Widespread tungsten isotope anomalies and W mobility in crustal and mantle rocks of the Eoarchean Saglek Block, northern Labrador, Canada: Implications for early Earth processes and W recycling

Well-resolved 182W isotope anomalies, relative to the present mantle, in Hadean–Archean terrestrial rocks have been interpreted to reflect the effects of variable late accretion and early mantle differentiation processes. To further explore these early Earth processes, we have carried out W concentration and isotopic measurements of Eoarchean ultramafic rocks, including lithospheric mantle rocks, meta-komatiites, a layered ultramafic body and associated crustal gneisses and amphibolites from the Uivak gneiss terrane of the Saglek Block, northern Labrador, Canada. These analyses are augmented by in situ W concentration measurements of individual phases in order to examine the major hosts of W in these rocks. Although the W budget in some rocks can be largely explained by a combination of their major phases, W in other rocks is hosted mainly in secondary grain-boundary assemblages, as well as in cryptic, unidentified W-bearing ‘nugget’ minerals. Whole rock W concentrations in the ultramafic rocks show unexpected enrichments relative, to elements with similar incompatibilities. By contrast, W concentrations are low in the Uivak gneisses. These data, along with the in situ W concentration data, suggest metamorphic transport/re-distribution of W from the regional felsic rocks, the Uivak gneiss precursors, to the spatially associated ultramafic rocks. All but one sample from the lithologically varied Eoarchean Saglek suite is characterized by generally uniform enrichments in 182W relative to Earth's modern mantle. Modeling shows that the W isotopic enrichments in the ultramafic rocks were primarily inherited from the surrounding 182W-rich felsic precursor rocks, and that the W isotopic composition of the original ultramafic rocks cannot be determined. The observed W isotopic composition of mafic to ultramafic rocks in intimate contact with ancient crust should be viewed with caution in order to plate constraints on the early Hf–W isotopic evolution of the Earth's mantle with regard to late accretionary processes. Although 182W anomalies can be erased via mixing in the convective mantle, recycling of 182W-rich crustal rocks into the mantle can produce new mantle sources with anomalous W isotopic compositions that can be tapped at much later times and, hence, this process should be considered as a mechanism for the generation of 182W-rich rocks at any subsequent time in Earth history.The NSERC Discovery Grants program to DGP U.S. NSF-CSEDI grant EAR1265169 (to RJW)

Tracing the metasomatic and magmatic evolution of continental mantle roots with Sr, Nd, Hf and Pb isotopes : a case study of Middle Atlas (Morocco) peridotite xenoliths

We studied clinopyroxenes from spinel-facies peridotite xenoliths sampled by the Quaternary intra-plate volcanism of the Middle Atlas (Morocco) and present new trace element and Sr–Nd–Hf isotope data. However, we focus in particular on Pb isotope data and 238U/204Pb and 232Th/204Pb ratios of these clinopyroxenes. This data allows us to investigate: (a) the timing of metasomatic events, (b) the prevalence and persistence of elevated 238U/204Pb, 232Th/238U and 232Th/204Pb in continental mantle roots and (c) the 238U/204Pb and 232Th/204Pb composition of putative basaltic melts generated from such metasomatised sub-continental lithospheric mantle (SCLM). Incompatible trace element concentrations in these clinopyroxenes are elevated, marked by high-field strength element depletion and fractionated elemental ratios (e.g., U/Nb, Zr/Hf) most consistent with enrichment due to carbonatitic liquids. Sr, Nd and Hf isotopes have an affinity to HIMU. U, Th and Pb abundances in the clinopyroxenes generally exceed estimates of primitive mantle clinopyroxene. Pb isotope compositions of these clinopyroxenes are radiogenic and vary between 206Pb/204Pb = 19.93–20.25, 207Pb/204Pb = 15.63–15.66 and 208Pb/204Pb = 39.72–40.23. These Pb isotope systematics result in generally negative Δ7/4 but positive Δ8/4; setting these samples distinctly apart from typical HIMU. These Pb isotope compositions are also distinct from the associated host volcanic rocks. 238U/204Pb and 232Th/204Pb of these clinopyroxenes, which range from 26 to 81 and 136 to 399, respectively, are elevated and more extreme than estimates of MORB- and HIMU-source mantle. The Pb isotope evolution of the clinopyroxenes suggests that the metasomatic enrichment is younger than 200 Ma, which discounts the volcanic activity due to the opening of the Atlantic and the onset of the collision of the African and Eurasian plates as processes generating the lithophile element and isotope composition of this continental mantle root. Instead, the enrichment is thought to be associated with the Quaternary intra-plate volcanism in the Middle Atlas. However, the erupted mafic melts have unradiogenic Pb isotopes and lower 238U/204Pb, 232Th/204Pb and 232Th/238U relative to the clinopyroxene and do not seem to have equilibrated with the clinopyroxenes. The high Th abundances and the high 232Th/238U also suggest that the metasomatism was due to carbonatitic liquids. When literature data for Pb isotopes in mantle minerals are considered, the Pb isotope range of Archean, Proterozoic and Phanerozoic continental mantle roots is remarkable in that they are similar to the convecting mantle. This observation does not support the existence of sub-continental lithospheric mantle with high 238U/204Pb and 232Th/204Pb for long periods of time. Consequently, the narrow range of Pb isotopes in SCLM worldwide suggests that only the youngest metasomatic events are recorded by incompatible elements such as U, Th and Pb. Numerical modelling of putative magmas generated from Middle Atlas SCLM by fractional, non-modal melting calculations yield extremely high 238U/204Pb and 232Th/204Pb ratios. For example, pure SCLM magmas generated from 0.5% to 10% melting are anticipated to have 232Th/204Pb ratios exceeding those known from terrestrial basalts

