Earth's evolving geodynamic regime recorded by titanium isotopes.

Earth's mantle has a two-layered structure, with the upper and lower mantle domains separated by a seismic discontinuity at about 660 km (refs. 1,2). The extent of mass transfer between these mantle domains throughout Earth's history is, however, poorly understood. Continental crust extraction results in Ti-stable isotopic fractionation, producing isotopically light melting residues3-7. Mantle recycling of these components can impart Ti isotope variability that is trackable in deep time. We report ultrahigh-precision 49Ti/47Ti ratios for chondrites, ancient terrestrial mantle-derived lavas ranging from 3.8 to 2.0 billion years ago (Ga) and modern ocean island basalts (OIBs). Our new Ti bulk silicate Earth (BSE) estimate based on chondrites is 0.052 ± 0.006‰ heavier than the modern upper mantle sampled by normal mid-ocean ridge basalts (N-MORBs). The 49Ti/47Ti ratio of Earth's upper mantle was chondritic before 3.5 Ga and evolved to a N-MORB-like composition between approximately 3.5 and 2.7 Ga, establishing that more continental crust was extracted during this epoch. The +0.052 ± 0.006‰ offset between BSE and N-MORBs requires that <30% of Earth's mantle equilibrated with recycled crustal material, implying limited mass exchange between the upper and lower mantle and, therefore, preservation of a primordial lower-mantle reservoir for most of Earth's geologic history. Modern OIBs record variable 49Ti/47Ti ratios ranging from chondritic to N-MORBs compositions, indicating continuing disruption of Earth's primordial mantle. Thus, modern-style plate tectonics with high mass transfer between the upper and lower mantle only represents a recent feature of Earth's history.

Rapid shifting of a deep magmatic source at Fagradalsfjall volcano, Iceland.

Recent Icelandic rifting events have illuminated the roles of centralized crustal magma reservoirs and lateral magma transport1-4, important characteristics of mid-ocean ridge magmatism1,5. A consequence of such shallow crustal processing of magmas4,5 is the overprinting of signatures that trace the origin, evolution and transport of melts in the uppermost mantle and lowermost crust6,7. Here we present unique insights into processes occurring in this zone from integrated petrologic and geochemical studies of the 2021 Fagradalsfjall eruption on the Reykjanes Peninsula in Iceland. Geochemical analyses of basalts erupted during the first 50 days of the eruption, combined with associated gas emissions, reveal direct sourcing from a near-Moho magma storage zone. Geochemical proxies, which signify different mantle compositions and melting conditions, changed at a rate unparalleled for individual basaltic eruptions globally. Initially, the erupted lava was dominated by melts sourced from the shallowest mantle but over the following three weeks became increasingly dominated by magmas generated at a greater depth. This exceptionally rapid trend in erupted compositions provides an unprecedented temporal record of magma mixing that filters the mantle signal, consistent with processing in near-Moho melt lenses containing 107-108 m3 of basaltic magma. Exposing previously inaccessible parts of this key magma processing zone to near-real-time investigations provides new insights into the timescales and operational mode of basaltic magma systems.

On the relative temperatures of Earth's volcanic hotspots and mid-ocean ridges.

Volcanic hotspots are thought to be fed by hot, active upwellings from the deep mantle, with excess temperatures (Tex) ~100° to 300°C higher than those of mid-ocean ridges. However, Tex estimates are limited in geographical coverage and often inconsistent for individual hotspots. We infer the temperature of oceanic hotspots and ridges simultaneously by converting seismic velocity to temperature. We show that while ~45% of plume-fed hotspots are hot (Tex ≥ 155°C), ~15% are cold (Tex ≤ 36°C) and ~40% are not hot enough to actively upwell (50°C ≤ Tex ≤ 136°C). Hot hotspots have an extremely high helium-3/helium-4 ratio and buoyancy flux, but cold hotspots do not. The latter may originate at upper mantle depths. Alternatively, the deep plumes that feed them may be entrained and cooled by small-scale convection.

