Nuvvuagittuq Research Articles

A Neoarchean (ca. 2500 Ma) age for jaspilite-carbonate BIF hosting purported micro-fossils from the Eoarchean (≥3750 Ma) Nuvvuagittuq supracrustal belt (Québec, Canada)

In the exploration of the origin and evolution of early life on Earth, age determinations of fossil occurrences are of critical importance. Purported microbial fossils preserved in chert and jasper are commonly assigned indirect dates due to a lack of suitable minerals for geochronology in the fossil-bearing horizons. Such indirect dating methods commonly result in age estimates that predate the hosted putative fossil structures, especially when considering possible formation of these structures in post-depositional hydrothermal/metamorphic events. Herein, we report a Neoarchean (ca. 2.5 Ga) U-Pb ID-TIMS zircon and apatite age for jaspilite and carbonate-bearing iron formation that hosts putative ferruginous “microbial fossil structures” in the Eoarchean Nuvvuagittuq supracrustal belt (NSB) in northern Québec (Canada). In situ oxygen isotope and REE compositions suggest apatite and calcite separated from jaspilite are hydrothermal in origin. Collectively, our results suggest that some of these ferruginous “microbial fossil structures” could be primary biogenic structures produced in an Eoarchean hydrothermal environment that survived subsequent late Archean metamorphism and deformation. In contrast, some are possibly abiogenic structures formed via Liesegang-type processes during late Archean hydrothermal activity. A broader assessment of the ages of putative biostructures in Eoarchean and Paleoarchean rocks, wherein incorrect age assignment remains a persistent problem, is therefore warranted.

Earth's earliest hydrosphere recorded by the oldest hydrothermally-altered oceanic crust: Triple oxygen and hydrogen isotopes in the 4.3-3.8 Ga Nuvvuagittuq belt, Canada

The origin, evolution, and the state of Earth's hydrosphere are relevant for the timing, style, and intensity of plate tectonics, continental and submarine weathering, and the emergence of the continents. We here present a study of triple oxygen isotopes of hydrothermally altered oceanic crust from the Nuvvuagittuq greenstone belt (NGB) in Canada (4.3-3.8 Ga), which provides a rare snapshot of the Earth's earliest hydrosphere on a planet without modern-style plate tectonics. High δ18O = 8-12‰, Δ′17O=-0.02 to −0.05‰, and δD of −30-40‰ values measured in the NGB metavolcanic rocks are interpreted to indicate that they represent the upper section of ancient oceanic crust (pillows, sediments) altered at low-temperature by seawater similar to modern submarine oceanic sections. Hydrothermal alteration was accompanied by silicification at low temperature (50-150°C) as evidenced by a positive correlation of δ18O with silica, elevated Δ′17O values, and triple oxygen isotope thermometry. We discuss the effects of 2.7 Ga metamorphism on the preservation of triple oxygen isotope compositions and show that the hydrothermal alteration is protolithic and predated metamorphism. Triple oxygen isotopes allow reconstruction of the isotopic compositions of seawater and suggest that the δ18O of the early oceans could have been comparable to that of the modern to perhaps −5‰ but silica-saturated. Models with an ancient ocean with δ18O of +3‰ or <−5‰ seawater result in worse fits to the data. Submarine weathering and hydrothermal silicification could have played a more important role in Eoarchean world with subdued role of subaerial weathering due to insignificant continental exposure that helped balancing seawater δ18O values to near modern values.

Metabolically diverse primordial microbial communities in Earth's oldest seafloor-hydrothermal jasper.

The oldest putative fossils occur as hematite filaments and tubes in jasper-carbonate banded iron formations from the 4280- to 3750-Ma Nuvvuagittuq Supracrustal Belt, Québec. If biological in origin, these filaments might have affinities with modern descendants; however, if abiotic, they could indicate complex prebiotic forms on early Earth. Here, we report images of centimeter-size, autochthonous hematite filaments that are pectinate-branching, parallel-aligned, undulated, and containing Fe2+-oxides. These microstructures are considered microfossils because of their mineral associations and resemblance to younger microfossils, modern Fe-bacteria from hydrothermal environments, and the experimental products of heated Fe-oxidizing bacteria. Additional clusters of irregular hematite ellipsoids could reflect abiotic processes of silicification, producing similar structures and thus yielding an uncertain origin. Millimeter-sized chalcopyrite grains within the jasper-carbonate rocks have 34S- and 33S-enrichments consistent with microbial S-disproportionation and an O2-poor atmosphere. Collectively, the observations suggest a diverse microbial ecosystem on the primordial Earth that may be common on other planetary bodies, including Mars.