A major element, PGE and Re-Os isotope study of Middle Atlas (Morocco) peridotite xenoliths : evidence for coupled introduction of metasomatic sulphides and clinopyroxene

We present major element and PGE (platinum-group-element) abundances in addition to Re–Os isotope data for 11 spinel-facies whole rock peridotites from a single maar from the Middle Atlas Mountains, Morocco. Major element systematics of these xenoliths are generally correlated with indices of depletion. FeO–MgO systematics appear to suggest spinel-facies melting in the range of 5 to 25%. However, Al2O3 abundances in these xenoliths appear elevated relative to primitive mantle (Prima). The Al2O3 abundances in conjunction with other major elements require distinct re-enrichment of the Middle Atlas continental mantle root due to melt/rock reaction and precipitation of amphibole and/or clinopyroxene from passing silicate melts akin to MORB or OIB that evolved in reverse direction along the melting curves in e.g. FeO–MgO space. Sc and V confirm the range of apparent depletion and also indicate that the currently preserved fO2 in these peridotites is distinctly different from fO2 conditions observed in subduction zones. The majority of these xenoliths have low Os and Ir (I-PGEs) concentrations relative to Prima and modelled sulphide- and clinopyroxene-depleted residues of mantle melting under low fO2, mid-ocean ridge-like conditions. Moreover, Pt and Pd (P-PGE) abundances are elevated when compared to their expected abundances after substantial melt extraction. Importantly, the systematically low Ir abundances in the majority of samples show well-correlated trends with Al2O3, MgO and Cu that are inconsistent with established melting trends. Os isotopes in the Middle Atlas xenoliths range from 187Os/188Os = 0.11604 to 0.12664 although most samples are close to chondritic. The Os isotope ratios are decoupled from 187Re/188Os but, together with Re abundances, also exhibit a good correlation with Al2O3, MgO and Cu. The major element, I-PGE and Os isotope correlations suggest that the initial melt depletion led to the exhaustion of sulphide and clinopyroxene (20 to 30%) without significant stabilization of I-PGE-rich alloys. During later modal metasomatism of the refractory Middle Atlas continental mantle root with silicate melts akin to MORB or OIB the introduction of clinopyroxene/amphibole reduced the volume of the melt inducing sulphur saturation in these melts causing precipitation of secondary sulphides. This coupled crystallization of pyroxenes and sulphides (chalcopyrite) resulted in the two-component mixing systematics exhibited by I-PGEs, Os isotopes with major elements and Cu preserved in the Middle Atlas continental mantle root

Mineral inclusions in diamonds from Karowe Mine, Botswana: super-deep sources for super-sized diamonds?

Mineral inclusions in diamonds play a critical role in constraining the relationship between diamonds and mantle lithologies. Here we report the first major and trace element study of mineral inclusions in diamonds from the Karowe Mine in north-east Botswana, along the western edge of the Zimbabwe Craton. From a total of 107 diamonds, 134 silicate, 15 oxide, and 22 sulphide inclusions were recovered. The results reveal that 53% of Karowe inclusion-bearing diamonds derived from eclogitic sources, 44% are peridotitic, 2% have a sublithospheric origin, and 1% are websteritic. The dominant eclogitic diamond substrates sampled at Karowe are compositionally heterogeneous, as reflected in wide ranges in the CaO contents (4–16 wt%) of garnets and the Mg# (69–92) and jadeite contents (14–48 mol%) of clinopyroxenes. Calculated bulk rock REEN patterns indicate that both shallow and deep levels of the subducted slab(s) were sampled, including cumulate-like protoliths. Peridotitic garnet compositions largely derive from harzburgite/dunite substrates (~90%), with almost half the garnets having CaO contents <1.8 wt%, consistent with pyroxene-free (dunitic) sources. The highly depleted character of the peridotitic diamond substrates is further documented by the high mean and median Mg# (93.1) of olivine inclusions. One low-Ca garnet records a very high Cr2O3 content (14.7 wt%), implying that highly depleted cratonic lithosphere at the time of diamond formation extended to at least 220 km depth. Inclusion geothermobarometry indicates that the formation of peridotitic diamonds occurred along a 39–40 mW/m2 model geotherm. A sublithospheric inclusion suite is established by three eclogitic garnets containing a majorite component, a feature so far unique within the Orapa cluster. These low- and high-Ca majoritic garnets follow pyroxenitic and eclogitic trends of majoritic substitution, respectively. The origin of the majorite-bearing diamonds is estimated to be between 330 to 420 km depth, straddling the asthenosphere–transition zone boundary. This new observation of superdeep mineral inclusions in Karowe diamonds is consistent with a sublithospheric origin for the exceptionally large diamonds from this mine

