A halogen budget of the bulk silicate Earth points to a history of early halogen degassing followed by net regassing

Halogens are important tracers of various planetary formation and evolution processes, and an accurate understanding of their abundances in the Earth’s silicate reservoirs can help us reconstruct the history of interactions among mantle, atmosphere, and oceans. The previous studies of halogen abundances in the bulk silicate Earth (BSE) are based on the assumption of constant ratios of element abundances, which is shown to result in a gross underestimation of the BSE halogen budget. Here we present a more robust approach using a log-log linear model. Using this method, we provide an internally consistent estimate of halogen abundances in the depleted mid-ocean ridge basalts (MORB)-source mantle, the enriched ocean island basalts (OIB)-source mantle, the depleted mantle, and BSE. Unlike previous studies, our results suggest that halogens in BSE are not more depleted compared to elements with similar volatility, thereby indicating sufficient halogen retention during planetary accretion. According to halogen abundances in the depleted mantle and BSE, we estimate that ∼87% of all stable halogens reside in the present-day mantle. Given our understanding of the history of mantle degassing and the evolution of crustal recycling, the revised halogen budget suggests that deep halogen cycle is characterized by efficient degassing in the early Earth and subsequent net regassing in the rest of Earth history. Such an evolution of deep halogen cycle presents a major step toward a more comprehensive understanding of ancient ocean alkalinity, which affects carbon partitioning within the hydrosphere, the stability of crustal and authigenic minerals, and the development of early life.

Numerous chondritic impactors and oxidized magma ocean set Earth’s volatile depletion

Earth’s surface environment is largely influenced by its budget of major volatile elements: carbon (C), nitrogen (N), and hydrogen (H). Although the volatiles on Earth are thought to have been delivered by chondritic materials, the elemental composition of the bulk silicate Earth (BSE) shows depletion in the order of N, C, and H. Previous studies have concluded that non-chondritic materials are needed for this depletion pattern. Here, we model the evolution of the volatile abundances in the atmosphere, oceans, crust, mantle, and core through the accretion history by considering elemental partitioning and impact erosion. We show that the BSE depletion pattern can be reproduced from continuous accretion of chondritic bodies by the partitioning of C into the core and H storage in the magma ocean in the main accretion stage and atmospheric erosion of N in the late accretion stage. This scenario requires a relatively oxidized magma ocean ($$\log _{10} f_{{\mathrm{O}}_2}$$ log 10 f O 2 $$\gtrsim$$ ≳ $${\mathrm{IW}}$$ IW $$-2$$ - 2 , where $$f_{{\mathrm{O}}_2}$$ f O 2 is the oxygen fugacity, $$\mathrm{IW}$$ IW is $$\log _{10} f_{{\mathrm{O}}_2}^{\mathrm{IW}}$$ log 10 f O 2 IW , and $$f_{{\mathrm{O}}_2}^{\mathrm{IW}}$$ f O 2 IW is $$f_{{\mathrm{O}}_2}$$ f O 2 at the iron-wüstite buffer), the dominance of small impactors in the late accretion, and the storage of H and C in oceanic water and carbonate rocks in the late accretion stage, all of which are naturally expected from the formation of an Earth-sized planet in the habitable zone.

Potassium isotope composition of Mars reveals a mechanism of planetary volatile retention

The abundances of water and highly to moderately volatile elements in planets are considered critical to mantle convection, surface evolution processes, and habitability. From the first flyby space probes to the more recent “Perseverance” and “Tianwen-1” missions, “follow the water,” and, more broadly, “volatiles,” has been one of the key themes of martian exploration. Ratios of volatiles relative to refractory elements (e.g., K/Th, Rb/Sr) are consistent with a higher volatile content for Mars than for Earth, despite the contrasting present-day surface conditions of those bodies. This study presents K isotope data from a spectrum of martian lithologies as an isotopic tracer for comparing the inventories of highly and moderately volatile elements and compounds of planetary bodies. Here, we show that meteorites from Mars have systematically heavier K isotopic compositions than the bulk silicate Earth, implying a greater loss of K from Mars than from Earth. The average “bulk silicate” δ41K values of Earth, Moon, Mars, and the asteroid 4-Vesta correlate with surface gravity, the Mn/Na “volatility” ratio, and most notably, bulk planet H2O abundance. These relationships indicate that planetary volatile abundances result from variable volatile loss during accretionary growth in which larger mass bodies preferentially retain volatile elements over lower mass objects. There is likely a threshold on the size requirements of rocky (exo)planets to retain enough H2O to enable habitability and plate tectonics, with mass exceeding that of Mars.

Isotopic evidence for the formation of the Moon in a canonical giant impact

Isotopic measurements of lunar and terrestrial rocks have revealed that, unlike any other body in the solar system, the Moon is indistinguishable from the Earth for nearly every isotopic system. This observation, however, contradicts predictions by the standard model for the origin of the Moon, the canonical giant impact. Here we show that the vanadium isotopic composition of the Moon is offset from that of the bulk silicate Earth by 0.18 ± 0.04 parts per thousand towards the chondritic value. This offset most likely results from isotope fractionation on proto-Earth during the main stage of terrestrial core formation (pre-giant impact), followed by a canonical giant impact where ~80% of the Moon originates from the impactor of chondritic composition. Our data refute the possibility of post-giant impact equilibration between the Earth and Moon, and implies that the impactor and proto-Earth mainly accreted from a common isotopic reservoir in the inner solar system.

The niobium and tantalum concentration in the mantle constrains the composition of Earth’s primordial magma ocean

The bulk silicate Earth (BSE), and all its sampleable reservoirs, have a subchondritic niobium-to-tantalum ratio (Nb/Ta). Because both elements are refractory, and Nb/Ta is fairly constant across chondrite groups, this can only be explained by a preferential sequestration of Nb relative to Ta in a hidden (unsampled) reservoir. Experiments have shown that Nb becomes more siderophile than Ta under very reducing conditions, leading the way for the accepted hypothesis that Earth’s core could have stripped sufficient amounts of Nb during its formation to account for the subchondritic signature of the BSE. Consequently, this suggestion has been used as an argument that Earth accreted and differentiated, for most of its history, under very reducing conditions. Here, we present a series of metal–silicate partitioning experiments of Nb and Ta in a laser-heated diamond anvil cell, at pressure and temperature conditions directly comparable to those of core formation; we find that Nb is more siderophile than Ta under any conditions relevant to a deep magma ocean, confirming that BSE’s missing Nb is in the core. However, multistage core formation modeling only allows for moderately reducing or oxidizing accretionary conditions, ruling out the need for very reducing conditions, which lead to an overdepletion of Nb from the mantle (and a low Nb/Ta ratio) that is incompatible with geochemical observations. Earth’s primordial magma ocean cannot have contained less than 2% or more than 18% FeO since the onset of core formation.