Using Zn and Ni behavior during magnetite precipitation in banded iron formations to determine its biological or abiotic origin

There is longstanding controversy about the genesis of magnetite in banded iron formations (BIFs), particularly concerning whether it is of abiogenic or biogenic origin. The composition of trace elements within magnetite produced by magnetotactic bacteria has been proposed as a promising marker for its biological origin; however further experimental evidence is required to investigate whether this also holds true for iron-metabolizing bacteria. Here, we compared the behavior of zinc (Zn) and nickel (Ni) in magnetite produced either abiogenically (ferrihydrite reacting with dissolved Fe2+) or biogenically (ferrihydrite reacting with dissolved Fe2+ generated via the dissimilatory iron-reducing bacterium - DIRB - Shewanella oneidensis MR-1). These abiotic and biotic incubations were applied for transforming three ferrihydrite (Fh) substrates: (1) Control Fh without added trace elements; (2) Zn-coprecipitated ferrihydrite (ZnFh); and (3) Ni-coprecipitated ferrihydrite (NiFh) in both NaHCO3 and HEPES buffer. X-ray diffraction revealed magnetite as the dominant transformation product for all reaction conditions, while siderite was only detected in experiments containing NaHCO3 as buffer. Based on similar initial dissolved Ni and Zn concentrations, we found opposing behavior of Zn and Ni where Zn showed enrichment in abiogenic magnetite, while Ni was more enriched in biogenic magnetite. Combining supposed Zn and Ni concentrations in Precambrian seawater and magnetite mineral grains from three formations deposited at different ages (i.e. 3.75 Ga Nuvvuagittuq Supracrustal Belt, 2.45 Ga Weeli Wolli Iron Formation, and 1.88 Ga Sokoman Iron Formation), we reconstructed potential Zn and Ni partition coefficients between Precambrian seawater and magnetite minerals. The reconstructed potential Zn and Ni partition coefficients suggested that these magnetite minerals from three formations were abiogenic. These differing behaviors suggest the possibility of using Zn and Ni partition coefficient ratios as a means of determining the presence or absence of DIRB in the formation of ancient magnetite deposits.

Calcium isotope evidence for early Archaean carbonates and subduction of oceanic crust

Continents are unique to Earth and played a role in coevolution of the atmosphere, hydrosphere, and biosphere. Debate exists, however, regarding continent formation and the onset of subduction-driven plate tectonics. We present Ca isotope and trace-element data from modern and ancient (4.0 to 2.8 Ga) granitoids and phase equilibrium models indicating that Ca isotope fractionations are dominantly controlled by geothermal gradients. The results require gradients of 500–750 °C/GPa, as found in modern (hot) subduction-zones and consistent with the operation of subduction throughout the Archaean. Two granitoids from the Nuvvuagittuq Supracrustal Belt, Canada, however, cannot be explained through magmatic processes. Their isotopic signatures were likely inherited from carbonate sediments. These samples (> 3.8 Ga) predate the oldest known carbonates preserved in the rock record and confirm that carbonate precipitation in Eoarchaean oceans provided an important sink for atmospheric CO2. Our results suggest that subduction-driven plate tectonic processes started prior to ~3.8 Ga.

Geochemical and textural investigations of the Eoarchean Ukaliq supracrustals, Northern Québec (Canada)

Structural, geochronological and geochemical studies of pre-3.75 Ga rocks of volcano-sedimentary protoliths in the Inukjuak domain in the Superior Province in Québec have been mostly focused on the Nuvvuagittuq Supracrustal Belt (NSB). The Porpoise Cove outcrops – at the southwestern limit of the NSB – are the de-facto “type locality” for the supracrustals of the Inukjuak Complex. Yet, it remains unclear whether the NSB rocks are geochemically distinct from, or are in fact common to, a host of other supracrustal enclaves locked in the dominantly gneissic Inukjuak domain. Here, we report detailed textural and geochemical studies for a suite of rocks from the Ukaliq Supracrustal Belt (USB), located approximately 3 km northeast of the NSB. We find that the USB and NSB have a similar protracted metamorphic history; both experienced amphibolite grade metamorphism and contain granitoid gneiss sheets, quartz-magnetite rocks (banded iron-formation s.l.) and quartz-biotite schists within amphibolitized rocks of basaltic affinity with local retrogressions. If the various Inukjuak supracrustal belts were once a part of a larger coherent (now dismembered) terrane, they should show similar emplacement ages and source chemistry. New zircon UPb geochronology from five gneissic units and two quartz-biotite (metasedimentary) schists reveal the oldest emplacement ages across all units of each individual rock type to be 3.68 ± 0.07 Ga (granitoid gneisses) and 3.65 ± 0.06 Ga (quartz-biotite schists). These new ages are similar to those documented as likely minimum emplacement ages of the NSB determined by UPb geochronology. Zircons from the quartz-biotite schist were also analyzed by ion microprobe for their UPb geochronology and were found to yield statistically identical, albeit more precise, ages than those obtained by LA-ICP-MS. Possible detrital zircons from the USB quartz-biotite schists were analyzed by ion microprobe for their coupled δ30SiNBS28 and δ18OVSMOW values with respective values between −0.75 and − 0.07‰ (δ30SiNBS28), and + 5.61 and + 6.59‰ (δ18OVSMOW). The δ18OVSMOW values, which are on average above mantle-derived zircon, indicate contribution of altered, non-mantle, derived material into the source of the rocks that weathered to form the quartz-biotite schists. Zircon mineral inclusions (quartz, feldspar, apatite, biotite, muscovite and other unrecognized Fe/Al/Si rich phases), along with the major- and trace element contents for the rocks were analyzed to substantiate this interpretation. Together with δ30SiNBS28, δ18OVSMOW, our results suggest that lithologies like authigenic silica and serpentinized rocks re-melted to form the parent melts that gave rise to zircons found in the USB quartz-biotite schists. Additional LuHf studies reported here on the same zircons also show similarities with NSB zircons. The εHf values showed a positive correlation with the measured UPb age from −22.7 ± 0.8 to +1.9 ± 1.1. The LuHf system also reveals that the USB, extracted at ca. 3.8 Ga, carries isotopic signatures of an older Hadean reservoir, having been formed from an Eoarchean mafic melt that incorporated them. Taken together, this supports a co-genetic origin for the NSB and the USB.