Extreme isotopic heterogeneity in Samoan clinopyroxenes constrains sediment recycling.

Lavas erupted at hotspot volcanoes provide evidence of mantle heterogeneity. Samoan Island lavas with high 87Sr/86Sr (>0.706) typify a mantle source incorporating ancient subducted sediments. To further characterize this source, we target a single high 87Sr/86Sr lava from Savai'i Island, Samoa for detailed analyses of 87Sr/86Sr and 143Nd/144Nd isotopes and major and trace elements on individual magmatic clinopyroxenes. We show the clinopyroxenes exhibit a remarkable range of 87Sr/86Sr-including the highest observed in an oceanic hotspot lava-encompassing ~30% of the oceanic mantle's total variability. These new isotopic data, data from other Samoan lavas, and magma mixing calculations are consistent with clinopyroxene 87Sr/86Sr variability resulting from magma mixing between a high silica, high 87Sr/86Sr (up to 0.7316) magma, and a low silica, low 87Sr/86Sr magma. Results provide insight into the composition of magmas derived from a sediment-infiltrated mantle source and document the fate of sediment recycled into Earth's mantle.

Remnants of early Earth differentiation in the deepest mantle-derived lavas.

The noble gas isotope systematics of ocean island basalts suggest the existence of primordial mantle signatures in the deep mantle. Yet, the isotopic compositions of lithophile elements (Sr, Nd, Hf) in these lavas require derivation from a mantle source that is geochemically depleted by melt extraction rather than primitive. Here, this apparent contradiction is resolved by employing a compilation of the Sr, Nd, and Hf isotope composition of kimberlites-volcanic rocks that originate at great depth beneath continents. This compilation includes kimberlites as old as 2.06 billion years and shows that kimberlites do not derive from a primitive mantle source but sample the same geochemically depleted component (where geochemical depletion refers to ancient melt extraction) common to most oceanic island basalts, previously called PREMA (prevalent mantle) or FOZO (focal zone). Extrapolation of the Nd and Hf isotopic compositions of the kimberlite source to the age of Earth formation yields a 143Nd/144Nd-176Hf/177Hf composition within error of chondrite meteorites, which include the likely parent bodies of Earth. This supports a hypothesis where the source of kimberlites and ocean island basalts contains a long-lived component that formed by melt extraction from a domain with chondritic 143Nd/144Nd and 176Hf/177Hf shortly after Earth accretion. The geographic distribution of kimberlites containing the PREMA component suggests that these remnants of early Earth differentiation are located in large seismically anomalous regions corresponding to thermochemical piles above the core-mantle boundary. PREMA could have been stored in these structures for most of Earth's history, partially shielded from convective homogenization.

Ancient helium and tungsten isotopic signatures preserved in mantle domains least modified by crustal recycling.

Rare high-3He/4He signatures in ocean island basalts (OIB) erupted at volcanic hotspots derive from deep-seated domains preserved in Earth's interior. Only high-3He/4He OIB exhibit anomalous 182W-an isotopic signature inherited during the earliest history of Earth-supporting an ancient origin of high 3He/4He. However, it is not understood why some OIB host anomalous 182W while others do not. We provide geochemical data for the highest-3He/4He lavas from Iceland (up to 42.9 times atmospheric) with anomalous 182W and examine how Sr-Nd-Hf-Pb isotopic variations-useful for tracing subducted, recycled crust-relate to high 3He/4He and anomalous 182W. These data, together with data on global OIB, show that the highest-3He/4He and the largest-magnitude 182W anomalies are found only in geochemically depleted mantle domains-with high 143Nd/144Nd and low 206Pb/204Pb-lacking strong signatures of recycled materials. In contrast, OIB with the strongest signatures associated with recycled materials have low 3He/4He and lack anomalous 182W. These observations provide important clues regarding the survival of the ancient He and W signatures in Earth's mantle. We show that high-3He/4He mantle domains with anomalous 182W have low W and 4He concentrations compared to recycled materials and are therefore highly susceptible to being overprinted with low 3He/4He and normal (not anomalous) 182W characteristic of subducted crust. Thus, high 3He/4He and anomalous 182W are preserved exclusively in mantle domains least modified by recycled crust. This model places the long-term preservation of ancient high 3He/4He and anomalous 182W in the geodynamic context of crustal subduction and recycling and informs on survival of other early-formed heterogeneities in Earth's interior.

