conditions in Middle Triassic (∼230 Ma) times and subsequent exhumation to an early HP (∼214 Ma) and a late LP stage (∼208 Ma) over a period of ∼16 and 6 Myr, respectively. Thus, early exhumation from a mantle depth of 120-100 km to about 60 km occurred at an average rate of 0.3 cm/y, while subsequent exhumation to a middle crustal level took place at approximately 0.54 cm/y. These exhumation rates are considerably slower than those obtained for UHP rocks in the Dora Maira and Kokchetav massifs (2-3 cm/y).Based on similar P-T estimates and trace element and Hf isotope compositions, Sulu amphibolites can be identified as retrograde UHP eclogites. The εHf₍₈₀₀₎ of +8 implies a significant input from the depleted mantle to the Sulu-Dabie terrane during the middle Neoproterozoic. Overgrown rims are characterized by a distinct trace element composition with low Lu/Hf and Th/U and significantly higher ¹⁷⁶Hf/¹⁷⁷Hf ratios than inherited cores, consistent with formation during/after garnet (re-)crystallization and fractionation of the Lu-Hf system during UHP metamorphism. The combined dataset suggests homogenization of the ¹⁷⁶Hf/¹⁷⁷Hf ratio within the metamorphic mineral assemblage and during protolith formation. Observed variations are explained by mixing of material from both domains during laser ablation, e.g., due to partial recrystallization of inherited cores.     

Magmatic and hydrothermal zircon growth during multiple orogenic cycles in an evolving mantle wedge

The Hongseong area of the Hongseong-Imjingang Belt in the central-western Korean Peninsula forms part of a subduction-collision system that is correlated with the Qinling-Dabie-Sulu Belt in China. Several serpentinized ultramafic bodies carrying blocks of metamorphosed mafic rocks occur in this area. Here we investigate zircon grains in serpentinites from Bibong(BB) and Wonnojeon(WNJ), and high-pressure(HP) mafic granulite from Baekdong(BD) localities based on U-Pb, REE and Lu-Hf analyses. The zircons from BD HP mafic granulite show distinct age peaks at 838 Ma, 617 Ma and 410 Ma, with minor peaks at1867 Ma, 1326 Ma and 167 Ma. The Neoproterozoic age peaks in these rocks as well as in the serpentinites suggest subduction-related melt-fluid interaction in the mantle wedge at this time. The older zircon grains ranging in age from the Early to Middle Paleoproterozoic might represent detrital grains from the basement rocks transferred to the wedge mantle through sediment subduction. The BD HP mafic granulite shows a Middle Paleozoic age peak(Devonian; 410 Ma). The 242-245 Ma age peaks in the compiled age data of zircon grains serpentinites from BB and WNJ correspond to a major Triassic event that further added melts and fluids into the ancient mantle wedge to crystallize new zircons. In the chondrite normalized rare earth element diagram, the magmatic zircon grains from the studied rocks show LREE depletion and HREE enrichment with sharply negative Eu and Pr anomalies and positive Ce and Sm anomalies. The REE patterns of hydrothermal zircons show LREE enrichment, and relatively flat patterns with negative Eu anomaly. Zircon Hf signature from the WNJ serpentinite show negative εHf(t)(-18.5 and-23.5) values indicating an enriched mantle source with TDM in the range of 1614 Ma and1862 Ma. Zircons from the BD HP mafic granulite also show slightly negative εHf(t)(average-4.3) and TDM in the range of 1365-1935 Ma. Our study provides evidence for multiple zircon growth in an evolving mantle wedge that witnessed melt and fluid interaction during different orogenic cycles.     

U–Pb age and origin of gem zircon from the New England sapphire fields,New South Wales,Australia

Chemical compositions and geochronological data utilising the laser ablation ICP-MS technique are presented for zircon megacrysts found in alluvial gem corundum deposits associated with Upper Cretaceous–Cenozoic alkali basalts in the Inverell district-New England field, New South Wales, eastern Australia. Three localities, Kings Plains, Swan Brook and Mary Anne Gully, produce gem-quality transparent dark brown and yellow zircon megacrysts, mostly under 10 mm in size. Although brown zircon shows relative enrichment in Hf and REE, there are no differences in relative transition metal concentrations between the colours. Chemical homogeneity within a single crystal indicates stable crystallisation conditions. The ²⁰⁶Pb/²³⁸U age of zircon megacrysts from these three localities define older and younger groups of 216–174 Ma and 45–37.7 Ma, respectively. The ?_Hf values of zircon megacrysts from Kings Plains show +7.51±0.34 in the older group and +10.72±0.31 in the younger group. Swan Brook zircons give +11.54±0.47 and +8.32±0.58, and Mary Anne Gully zircons are +13.67±0.63 and +8.50±0.48, respectively. These zircons from New England alluvial gem deposits have two main formational events around Upper Triassic–Lower Jurassic and Eocene episodes. Most originated from lithospheric mantle and all were brought-up by later host basaltic magmas.     