Widespread poly-metamorphosed Archean granitoid gneisses and supracrustal enclaves of the southern Inukjuak Domain, Québec (Canada)

The ~12,000 km2 Inukjuak Domain in northern Québec is part of the Archean Minto Block in the northwestern Superior Province of Canada. Eoarchean (ca. >3800–3780 Ma) rocks of the Nuvvuagittuq supracrustal belt (NSB) are the best known occurrence of otherwise abundant <1 m to km-scale supracrustal enclaves dispersed throughout the Innuksuac Complex. The supracrustals are dominantly amphibolites, with subordinate intermediate-, mafic- and ultramafic schists, quartzo-feldspathic (trondhjemitic and granodioritic) sills, dikes and sheets, banded iron-formations and quartz-pyroxene±magnetite rocks, and (detrital) fuchsitic quartzites. Supracrustal assemblages are in turn hosted by variably deformed granite-granitoid gneisses metamorphosed to amphibolite facies. Locally, retrogression is expressed as pervasive chloritization and development of jaspilite box veinings. This metamorphic history precludes preservation of original fragile microfossil shapes. Despite its importance as one of the few terranes to host Eoarchean supracrustal assemblages, limited geochronology was previously available for rocks beyond the ~8 km2 NSB. Here, we report new major-, minor-, and trace-element geochemistry and metamorphic petrology coupled with UPb zircon geochronology, from rocks within and surrounding the NSB. These include the little-studied but volumetrically significant Voizel suite gneisses. Results show that intra-NSB fold belt rocks of the Central Tonalitic Gneiss (CTG) preserve mainly ca. 3650 Ma zircons. Beyond the NSB, the Voizel gneisses – previously considered contemporaneous with the CTG – are instead about 100 Myr younger (~3550 Ma). Tonalitic (ortho)gneisses at the margin of the NSB were previously assigned a ca. 3650 Ma age, and the surrounding Boizard suite gneisses may be about 2700 Ma. We find the Boizard rocks contain inherited zircon cores up to ca. 3700 Ma, with younger overgrowths dated at ca. 2700 Ma. A tonalitic gneiss that transects another highly deformed supracrustal enclave north of the NSB – dubbed the Ukaliq Supracrustal Belt – yields maximum concordant zircon ages of 3653 ± 16 Ma (2σ). Detrital zircons from Ukaliq and Nuvvuagittuq quartzites and quartz-biotite schists define a maximum age of ca. 3780 Ma. No indication of UPb zircon ages older than about 3800 Ma exist in this terrane from our geochronological surveys. New reconnaissance sampling of gneisses to the west of the NSB fold belt yielded more zircon-bearing rocks with ages of ca. 3760 Ma. This discovery of more pre-3700 Ma rocks beyond the NSB outcrops calls attention to the existence of hitherto unidentified but widespread scattered occurrences of Eoarchean and Paleoarchean rocks throughout the region.

The nature of Earth’s first crust

Recycling of crust into the mantle has left only small remnants at Earth’s surface of crust produced within a billion years of Earth formation. Few, if any, of these ancient crustal rocks represent the first crust that existed on Earth. Understanding the nature of the source materials of these ancient rocks and the mechanism of their formation has been the target of decades of geological and geochemical study. This traditional approach has been expanded recently through the ability to simultaneously obtain U-Pb age and initial Hf isotope data for zircons from many of these ancient, generally polymetamorphic, rocks. The addition of information from the short-lived radiometric systems 146Sm-142Nd and 182Hf-182W allows resolution of some of the ambiguities that have clouded the conclusions derived from the long-lived systems. The most apparent of these is clear documentation that Earth experienced major chemical differentiation events within the first tens to hundreds of millions of years of its formation, and that Earth’s most ancient crustal rocks were derived from these differentiated sources, not from primitive undifferentiated mantle. Eoarchean rocks from the North Atlantic Craton and the Anshan Complex of the North China Craton have sources in an incompatible-element-depleted mantle that dates to 4.4–4.5 Ga. Hadean/Eoarchean rocks from two localities in Canada show the importance of remelting of Hadean mafic crust to produce Eoarchean felsic crust. The mafic supracrustal rocks of the Nuvvuagittuq Greenstone Belt are a possible example of the Hadean mafic basement that is often called upon to serve as the source for the high-silica rocks that define continental crust. Many, but not all, ancient terranes show a shift in the nature of the sources for crustal rocks, and possibly the physical mechanism of crust production, between 3.0–3.6 Ga. This transition may reflect the initiation of modern plate tectonics. Eoarchean/Hadean rocks from some terranes, however, also display compositional characteristics expected for convergent margin volcanism suggesting that at least some convergent margin related magmatism began in the Hadean. The persistence of isotopic variability in 142Nd/144Nd into the mid-Archean, and the eventual reduction in that variability by the end of the Archean, provides new information on the efficiency by which mantle convection recombined the products of Hadean silicate-Earth differentiation. The rate of crust production and recycling in the Hadean/Archean, however, is not resolved by these data beyond the observation that extreme isotopic compositions, such as expected for Hadean evolved, continent-like, crust are not observed in the preserved Eoarchean rock record. The lack of correlation between 142Nd/144Nd and 182W/184W variation in Archean rocks suggests that these two systems track different processes; the Sm-Nd system mantle-crust differentiation while Hf-W is dominated by core formation. The major silicate differentiation controlling Sm/Nd fractionation occurred at ∼4.4 Ga, possibly as a result of the Moon-forming impact, after the extinction of 182Hf.