An oxygen isotope test for the origin of Archean mantle roots

The origin of the peridotites that form cratonic mantle roots is a central issue in understanding the history and survival of Earth’s oldest continents. A long-standing hypothesis holds that the unusual bulk compositions of some cratonic peridotites stem from their origin as subducted oceanic serpentinite, dehydrated during subduction to form rigid buoyant keels (Schulze, 1986; Canil and Lee, 2009). We present oxygen isotope data from 93 mantle peridotites from five different Archean cratons to evaluate their possible origin as serpentinites. Cratonic mantle peridotite shows remarkably uniform δ18O values, identical to modern MORB-source mantle, that do not vary with bulk rock Si-enrichment or Ca-depletion. These data clearly conflict with any model for cratonic lithosphere that invokes serpentinite as a protolith for cratonic peridotite, and place additional constraints on cratonic mantle origins. We posit that the uniform δ18O was produced by sub-arc and/or MOR depletion processes and that the Si-enriched nature of some samples is unlikely to be related to slab melt infiltration. Instead, we suggest a peridotitic source of Si-enrichment, derived from ascending mantle melts, or a water-fluxed depleted mantle. These variably Si-enriched, cratonic mantle protoliths were then collisionally compressed into the thick cratonic roots that have protected Earth’s oldest continental crust for over 2.5 Gyr

Early Eocene Arctic volcanism from carbonate-metasomatized mantle

Melilitite, nephelinite, basanite, and alkali basalt, along with phonolite differentiates, form the Freemans Cove Complex (FCC) in the south-eastern extremity of Bathurst Island (Nunavut, Canada). New 40Ar/39Ar chronology indicates their emplacement between ~ 56 and ~ 54 million years ago within a localized extensional structure. Melilitites and nephelinites, along with phonolite differentiates, likely relate to the beginning and end phases of extension, whereas alkali basalts were emplaced during a main extensional episode at ~ 55 Ma. The melilitites, nephelinites, and alkali basalts show no strong evidence for significant assimilation of crust, in contrast to some phonolites. Partial melting occurred within both the garnet- and spinel-facies mantle and sampled sources with He, O, Nd, Hf, and Os isotope characteristics indicative of peridotite with two distinct components. The first, expressed in higher degree partial melts, represents a relatively depleted component (“A”; 3He/4He ~ 8 RA, εNdi ~ + 3 εHfi ~ + 7, γOsi ~ 0). The second was an enriched component (“B” 3He/4He + 70) sampled by the lowest degree partial melts and represents carbonate-metasomatized peridotite. Magmatism in the FCC shows that rifting extended from the Labrador Sea to Bathurst Island and reached a zenith at ~ 55 Ma, during the Eurekan orogeny. The incompatible trace-element abundances and isotopic signatures of FCC rocks indicate melt generation occurred at the base of relatively thin lithosphere at the margin of a thick craton, with no mantle plume influence. FCC melt compositions are distinct from other continental rift magmatic provinces worldwide, and their metasomatized mantle source was plausibly formed synchronously with emplacement of Cretaceous kimberlites. The FCC illustrates that the range of isotopic compositions preserved in continental rift magmas are likely to be dominated by temporal changes in the extent of partial melting, as well as by the timing and degree of metasomatism recorded in the underlying continental lithosphere

Comment on “Discovery of davemaoite, CaSiO₃-perovskite, as a mineral from the lower mantle”

Tschauner et al. (Reports, 11 November 2021, p. 891) present evidence that diamond GRR-1507 formed in the lower mantle. Instead, the data support a much shallower origin in cold, subcratonic lithospheric mantle. X-ray diffraction data are well matched to phases common in microinclusion-bearing lithospheric diamonds. The calculated bulk inclusion composition is too imprecise to uniquely confirm CaSiO₃ stoichiometry and is equally consistent with inclusions observed in other lithospheric diamonds

Fingerprinting the Cretaceous-Paleogene boundary impact with Zn isotopes

Numerous geochemical anomalies exist at the K-Pg boundary that indicate the addition of extraterrestrial materials; however, none fingerprint volatilization, a key process that occurs during large bolide impacts. Stable Zn isotopes are an exceptional indicator of volatility-related processes, where partial vaporization of Zn leaves the residuum enriched in its heavy isotopes. Here, we present Zn isotope data for sedimentary rock layers of the K-Pg boundary, which display heavier Zn isotope compositions and lower Zn concentrations relative to surrounding sedimentary rocks, the carbonate platform at the impact site, and most carbonaceous chondrites. Neither volcanic events nor secondary alteration during weathering and diagenesis can explain the Zn concentration and isotope signatures present. The systematically higher Zn isotope values within the boundary layer sediments provide an isotopic fingerprint of partially evaporated material within the K-Pg boundary layer, thus earmarking Zn volatilization during impact and subsequent ejecta transport associated with an impact at the K-Pg