Deep-mantle krypton reveals Earth's early accretion of carbonaceous matter.

Establishing when, and from where, carbon, nitrogen and water were delivered to Earth is a fundamental objective in understanding the origin of habitable planets such as Earth. Yet, volatile delivery to Earth remains controversial1-5. Krypton isotopes provide insights on volatile delivery owing to their substantial isotopic variations among sources6-10, although pervasive atmospheric contamination has hampered analytical efforts. Here we present the full suite of krypton isotopes from the deep mantle of the Galápagos and Iceland plumes, which have the most primitive helium, neon and tungsten isotopic compositions11-16. Except for 86Kr, the krypton isotopic compositions are similar to a mixture of chondritic and atmospheric krypton. These results suggest early accretion of carbonaceous material by proto-Earth and rule out any combination of hydrodynamic loss with outgassing of the deep or shallow mantle to explain atmospheric noble gases. Unexpectedly, the deep-mantle sources have a deficit in the neutron-rich 86Kr relative to the average composition of carbonaceous meteorites, which suggests a nucleosynthetic anomaly. Although the relative depletion of neutron-rich isotopes on Earth compared with carbonaceous meteorites has been documented for a range of refractory elements1,17,18, our observations suggest such a depletion for a volatile element. This finding indicates that accretion of volatile and refractory elements occurred simultaneously, with krypton recording concomitant accretion of non-solar volatiles from more than one type of material, possibly including outer Solar System planetesimals.

Capture of nebular gases during Earth's accretion is preserved in deep-mantle neon.

Evidence for the capture of nebular gases by planetary interiors would place important constraints on models of planet formation. These constraints include accretion timescales, thermal evolution, volatile compositions and planetary redox states1-7. Retention of nebular gases by planetary interiors also constrains the dynamics of outgassing and volatile loss associated with the assembly and ensuing evolution of terrestrial planets. But evidence for such gases in Earth's interior remains controversial8-14. The ratio of the two primordial neon isotopes, 20Ne/22Ne, is significantly different for the three potential sources of Earth's volatiles: nebular gas15, solar-wind-irradiated material16 and CI chondrites17. Therefore, the 20Ne/22Ne ratio is a powerful tool for assessing the source of volatiles in Earth's interior. Here we present neon isotope measurements from deep mantle plumes that reveal 20Ne/22Ne ratios of up to 13.03 ± 0.04 (2 standard deviations). These ratios are demonstrably higher than those for solar-wind-irradiated material and CI chondrites, requiring the presence of nebular neon in the deep mantle. Furthermore, we determine a 20Ne/22Ne ratio for the primordial plume mantle of 13.23 ± 0.22 (2 standard deviations), which is indistinguishable from the nebular ratio, providing robust evidence for a reservoir of nebular gas preserved in the deep mantle today. The acquisition of nebular gases requires planetary embryos to grow to sufficiently large mass before the dissipation of the protoplanetary disk. Our observations also indicate distinct 20Ne/22Ne ratios between deep mantle plumes and mid-ocean-ridge basalts, which is best explained by addition of a chondritic component to the shallower mantle during the main phase of Earth's accretion and by subsequent recycling of seawater-derived neon in plate tectonic processes.

Publisher Correction: Xenon isotopic constraints on the history of volatile recycling into the mantle.

In this Letter, owing to a production error, the arrows in the middle panel of Fig. 1 were wrongly coloured and there were some some typos elsewhere. These errors have been corrected online.

Xenon isotopic constraints on the history of volatile recycling into the mantle.

The long-term exchange of volatile species (such as water, carbon, nitrogen and the noble gases) between deep Earth and surface reservoirs controls the habitability of the Earth's surface. The present-day volatile budget of the mantle reflects the integrated history of outgassing and retention of primordial volatiles delivered to the planet during accretion, volatile species generated by radiogenic ingrowth and volatiles transported into the mantle from surface reservoirs over time. Variations in the distribution of volatiles between deep Earth and surface reservoirs affect the viscosity, cooling rate and convective stress state of the solid Earth. Accordingly, constraints on the flux of surface volatiles transported into the deep Earth improve our understanding of mantle convection and plate tectonics. However, the history of surface volatile regassing into the mantle is not known. Here we use mantle xenon isotope systematics to constrain the age of initiation of volatile regassing into the deep Earth. Given evidence of prolonged evolution of the xenon isotopic composition of the atmosphere1,2, we find that substantial recycling of atmospheric xenon into the deep Earth could not have occurred before 2.5 billion years ago. Xenon concentrations in downwellings remained low relative to ambient convecting mantle concentrations throughout the Archaean era, and the mantle shifted from a net degassing to a net regassing regime after 2.5 billion years ago. Because xenon is carried into the Earth's interior in hydrous mineral phases3-5, our results indicate that downwellings were drier in the Archaean era relative to the present. Progressive drying of the Archean mantle would allow slower convection and decreased heat transport out of the mantle, suggesting non-monotonic thermal evolution of the Earth's interior.