Geochemistry and petrogenesis of the early Archean mafic crust from the Saglek-Hebron Complex (Northern Labrador)

The Saglek-Hebron Complex located in Northern Labrador, Canada, is one of the oldest granite-greenstone terrains on Earth. It is dominated by granitoids as old as 3.9 Ga and several enclaves of supracrustal rocks. We present here the largest whole-rock major and trace element geochemical dataset (over 100 samples) on the mantle-derived rocks from the Saglek-Hebron Complex to constrain their petrogenesis. The mafic amphibolites are metavolcanic rocks basaltic in composition, have tholeiitic affinities, and exhibit relatively homogeneous compositions with flat rare-earth element profiles. They include incompatible element enriched and depleted compositions, both which appear to be related by fractional crystallization of a gabbroic assemblage within volcanic flows. The enriched mafic rocks exhibit higher Ti contents compared to the more depleted mafic rocks, representing, respectively, evolved liquids and pyroxene-rich cumulate-liquid mixtures. Previous work has suggested the occurrence of two distinct supracrustal units in the Saglek-Hebron Complex, the Eoarchean Nulliak assemblage and the Mesoarchean Upernavik assemblage. Here we report that the petrological and geochemical composition of both assemblages is indistinguishable. This suggests either that the Nulliak and Upernavik metavolcanic rocks represent a single unit, or that they were formed by identical processes in a comparable context, despite an age difference of ∼400 Ma. Contrary to some other early metavolcanic belts, such as the Isua supracrustal belt and Nuvvuagittuq greenstone belt, none of the metavolcanic rocks from the Saglek-Hebron Complex studied here exhibit geochemical compositions that could be reminiscent of suprasubduction environments. The Saglek-Hebron Complex also includes two compositionally distinct groups of ultramafic rocks characterized by different Al/Ti ratios, Fe contents and controlled by olivine fractionation with different Fo contents. Ultramafic rocks from both groups appear to be cumulates derived from distinct parental magmas with a komatiitic basalt composition. One of these parental magmas may be genetically linked through fractional crystallization with the mafic metavolcanic rocks, whereas the other group is more difficult, at least geochemically, to relate to the Saglek-Hebron basaltic rocks.

A comparison of bulk versus laser ablation trace element analyses in banded iron formations: Insights into the mechanisms leading to compositional variability

Banded iron formations (BIF) represent one of the few chemical sedimentary archives available for exploring the redox state of the Precambrian atmosphere-ocean system and the marine availability of biologically critical trace nutrients through time. Temporal records compiled for a number of trace elements show a relatively wide spread in concentrations spanning several orders of magnitude within a single deposit. It has been suggested that this spread is present in both bulk rock digestion and laser ablation data, however, the comparability of data from the two methods has not been thoroughly evaluated. Here, we provide a statistical assessment of how comparable laser ablation data of individual BIF hematite and magnetite grains are to one another, as well as how closely averages of laser ablation data approximate bulk rock values. To do so, we use (laser ablation)-high resolution inductively coupled plasma mass spectrometry ((LA)-HR-ICP-MS) data from 14 BIF slabs and corresponding powders that span four different formations. We focus in particular on BIF from the ≥3.75 Ga Nuvvuagittuq Supracrustal Belt (Québec, Canada) and multiple BIF deposits of the 2.6–2.45 Ga Hamersley Group (North Western Australia), representing deposits separated by over a billion years and of differing metamorphic grade. The scaling between selected transition metals is also evaluated in light of expectations for possible delivery mechanisms of trace elements from seawater to BIF precursor sediments – the adsorption to hydrous ferric oxides, biological vectors, and detrital influence. Our findings show that average trace element concentrations between bulk versus laser ablation data typically vary within an order of magnitude. Furthermore, reproducibility between the two methods appears to be independent of formation age, metamorphic grade, or depositional setting. These findings underscore the overall fidelity of the BIF record at capturing seawater compositional signatures at various scales. We demonstrate that evaluations of ancient seawater chemistry using the BIF record are best served by a combined approach utilizing both bulk rock and laser ablation data, as bulk methods offer the most conservative proxy data for ancient seawater composition but may mask significant enrichments or depletions that are detectable at the grain-scale by laser ablation.