Ti-in-zircon thermometry: applications and limitations

The titanium concentrations of 484 zircons with U-Pb ages of ∼1 Ma to 4.4 Ga were measured by ion microprobe. Samples come from 45 different igneous rocks (365 zircons), as well as zircon megacrysts (84) from kimberlite, Early Archean detrital zircons (32), and zircon reference materials (3). Samples were chosen to represent a large range of igneous rock compositions. Most of the zircons contain less than 20 ppm Ti. Apparent temperatures for zircon crystallization were calculated using the Ti-in-zircon thermometer (Watson et al. 2006, Contrib Mineral Petrol 151:413–433) without making corrections for reduced oxide activities (e.g., TiO₂ or SiO₂), or variable pressure. Average apparent Ti-in-zircon temperatures range from 500° to 850°C, and are lower than either zircon saturation temperatures (for granitic rocks) or predicted crystallization temperatures of evolved melts (∼15% melt residue for mafic rocks). Temperatures average: 653 ± 124°C (2 standard deviations, 60 zircons) for felsic to intermediate igneous rocks, 758 ± 111°C (261 zircons) for mafic rocks, and 758 ± 98°C (84 zircons) for mantle megacrysts from kimberlite. Individually, the effects of reduced or , variable pressure, deviations from Henry’s Law, and subsolidus Ti exchange are insufficient to explain the seemingly low temperatures for zircon crystallization in igneous rocks. MELTs calculations show that mafic magmas can evolve to hydrous melts with significantly lower crystallization temperature for the last 10–15% melt residue than that of the main rock. While some magmatic zircons surely form in such late hydrous melts, low apparent temperatures are found in zircons that are included within phenocrysts or glass showing that those zircons are not from evolved residue melts. Intracrystalline variability in Ti concentration, in excess of analytical precision, is observed for nearly all zircons that were analyzed more than once. However, there is no systematic change in Ti content from core to rim, or correlation with zoning, age, U content, Th/U ratio, or concordance in U-Pb age. Thus, it is likely that other variables, in addition to temperature and , are important in controlling the Ti content of zircon. The Ti contents of igneous zircons from different rock types worldwide overlap significantly. However, on a more restricted regional scale, apparent Ti-in-zircon temperatures correlate with whole-rock SiO₂ and HfO₂ for plutonic rocks of the Sierra Nevada batholith, averaging 750°C at 50 wt.% SiO₂ and 600°C at 75 wt.%. Among felsic plutons in the Sierra, peraluminous granites average 610 ± 88°C, while metaluminous rocks average 694 ± 94°C. Detrital zircons from the Jack Hills, Western Australia with ages from 4.4 to 4.0 Ga have apparent temperatures of 717 ± 108°C, which are intermediate between values for felsic rocks and those for mafic rocks. Although some mafic zircons have higher Ti content, values for Early Archean detrital zircons from a proposed granitic provenance are similar to zircons from many mafic rocks, including anorthosites from the Adirondack Mts (709 ± 76°C). Furthermore, the Jack Hills zircon apparent Ti-temperatures are significantly higher than measured values for peraluminous granites (610 ± 88°C). Thus the Ti concentration in detrital zircons and apparent Ti-in-zircon temperatures are not sufficient to independently identify parent melt composition. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

U-Pb age and genetic significance of heterogeneous zircon populations in rocks from the Favourable Lake area,Northwestern Ontario

The study evaluates the relationships between measured U-Pb ages and zircon characteristics of five morphologically, texturally, and isotopically complex zircon populations and compares the zircon development stages to the orogenic evolution of the Favourable Lake area. Two distinct zircon types from a hornblendite xenolith in a granitoid batholith of the Sachigo subprovince of the Superior Province yield U-Pb ages of 2729.0±6.8 Ma and 2714.8 _–6.4 ^+7.4 Ma, which date specific metamorphic phases coinciding with major plutonic pulses in the batholith. Zircons from a metamorphosed felsic dike, crosscutting the hornblendite, consist of an old zircon component with a minimum age of 2788 Ma possibly reflecting igneous crystallization 2950 Ma ago, and a younger component with an inferred age of 2725±15 Ma, probably reflecting metamorphism during batholith emplacement.In the Berens River subprovince to the south, granodiorite forms both a late tectonic phase in a large batholith and a post-tectonic pluton intruded into the batholith, yet zircons from these granodiorites have identical ages of 2697.3±1.7 Ma and 2696.2±1.2 Ma, respectively. The late tectonic granodiorite also contains inherited zircons with a minimum age of 2767 Ma which are indirect evidence for the presence of old sialic crust in this subprovince. Zircons from a sheared monzonite near the boundary fault between the two subprovinces yield an upper intercept age of 2769 _–26 ⁺⁶³ Ma, which we interpret as the intrusion age of the monzonite. This rock is older than most dated units in the surrounding batholiths and suggests that the boundary is a long-lived Archean structure.A lower intercept age of about 1750 Ma for zircons of the hornblendite is the result of chemical alteration of the zircons. This, and a similar lower intercept age shown by the sheared monzonite zircons, are thought to reflect increased fluid activity and possibly shearing during the Early Proterozoic Hudsonian orogeny which occurred in the Churchill Province to the northwest. A later Pb-loss mainly from near-surface domains of the zircons is indicated by lower intercept ages of about 500–100 Ma.Publication approved by the Director, Ontario Geological Survey