Early differentiation and volatile accretion recorded in deep-mantle neon and xenon.

The isotopes (129)Xe, produced from the radioactive decay of extinct (129)I, and (136)Xe, produced from extinct (244)Pu and extant (238)U, have provided important constraints on early mantle outgassing and volatile loss from Earth. The low ratios of radiogenic to non-radiogenic xenon ((129)Xe/(130)Xe) in ocean island basalts (OIBs) compared with mid-ocean-ridge basalts (MORBs) have been used as evidence for the existence of a relatively undegassed primitive deep-mantle reservoir. However, the low (129)Xe/(130)Xe ratios in OIBs have also been attributed to mixing between subducted atmospheric Xe and MORB Xe, which obviates the need for a less degassed deep-mantle reservoir. Here I present new noble gas (He, Ne, Ar, Xe) measurements from an Icelandic OIB that reveal differences in elemental abundances and (20)Ne/(22)Ne ratios between the Iceland mantle plume and the MORB source. These observations show that the lower (129)Xe/(130)Xe ratios in OIBs are due to a lower I/Xe ratio in the OIB mantle source and cannot be explained solely by mixing atmospheric Xe with MORB-type Xe. Because (129)I became extinct about 100 million years after the formation of the Solar System, OIB and MORB mantle sources must have differentiated by 4.45 billion years ago and subsequent mixing must have been limited. The Iceland plume source also has a higher proportion of Pu- to U-derived fission Xe, requiring the plume source to be less degassed than MORBs, a conclusion that is independent of noble gas concentrations and the partitioning behaviour of the noble gases with respect to their radiogenic parents. Overall, these results show that Earth's mantle accreted volatiles from at least two separate sources and that neither the Moon-forming impact nor 4.45 billion years of mantle convection has erased the signature of Earth's heterogeneous accretion and early differentiation.

147Sm-143Nd systematics of Earth are inconsistent with a superchondritic Sm/Nd ratio.

The relationship between the compositions of the Earth and chondritic meteorites is at the center of many important debates. A basic assumption in most models for the Earth's composition is that the refractory elements are present in chondritic proportions relative to each other. This assumption is now challenged by recent (142)Nd/(144)Nd ratio studies suggesting that the bulk silicate Earth (BSE) might have an Sm/Nd ratio 6% higher than chondrites (i.e., the BSE is superchondritic). This has led to the proposal that the present-day (143)Nd/(144)Nd ratio of BSE is similar to that of some deep mantle plumes rather than chondrites. Our reexamination of the long-lived (147)Sm-(143)Nd isotope systematics of the depleted mantle and the continental crust shows that the BSE, reconstructed using the depleted mantle and continental crust, has (143)Nd/(144)Nd and Sm/Nd ratios close to chondritic values. The small difference in the ratio of (142)Nd/(144)Nd between ordinary chondrites and the Earth must be due to a process different from mantle-crust differentiation, such as incomplete mixing of distinct nucleosynthetic components in the solar nebula.

Preserving noble gases in a convecting mantle.

High (3)He/(4)He ratios sampled at many ocean islands are usually attributed to an essentially undegassed lower-mantle reservoir with high (3)He concentrations. A large and mostly undegassed mantle reservoir is also required to balance the Earth's (40)Ar budget, because only half of the (40)Ar produced from the radioactive decay of (40)K is accounted for by the atmosphere and upper mantle. However, geophysical and geochemical observations suggest slab subduction into the lower mantle, implying that most or all of Earth's mantle should have been processed by partial melting beneath mid-ocean ridges and hotspot volcanoes. This should have left noble gases in both the upper and the lower mantle extensively outgassed, contrary to expectations from (3)He/(4)He ratios and the Earth's (40)Ar budget. Here we suggest a simple solution: recycling and mixing of noble-gas-depleted slabs dilutes the concentrations of noble gases in the mantle, thereby decreasing the rate of mantle degassing and leaving significant amounts of noble gases in the processed mantle. As a result, even when the mass flux across the 660-km seismic discontinuity is equivalent to approximately one lower-mantle mass over the Earth's history, high (3)He contents, high (3)He/(4)He ratios and (40)Ar concentrations high enough to satisfy the (40)Ar mass balance of the Earth can be preserved in the lower mantle. The differences in (3)He/(4)He ratios between mid-ocean-ridge basalts and ocean island basalts, as well as high concentrations of (3)He and (40)Ar in the mantle source of ocean island basalts, can be explained within the framework of different processing rates for the upper and the lower mantle. Hence, to preserve primitive noble gas signatures, we find no need for hidden reservoirs or convective isolation of the lower mantle for any length of time.