Using the magmatic record to constrain the growth of continental crust—The Eoarchean zircon Hf record of Greenland

Southern West Greenland contains some of the best-studied and best-preserved magmatic Eoarchean rocks on Earth, and these provide an excellent vantage point from which to view long-standing questions regarding the growth of the earliest continental crust. In order to address the questions surrounding early crustal growth and complementary mantle depletion, we present Laser Ablation Split Stream (LASS) analyses of the U–Pb and Hf isotope compositions of zircon from eleven samples of the least-altered meta-igneous rocks from the Itsaq (Amîtsoq) Gneisses of the Isukasia and Nuuk regions of southern West Greenland. This analytical technique allows a less ambiguous approach to determining the age and Hf isotope composition of complicated zircon. Results corroborate previous findings that Eoarchean zircon from the Itsaq Gneiss (∼3.85 Ga to ∼3.63 Ga) were derived from a broadly chondritic source. In contrast to the Sm–Nd whole rock isotope record for southern West Greenland, the zircon Lu–Hf isotope record provides no evidence for early mantle depletion, nor does it suggest the presence of crust older than ∼3.85 Ga in Greenland.Utilizing LASS U–Pb and Hf data from the Greenland zircons studied here, we demonstrate the importance of focusing on the magmatic (rather than detrital) zircon record to more confidently understand early crustal growth and mantle depletion. We compare the Greenland Hf isotope data with other Eoarchean magmatic complexes such as the Acasta Gneiss Complex, Nuvvuagittuq greenstone belt, and the gneissic complexes of southern Africa, and all lack zircons with suprachondritic Hf isotope compositions. In total, these data suggest only a very modest volume of crust was produced during (or survived from) the Hadean and earliest Eoarchean. There remains no record of planet-scale early Earth mantle depletion in the Hf isotope record prior to 3.8 Ga.

Mineral inclusion assemblage and detrital zircon provenance

Mineral inclusions are common in magmatic zircon and a potentially rich source of petrologic information. Controls on the relative proportions of inclusion phases, specifically early-crystallizing minerals such as apatite and late-crystallizing phases such as quartz, K-feldspar, and muscovite, have not been systematically studied. For instance, apatite dominates many magmatic zircon inclusion suites, and selective replacement of apatite over other phases has been proposed as a mechanism for generating apatite-poor inclusion assemblages in detrital zircons. However, the extent to which apatite inclusion abundance is influenced by source rock composition has not been established. The preservation of characteristic minerals in granite series, such as differences in magnetite and ilmenite abundances due to varying redox, have also not been systematically explored as inclusion phases in zircon. We surveyed zircon inclusion assemblages in Phanerozoic granitoids of a range of compositions and found a broadly inverse relationship between the presence of apatite in the inclusion suite and whole-rock SiO2 content. Selective loss of apatite is evident from deficits in apatite content among inclusions in contact with cracks in both detrital zircons and some granitoid zircons with independent evidence for fluid ingress (i.e., secondary phases filling open cracks). In cases where microstructural observations can identify primary inclusion assemblages (versus those impacted by fluid ingress), the relative occurrence of apatite can be used to broadly predict source rock SiO2 content. There is little relationship between whole-rock chemistry and the abundance of late-crystallizing phases or the relative proportions of quartz, plagioclase, and alkali feldspar. The presence of ilmenite not in contact with cracks in the host zircon likely points to origins in ilmenite-series (i.e., reduced) magmas, but the presence of magnetite is less diagnostic. Using the apatite abundance metric, detrital Hadean zircons from Jack Hills (Western Australia), appear to derive from felsic rather than intermediate or mafic granitoids and detrital Eoarchean zircons from Nuvvuagittuq Supracrustal Belt (Quebec) may derive from intermediate to felsic granitoids. No Fe-Ti oxides have been identified in Nuvvuagittuq zircons, but rare ilmenite in Jack Hills zircons points to origins of at least some part of the population in ilmenite-series magmas.

Applications of biotite inclusion composition to zircon provenance determination

Detrital zircons are the only confirmed surviving remnants of >4.03 Ga crust while younger detrital zircons provide a parallel record of more recent crustal evolution to that preserved in crystalline rocks. Zircons often preserve inclusions that may provide clues as to the origins of out-of-context grains in the sedimentary record. Previous studies have established that inclusions of biotite in magmatic zircon are compositionally well-matched to biotite in the source rock matrix, although a direct application to ancient detrital zircons has not been made. A number of studies have documented variations in the Fe, Mg, and Al contents of magmatic biotite from different source rocks and tectonic settings, suggesting that biotite inclusions may indeed serve as provenance indicators for detrital zircons. Consistent with earlier studies, we find that the FeO⁎/MgO ratio of magmatic biotite from continental arcs, collisional, and within-plate settings varies with relative oxidation state as well as whole-rock FeO⁎/MgO, while its Al2O3/(FeO⁎ + MgO) varies with whole-rock A/CNK (molar Al/(2⋅Ca + Na + K)). Biotite from oxidized metaluminous and reduced S-type granitoids can be readily distinguished from each other using FeO⁎/MgO and Al2O3/(FeO⁎ + MgO), while biotite from reduced I-type and oxidized peraluminous granites may in some cases be more ambiguous. Biotite from peralkaline and reduced A-type granites are also distinguishable from all other categories by Al2O3/(FeO⁎ + MgO) and FeO⁎/MgO, respectively. Biotite inclusions in Hadean zircons from Jack Hills, Western Australia indicate a mixture of metaluminous and reduced S-type host rocks, while inclusions in 3.6–3.8 Ga detrital zircons from the Nuvvuagittuq Supracrustal Belt indicate more oxidized peraluminous magmas. These results highlight the diversity of felsic materials on the early Earth and suggest that biotite inclusions are applicable to zircon provenance throughout the sedimentary record.