Shipboard Characterization of Tuvalu, Samoa, and Lau Dredge Samples Using Laser-Induced Breakdown Spectroscopy (LIBS).

Chemical analysis using laser-induced breakdown spectroscopy (LIBS) is well suited for field applications and was applied here for shipboard characterization of a large sample set during the RR1310 rock dredging expedition to the Tuvalu Seamounts. Although recently the most common data treatment for LIBS has consisted of a partial least squares approach to define sample groupings, we show that quantitative data of useful quality can be obtained with a univariate approach. Here, our analysis goal was a quantitative comparison of the total alkali (Na2O + K2O) versus silica (SiO2) contents of 586 representative dredge samples with known ranges in common rock types. Out of those samples, >400 form a single large group of alkalic basalts with minor basanites/tephrites (SiO2: 43-48 wt%, Na2O + K2O: 3-5 wt%), similar to known shield-stage compositions of the Rurutu and Samoa hotspots in the sampling area. In contrast, several dredge hauls contain samples with compositions that do not overlap with the majority of samples. This includes three dredges performed on the northern boundary of the Lau Basin that contain similar SiO2 compositions, but slightly higher total alkali (Na2O+K2O) content. Despite this difference, they classify as basanite/tephrite, similar to a subset of the main group. More importantly, similar compositions were previously reported from the same tectonic boundary, ascribed to hotspot mantle source material mixed into the Lau Basin back-arc. Although the quality of the compositional data suffices to enable sample selection for time-intensive analyses, higher precision is required for more in-depth petrogenetic interpretation. Error analysis based on repeat standard measurements suggests averaging 100 spectra per sample is optimal here, while use of a higher resolution spectrometer, together with better laser control, would improve results and interpretations.

On the relative motions of long-lived Pacific mantle plumes.

Mantle plumes upwelling beneath moving tectonic plates generate age-progressive chains of volcanos (hotspot chains) used to reconstruct plate motion. However, these hotspots appear to move relative to each other, implying that plumes are not laterally fixed. The lack of age constraints on long-lived, coeval hotspot chains hinders attempts to reconstruct plate motion and quantify relative plume motions. Here we provide 40Ar/39Ar ages for a newly identified long-lived mantle plume, which formed the Rurutu hotspot chain. By comparing the inter-hotspot distances between three Pacific hotspots, we show that Hawaii is unique in its strong, rapid southward motion from 60 to 50 Myrs ago, consistent with paleomagnetic observations. Conversely, the Rurutu and Louisville chains show little motion. Current geodynamic plume motion models can reproduce the first-order motions for these plumes, but only when each plume is rooted in the lowermost mantle.

Tungsten-182 heterogeneity in modern ocean island basalts.

New tungsten isotope data for modern ocean island basalts (OIB) from Hawaii, Samoa, and Iceland reveal variable 182W/184W, ranging from that of the ambient upper mantle to ratios as much as 18 parts per million lower. The tungsten isotopic data negatively correlate with 3He/4He. These data indicate that each OIB system accesses domains within Earth that formed within the first 60 million years of solar system history. Combined isotopic and chemical characteristics projected for these ancient domains indicate that they contain metal and are repositories of noble gases. We suggest that the most likely source candidates are mega-ultralow-velocity zones, which lie beneath Hawaii, Samoa, and Iceland but not beneath hot spots whose OIB yield normal 182W and homogeneously low 3He/4He.

Preservation of Earth-forming events in the tungsten isotopic composition of modern flood basalts.