Non-equilibrium degassing and a primordial source for helium in ocean-island volcanism.

Radioactive decay of uranium and thorium produces 4He, whereas 3He in the Earth's mantle is not produced by radioactive decay and was only incorporated during accretion-that is, it is primordial. 3He/4He ratios in many ocean-island basalts (OIBs) that erupt at hotspot volcanoes, such as Hawaii and Iceland, can be up to sixfold higher than in mid-ocean ridge basalts (MORBs). This is inferred to be the result of outgassing by melt production at mid-ocean ridges in conjunction with radiogenic ingrowth of 4He, which has led to a volatile-depleted upper mantle (MORB source) with low 3He concentrations and low 3He/4He ratios. Consequently, high 3He/4He ratios in OIBs are conventionally viewed as evidence for an undegassed, primitive mantle source, which is sampled by hot, buoyantly upwelling deep-mantle plumes. However, this conventional model provides no viable explanation of why helium concentrations and elemental ratios of He/Ne and He/Ar in OIBs are an order of magnitude lower than in MORBs. This has been described as the 'helium concentration paradox' and has contributed to a long-standing controversy about the structure and dynamics of the Earth's mantle. Here we show that the helium concentration paradox, as well as the full range of noble-gas concentrations observed in MORB and OIB glasses, can self-consistently be explained by disequilibrium open-system degassing of the erupting magma. We show that a higher CO2 content in OIBs than in MORBs leads to more extensive degassing of helium in OIB magmas and that noble gases in OIB lavas can be derived from a largely undegassed primitive mantle source.

Krypton in the Chassigny meteorite shows Mars accreted chondritic volatiles before nebular gases.

Volatile elements are thought to have been delivered to Solar System terrestrial planets late in their formation through accretion of chondritic meteorites. Mars can provide information on inner Solar System volatile delivery during the earliest planet formation stages. We measured krypton isotopes in the martian meteorite Chassigny, representative of the planet's interior. We found chondritic krypton isotope ratios, which imply early incorporation of chondritic volatiles. The atmosphere of Mars has different (solar-type) krypton isotope ratios, indicating that it is not a product of magma ocean outgassing or fractionation of interior volatiles. Atmospheric krypton instead originates from accretion of solar nebula gas after formation of the mantle but before nebular dissipation. Our observations contradict the common hypothesis that during planet formation, chondritic volatile delivery occurred after solar gas acquisition.

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.

Interstellar chemistry recorded in organic matter from primitive meteorites.

Organic matter in extraterrestrial materials has isotopic anomalies in hydrogen and nitrogen that suggest an origin in the presolar molecular cloud or perhaps in the protoplanetary disk. Interplanetary dust particles are generally regarded as the most primitive solar system matter available, in part because until recently they exhibited the most extreme isotope anomalies. However, we show that hydrogen and nitrogen isotopic compositions in carbonaceous chondrite organic matter reach and even exceed those found in interplanetary dust particles. Hence, both meteorites (originating from the asteroid belt) and interplanetary dust particles (possibly from comets) preserve primitive organics that were a component of the original building blocks of the solar system.

Isotopic compositions of cometary matter returned by Stardust.

Hydrogen, carbon, nitrogen, and oxygen isotopic compositions are heterogeneous among comet 81P/Wild 2 particle fragments; however, extreme isotopic anomalies are rare, indicating that the comet is not a pristine aggregate of presolar materials. Nonterrestrial nitrogen and neon isotope ratios suggest that indigenous organic matter and highly volatile materials were successfully collected. Except for a single (17)O-enriched circumstellar stardust grain, silicate and oxide minerals have oxygen isotopic compositions consistent with solar system origin. One refractory grain is (16)O-enriched, like refractory inclusions in meteorites, suggesting that Wild 2 contains material formed at high temperature in the inner solar system and transported to the Kuiper belt before comet accretion.