Sluggish Hadean geodynamics: Evidence from coupled 146,147Sm–142,143Nd systematics in Eoarchean supracrustal rocks of the Inukjuak domain (Québec)

The discovery of deficits in 142Nd/144Nd in mafic rocks of the Nuvvuagittuq supracrustal belt (NSB) has triggered a debate about the possible preservation of Hadean (pre-3.85 Ga) crustal remnants in the little-known but areally extensive Innuksuac complex (3.6–3.8 Ga, Inukjuak domain, Northeast Superior Province, Canada). Geochronological investigations in the NSB, however, are hampered by the poor preservation and highly disturbed isotopic record of various mafic (amphibolite) lithologies that host the 142Nd anomalies. Here we present 146Sm–142Nd and 147Sm–143Nd data for rocks of extrusive magmatic and sedimentary protoliths from the Ukaliq supracrustal belt, a newly discovered volcano-sedimentary enclave enclosed in granitoid gneisses of the Inukjuak domain. Our study also includes the first 146Sm–142Nd data for quartz-magnetite rocks (banded iron-formation; BIF) of the NSB and the Eoarchean Isua supracrustal belt (ISB) in southern West Greenland. We show that Ukaliq amphibolites carry variably negative 142Nd anomalies, ranging from 0 to −10 ppm, which are positively correlated with their Sm/Nd ratio. If considered as an isochron relationship, the 146Sm–142Nd array yields an apparent Hadean emplacement age of 4215−76+50 Ma. The negative 142Nd anomalies, however, appear to be mainly restricted to amphibolites with boninitic affinities, likely reflecting inheritance from an enriched mantle source. In contrast, tholeiitic and ultramafic lavas have normal μ142Nd regardless of their Sm/Nd ratio. Furthermore, BIF from Ukaliq and Nuvvuagittuq lack the negative 142Nd anomalies that should have been produced by in situ decay of 146Sm had these sediments been deposited prior to ca. 4.1 Ga. Instead, they exhibit μ142Nd identical to that measured in Isua BIF. Collectively, our results suggest that the 146Sm–142Nd array characterizing mafic lithologies of Ukaliq and Nuvvuagittuq is an inherited signature with doubtful chronological significance. We interpret the volcanic protoliths of the Innuksuac complex to have been produced by metasomatically triggered melting of a variably enriched Eoarchean mantle, following addition of felsic melts and/or fluids derived from a foundering Hadean mafic crust. Application of coupled 146,147Sm–142,143Nd chronometry to Ukaliq lavas yields a model age of differentiation of 4.36−0.06+0.05 Ga for this Hadean precursor. This is similar to late-stage crystallization ages inferred for the lunar and terrestrial magma oceans. The long-term preservation of Earth's primordial crust points to subdued lithospheric recycling in the post-magma ocean Earth.

Geochemistry and Nd isotopic characteristics of Earth's Hadean mantle and primitive crust

Abstract The Isua supracrustal belt (ISB) and the Nuvvuagittuq greenstone belt (NGB) are among the oldest suites of mafic volcanic rocks preserved on Earth and are the best candidates for representing its early crust. Despite the possible 500 Ma age difference between the belts, these mantle-derived rocks show compositional similarities, with features resembling rocks formed in subduction initiation environments. With the addition of new 142Nd data for the Garbenschiefer unit of the ISB reported here, high precision 142Nd data are now available for all the mafic lithologies from both belts. Mantle-derived rocks from both the ISB and NGB belts exhibit a range of 142Nd/144Nd ratios. The datasets for the two belts, however, are significantly different, suggesting a different origin for their 142Nd anomalies. Nearly all ISB samples have excesses in 142Nd, including the newly analyzed Garbenschiefer boninitic amphibolites (mean of + 12 ppm ). Excesses in 142Nd/144Nd compared to the Nd standard for all the ISB rocks range between +8 and + 20 ppm , with a near Gaussian distribution around + 12 ppm . This distribution could simply reflect the analytical error (±5 ppm) around a single 142Nd/144Nd ratio indicating that the samples formed after the extinction of 146Sm from a source with a nearly uniform 142Nd/144Nd ratio. In contrast, the NGB shows a range of 142Nd/144Nd ratios from +8 to − 18 ppm relative to the modern Nd standard and displays a flat distribution of 142Nd/144Nd ratios. The ISB samples show no significant correlation between their 142Nd/144Nd and Sm/Nd ratios, consistent with their formation in the Eoarchean via melting of a Hadean depleted mantle. In contrast, all NGB samples display a 142Nd/144Nd vs. Sm/Nd correlation, consistent with their crystallization in the Hadean. The mantle sources for both the ISB and NGB mantle-derived rocks have a similar 142Nd/144Nd ratio at the possible age of formation of the NGB (∼4.3 Ga) suggesting the derivation of ISB and NGB rocks from a common early-formed depleted mantle source formed between 4.47 and 4.42 Ga with a 147Sm/144Nd ratio ∼0.218. This mantle appears to have been an important source component involved in the formation of the primitive crust during most of the Hadean and Eoarchean eons.