How much of Earth's compositional variation dates to processes that occurred during planet formation remains an unanswered question. High-precision tungsten isotopic data from rocks from two large igneous provinces, the North Atlantic Igneous Province and the Ontong Java Plateau, reveal preservation to the Phanerozoic of tungsten isotopic heterogeneities in the mantle. These heterogeneities, caused by the decay of hafnium-182 in mantle domains with high hafnium/tungsten ratios, were created during the first ~50 million years of solar system history, indicating that portions of the mantle that formed during Earth's primary accretionary period have survived to the present.

Anionic chemistry of noble gases: formation of Mg-NG (NG = Xe, Kr, Ar) compounds under pressure.

While often considered to be chemically inert, the reactivity of noble gas elements at elevated pressures is an important aspect of fundamental chemistry. The discovery of Xe oxidation transformed the doctrinal boundary of chemistry by showing that a complete electron shell is not inert to reaction. However, the reductive propensity, i.e., gaining electrons and forming anions, has not been proposed or examined for noble gas elements. In this work, we demonstrate, using first-principles electronic structure calculations coupled to an efficient structure prediction method, that Xe, Kr, and Ar can form thermodynamically stable compounds with Mg at high pressure (≥125, ≥250, and ≥250 GPa, respectively). The resulting compounds are metallic and the noble gas atoms are negatively charged, suggesting that chemical species with a completely filled shell can gain electrons, filling their outermost shell(s). Moreover, this work indicates that Mg2NG (NG = Xe, Kr, Ar) are high-pressure electrides with some of the electrons localized at interstitial sites enclosed by the surrounding atoms. Previous predictions showed that such electrides only form in Mg and its compounds at very high pressures (>500 GPa). These calculations also demonstrate strong chemical interactions between the Xe 5d orbitals and the quantized interstitial quasiatom (ISQ) orbitals, including the strong chemical bonding and electron transfer, revealing the chemical nature of the ISQ.

Anomalous sulphur isotopes in plume lavas reveal deep mantle storage of Archaean crust.

Basaltic lavas erupted at some oceanic intraplate hotspot volcanoes are thought to sample ancient subducted crustal materials. However, the residence time of these subducted materials in the mantle is uncertain and model-dependent, and compelling evidence for their return to the surface in regions of mantle upwelling beneath hotspots is lacking. Here we report anomalous sulphur isotope signatures indicating mass-independent fractionation (MIF) in olivine-hosted sulphides from 20-million-year-old ocean island basalts from Mangaia, Cook Islands (Polynesia), which have been suggested to sample recycled oceanic crust. Terrestrial MIF sulphur isotope signatures (in which the amount of fractionation does not scale in proportion with the difference in the masses of the isotopes) were generated exclusively through atmospheric photochemical reactions until about 2.45 billion years ago. Therefore, the discovery of MIF sulphur in these young plume lavas suggests that sulphur--probably derived from hydrothermally altered oceanic crust--was subducted into the mantle before 2.45 billion years ago and recycled into the mantle source of Mangaia lavas. These new data provide evidence for ancient materials, with negative Δ(33)S values, in the mantle source for Mangaia lavas. Our data also complement evidence for recycling of the sulphur content of ancient sedimentary materials to the subcontinental lithospheric mantle that has been identified in diamond-hosted sulphide inclusions. This Archaean age for recycled oceanic crust also provides key constraints on the length of time that subducted crustal material can survive in the mantle, and on the timescales of mantle convection from subduction to upwelling beneath hotspots.

Nickel and helium evidence for melt above the core-mantle boundary.

High (3)He/(4)He ratios in some basalts have generally been interpreted as originating in an incompletely degassed lower-mantle source. This helium source may have been isolated at the core-mantle boundary region since Earth's accretion. Alternatively, it may have taken part in whole-mantle convection and crust production over the age of the Earth; if so, it is now either a primitive refugium at the core-mantle boundary or is distributed throughout the lower mantle. Here we constrain the problem using lavas from Baffin Island, West Greenland, the Ontong Java Plateau, Isla Gorgona and Fernandina (Galapagos). Olivine phenocryst compositions show that these lavas originated from a peridotite source that was about 20 per cent higher in nickel content than in the modern mid-ocean-ridge basalt source. Where data are available, these lavas also have high (3)He/(4)He. We propose that a less-degassed nickel-rich source formed by core-mantle interaction during the crystallization of a melt-rich layer or basal magma ocean, and that this source continues to be sampled by mantle plumes. The spatial distribution of this source may be constrained by nickel partitioning experiments at the pressures of the core-mantle boundary.

An ancient recipe for flood-basalt genesis.

Large outpourings of basaltic lava have punctuated geological time, but the mechanisms responsible for the generation of such extraordinary volumes of melt are not well known. Recent geochemical evidence suggests that an early-formed reservoir may have survived in the Earth's mantle for about 4.5 billion years (ref. 2), and melts of this reservoir contributed to the flood basalt emplaced on Baffin Island about 60 million years ago. However, the volume of this ancient mantle domain and whether it has contributed to other flood basalts is not known. Here we show that basalts from the largest volcanic event in geologic history--the Ontong Java plateau--also exhibit the isotopic and trace element signatures proposed for the early-Earth reservoir. Together with the Ontong Java plateau, we suggest that six of the largest volcanic events that erupted in the past 250 million years derive from the oldest terrestrial mantle reservoir. The association of these large volcanic events with an ancient primitive mantle source suggests that its unique geochemical characteristics--it is both hotter (it has greater abundances of the radioactive heat-producing elements) and more fertile than depleted mantle reservoirs-may strongly affect the generation of flood basalts.

Evidence for the survival of the oldest terrestrial mantle reservoir.

Helium is a powerful tracer of primitive material in Earth's mantle. Extremely high (3)He/(4)He ratios in some ocean-island basalts suggest the presence of relatively undegassed and undifferentiated material preserved in Earth's mantle. However, terrestrial lavas with high (3)He/(4)He ratios have never been observed to host the primitive lead-isotopic compositions that are required for an early (roughly 4.5 Gyr ago) formation age. Here we show that Cenozoic-era Baffin Island and West Greenland lavas, previously found to host the highest terrestrial-mantle (3)He/(4)He ratios, exhibit primitive lead-isotope ratios that are consistent with an ancient mantle source age of 4.55-4.45 Gyr. The Baffin Island and West Greenland lavas also exhibit (143)Nd/(144)Nd ratios similar to values recently proposed for an early-formed (roughly 4.5 Gyr ago) terrestrial mantle reservoir. The combined helium-, lead- and Nd-isotopic compositions in Baffin Island and West Greenland lavas therefore suggest that their source is the most ancient accessible reservoir in the Earth's mantle, and it may be parental to all mantle reservoirs that give rise to modern volcanism.

The return of subducted continental crust in Samoan lavas.

Substantial quantities of terrigenous sediments are known to enter the mantle at subduction zones, but little is known about their fate in the mantle. Subducted sediment may be entrained in buoyantly upwelling plumes and returned to the Earth's surface at hotspots, but the proportion of recycled sediment in the mantle is small, and clear examples of recycled sediment in hotspot lavas are rare. Here we report remarkably enriched 87Sr/86Sr and 143Nd/144Nd isotope signatures in Samoan lavas from three dredge locations on the underwater flanks of Savai'i island, Western Samoa. The submarine Savai'i lavas represent the most extreme 87Sr/86Sr isotope compositions reported for ocean island basalts to date. The data are consistent with the presence of a recycled sediment component (with a composition similar to the upper continental crust) in the Samoan mantle. Trace-element data show affinities similar to those of the upper continental crust--including exceptionally low Ce/Pb and Nb/U ratios--that complement the enriched 87Sr/86Sr and 143Nd/144Nd isotope signatures. The geochemical evidence from these Samoan lavas significantly redefines the composition of the EM2 (enriched mantle 2; ref. 9) mantle endmember, and points to the presence of an ancient recycled upper continental crust component in the Samoan mantle plume.