Protocrustal evolution of the Nuvvuagittuq Supracrustal Belt as determined by high precision zircon Lu–Hf and U–Pb isotope data

The Nuvvuagittuq Supracrustal Belt (NSB) in northern Quebec, Canada, represents one of the oldest known crustal fragments preserved in the Earth's crust. Its age has, however, been disputed and different authors present crustal formation ages varying from ca. 3.8 Ga to 4.4 Ga (e.g. O'Neil et al., 2012; Guitreau et al., 2013). Here we report new high precision U–Pb geochronological and coupled Lu–Hf isotope data from zircons that reveal the age of the NSB and provide new constraints on the source rocks to this piece of early crust. Two rocks have been analysed, a felsic schist, interpreted to represent a volcanite, and a mylonitic tonalite that is intrusive into the NSB. The felsic schist was emplaced at 3771+5/−3 Ma, dating the formation of the NSB. The Lu–Hf model age indicates that the parental melt to the felsic schist was extracted from the mantle at this age or within a few tens of million years, but no more than 300 m.y., before its extrusion. This mantle extraction age provides an absolute maximum age for the NSB, but the most probable age of its protocrust is ca. 3.8 Ga. The mylonitic tonalite was emplaced at 3667+3/−1 Ma. Its Lu–Hf isotopic composition reveals the presence of an older crustal component than that of the NSB, requiring that its precursor melt formed from a Hadean source that was older than the NSB. Based on recent models for Archean TTG formation, we propose that this source represents re-melted Hadean hydrated crust that must have been translated below the NSB at ca. 3667 Ma.

Tungsten isotope composition of the Acasta Gneiss Complex

High-precision tungsten (182W/184W) isotope measurements on well-characterised mafic and felsic samples of the ca. 3960 Ma Acasta Gneiss Complex (AGC; Northwest Territories, Canada) show radiogenic ε182W values between +0.06 to +0.15. Two ca. 3600 Ma felsic samples from this terrane have ε182W ∼ 0 and are the oldest samples so far documented to have a W isotopic composition indistinguishable from that of the modern mantle. The ε182W data are correlated with ε142Nd (Roth et al., 2014) and we attribute this variability to incomplete metamorphic homogenisation of the 3960 Ma protolith with more recent material in a 3370 Ma tectono-thermal event. Notably, the value of the positive ε182W anomalies seen in the 3960 Ma AGC samples that are least affected by metamorphic homogenisation is comparable to that observed in other early Archean rocks (Isua Supracrustal Belt, Greenland; Nuvvuagittuq Supracrustal Belt, Canada) and the late Archean Kostomuksha komatiites (Karelia). This demonstrates a globally constant signature. We infer that the presence of a pre-late veneer mantle represents the most straightforward interpretation of a uniform distribution of εW182∼+0.15 value in Archean rocks of different ages. We show that such a notion is compatible with independent constraints from highly siderophile element abundances in mafic and ultra-mafic Archean mantle-derived rocks. The absence of anomalous ε182W and ε142Nd so far measured in samples younger than ca. 2800 Ma suggests progressive convective homogenisation of silicate reservoirs. The downward mixing of an upper mantle rich in late-delivered meteoritic material might account for these combined observations.

Atmospheric record in the Hadean Eon from multiple sulfur isotope measurements in Nuvvuagittuq Greenstone Belt (Nunavik, Quebec)

Mass-independent fractionation of sulfur isotopes (S-MIF) results from photochemical reactions involving short-wavelength UV light. The presence of these anomalies in Archean sediments [(4-2.5 billion years ago, (Ga)] implies that the early atmosphere was free of the appropriate UV absorbers, of which ozone is the most important in the modern atmosphere. Consequently, S-MIF is considered some of the strongest evidence for the lack of free atmospheric oxygen before 2.4 Ga. Although temporal variations in the S-MIF record are thought to depend on changes in the abundances of gas and aerosol species, our limited understanding of photochemical mechanisms complicates interpretation of the S-MIF record in terms of atmospheric composition. Multiple sulfur isotope compositions (δ(33)S, δ(34)S, and δ(36)S) of the >3.8 billion-year-old Nuvvuagittuq Greenstone Belt (Ungava peninsula) have been investigated to track the early origins of S-MIF. Anomalous S-isotope compositions (Δ(33)S up to +2.2‰) confirm a sedimentary origin of sulfide-bearing banded iron and silica-rich formations. Sharp isotopic transitions across sedimentary/igneous lithological boundaries indicate that primary surficial S-isotope compositions have been preserved despite a complicated metamorphic history. Furthermore, Nuvvuagittuq metasediments recorded coupled variations in (33)S/(32)S, (34)S/(32)S, and (36)S/(32)S that are statistically indistinguishable from those identified several times later in the Archean. The recurrence of the same S-isotope pattern at both ends of the Archean Eon is unexpected, given the complex atmospheric, geological, and biological pathways involved in producing and preserving this fractionation. It implies that, within 0.8 billion years of Earth's formation, a common mechanism for S-MIF production was established in the atmosphere.

New insights into the Hadean mantle revealed by 182W and highly siderophile element abundances of supracrustal rocks from the Nuvvuagittuq Greenstone Belt, Quebec, Canada

Tungsten concentration and isotopic data, coupled with highly siderophile element (HSE) concentration and Os isotopic data for ≥3.66billionyear-old ultramafic, mafic, and felsic supracrustal rocks from the Nuvvuagittuq Greenstone Belt, were investigated to place additional constraints on the nature and origin of 182W heterogeneities in the early Earth. The absolute and relative abundances of HSE in the mafic and ultramafic rocks are generally similar to those in modern rocks with comparable MgO contents. Further, most samples plot close to 3.8 to 4.4Ga reference lines on a 187Re–187Os isochron diagram, indicating that HSE abundances in most Nuvvuagittuq samples remained undisturbed by post-Eoarchean metamorphic events. All Nuvvuagittuq samples analyzed show well-resolved 182W excesses, ranging from +6 to +17ppm, compared with the modern isotopic composition of W. The observed level of HSE abundances, coupled with the 182W enrichments of these rocks is seemingly inconsistent with their derivation from mantle that was isolated from a HSE-rich and 182W-depleted late accretionary component. However, the absence of correlation between W and MgO contents, as well as variable W enrichment relative to elements with similar incompatibilities suggest that the W in the Nuvvuagittuq samples involved fluid transport of the W in either the crust or the mantle, and that it has little genetic relationship with the HSE. Given the lack of evidence for extensive redistribution of W in the crust, the HSE and W elemental and isotopic systematics of the Nuvvuagittuq rocks may be explained by a model whereby peridotitic mantle, with modern-like HSE abundances, was metasomatized by fluids derived from a 182W-rich crustal component that had been recycled into the mantle via subduction or delamination. The source of the 182W excess carried by this crustal component remains enigmatic. It was most likely inherited from either pre-late accretionary, or early-depleted parental mantle reservoirs.

Eoarchean to Neoarchean evolution of the Nuvvuagittuq Supracrustal belt: New insights from U-Pb zircon geochronology

The Nuvvuagittuq Supracrustal belt in northern Quebec is a rare ∼9 km2 fragment of the Earth9s early crust. The belt contains a metamorphosed volcano-sedimentary sequence that is at least Eoarchean in age, including amphibolites of the Ujaraaluk Unit that may have protoliths as ancient as 4400 million years old (Ma; O9Neil and others, 2012). Upper amphibolite facies metamorphism and high-strain deformation have obscured many primary field relationships and disturbed whole-rock isotope systematics, leading to debate over the interpretation of previous geochronological data. We report new SHRIMP U-Pb isotopic analyses of zircons from key meta-igneous and newly identified metasedimentary units of the belt. The analyzed samples fall into four categories: (a) felsic gneisses, including sheets interlayered with the supracrustal assemblage and a tonalitic orthogneiss at the margin of the belt; (b) a newly identified metasedimentary unit; (c) fuchsite-bearing quartz-rich layers; (d) mafic gneisses, including a garnet-biotite amphibolite from the Ujaraaluk Unit and a meta-gabbro. The felsic lithologies place constraints on the minimum age of the supracrustal assemblage; oscillatory-zoned zircons separated from a felsic orthogneiss sheet form a discordant array with an upper intercept age of 3774 ± 32 Ma, and the tonalitic orthogneiss yielded oscillatory zoned zircons with an upper intercept age of 3781 ± 11 Ma. A metasedimentary unit, dominated by quartz, albite and clinozoisite, has been identified within a lower strain domain, interfolded with amphibolites of the Ujaraaluk Unit. A sample of this unit yielded zircons with highly variable CL structures and near concordant ages of between 3390 and 3780 Ma. Zircons from a fuchsite-bearing quartz layer have oscillatory zonation similar to the orthogneiss grains, and define an upper intercept age of 3794 ± 16 Ma. Petrologic observations and geochemical data suggest that this lithology is a metasomatically altered felsic orthogneiss band, rather than a meta-sedimentary rock belonging to the supracrustal package. Electron microscopy of polished thin sections was used to locate zircons within 6 samples of the Ujaraaluk Unit amphibolites and two samples of meta-gabbro. Large (≤500 μm) zircons separated from a garnet-biotite amphibolite, together with grains from a meta-gabbro, are sector zoned and yield ages of 2700 to 2640 Ma, recording the timing of pervasive high-temperature metamorphism in the region. The new zircon U-Pb data add important new detail to the geological history of the Nuvvuagittuq belt. The volcano-sedimentary sequence and mafic-ultramafic intrusive rocks were formed prior to 3800 million years ago. Subsequent geological evolution included extensive and protracted early Archean TTG magmatism and crustal re-melting, Paleo- to Mesoarchean uplift and sedimentation and Neoarchean high-grade metamorphism and regional magmatism during consolidation of the Superior craton.