Depletion Of Volatile Elements Research Articles

Iron alloys of volatile elements in the deep Earth's interior.

Investigations into the compositional model of the Earth, particularly the atypical concentrations of volatile elements within the silicate portion of the early Earth, have attracted significant interest due to their pivotal role in elucidating the planet's evolution and dynamics. To understand the behavior of such volatile elements, an established 'volatility trend' has been used to explain the observed depletion of certain volatile elements. However, elements such as Se and Br remain notably over-depleted in the silicate Earth. Here we show the results from first-principles simulations that explore the potential for these elements to integrate into hcp-Fe through the formation of substitutional alloys, long presumed to be predominant constituents of the Earth's core. Based on our findings, the thermodynamic stability of these alloys suggests that these volatile elements might indeed be partially sequestered within the Earth's core. We suggest potential reservoirs for volatile elements within the deep Earth, augmenting our understanding of the deep Earth's composition.

Origin of moderately volatile element depletion on differentiated bodies: Insights from the evaporation of indium from silicate melts

In comparison with the Sun and CI chondrites, moderately volatile elements (MVEs) are depleted in terrestrial planets and other small, rocky differentiated bodies in the inner solar system. The abundances of most MVEs in the bulk silicate Earth (BSE) fall on a trend that defines a near log-linear decrease with their 50% nebular condensation temperature (Tc50). This temperature scale has traditionally been used to infer elemental volatility during planetary formation and accretion, however, indium (In) deviates from this correlation. Despite being a siderophile element that could have been depleted by core formation, In is overabundant for its calculated Tc50 in the BSE, as well as in the silicate portions of other small bodies (e.g., Moon and Vesta). This overabundance of In indicates that Tc50, calculated under nebular conditions, may not be applicable to planetary evaporation that occurs at much higher oxygen fugacity (fO2) and pressure than nominal nebular conditions. Here, we conduct a series of evaporation experiments for basaltic melts to quantify the volatility of In under conditions relevant to planetary evaporation. Our results show that, when using the evaporation temperature (Te1, refers to the temperature at which 1% of element i has evaporated from liquid to gas phase under equilibrium) as the volatility scale, the abundances of volatile elements, including In, of the Moon and Vesta display a progressive depletion with increasing volatility (decreasing Te1). This smooth depletion pattern contrasts with the overabundance of In shown on the Tc50 scale, suggesting that volatile depletion on small bodies occurred under non-nebular environment instead of during nebular condensation. On the other hand, the volatile element composition of the BSE (including In) could be explained by integrating (i) early accreted precursor materials of the proto-Earth that underwent volatile loss under conditions more oxidizing than those of the solar nebula with (ii) late added volatile-rich materials.

Nickel-rich, volatile depleted iron meteorites: Relationships and formation processes

Ungrouped iron meteorites Tishomingo, Willow Grove, and Chinga, and group IVB iron meteorites, are Ni-rich. Similarities include enrichments of 10–100 × CI for some refractory siderophile elements, and equivalent depletions in more volatile siderophile elements. Superimposed on the overall enrichment/depletion trend, certain siderophile elements (P, W, Fe, Mo) are depleted relative to elements of similar volatility. All three ungrouped irons derive from parent bodies formed in the early Solar System. Willow Grove and Chinga are characterized by cosmic ray exposure corrected 182W/184W consistent with metal-silicate segregation on their parent bodies within 1–3 Myr of Solar System formation, within the age range determined for segregation of magmatic iron meteorite parent bodies, including group IVB irons. Tishomingo is characterized by a younger model age 4–5 Myr subsequent to Solar System formation, reflecting either late stage melting resulting from 26Al decay, or an impact resetting. The discovery of stishovite in Tishomingo, indicating exposure to a minimum shock pressure of 8–9 GPa, is consistent with the latter.Stishovite in Tishomingo and chromite included in troilite-daubréelite in IVB irons allows oxygen isotopic composition comparison between these meteorites. Different mass independent oxygen isotopic compositions of IVB irons and Tishomingo indicate genetically distinct parent bodies. By contrast, mass independent Mo isotopic compositions overlap within analytical uncertainties, indicating a similar, carbonaceous chondrite (CC) type genetic heritage. Molybdenum and 183W isotopic data for Chinga and Willow Grove indicate derivation from CC type parent bodies. Willow Grove shares Mo and 183W isotopic compositions with the Ni-rich South Byron Trio (SBT) grouplet and the Milton pallasite. These Ni-rich meteorites likely formed in the same general nebular environment as other CC planetesimals, likely the outer Solar System.Highly siderophile element (HSE) abundances of Willow Grove and Tishomingo are similar to some IVB meteorites, consistent with formation by moderate degrees of fractional crystallization from initial metallic melts with low S and P, and modestly fractionated HSE. The comparable HSE abundances of Tishomingo and Willow Grove to some IVB irons, yet substantially higher Ni concentrations, indicate formation on parent bodies with lower bulk HSE abundances or HSE concentration in proportionally smaller volumes of metal. HSE abundances in Chinga are considerably lower than in IVB irons, highly fractionated, and processes responsible for these remain elusive.For IVB irons and these ungrouped irons, high temperature condensation likely dominated the enrichment and depletion of the refractory and volatile siderophile elements, respectively. Parent body degassing may have also played a role. Relative depletion of volatile siderophile elements is not, however, a universal feature of high-Ni meteorites. The SBT and Milton pallasite are Ni-rich, but less depleted in the more volatile siderophile elements. Nickel enrichment was likely driven by oxidation of Fe metal during parent body accretion or core segregation. Oxidation of the Tishomingo and Willow Grove parent bodies may have occurred at ∼ IW + 1, indicated by relative Mo and W depletions due to metal/water reaction during differentiation. Late-stage reduction, indicated by the presence of Cr-bearing sulfides in Tishomingo and IVB irons, may have resulted from exhaustion of the oxidant.

Sierra Gorda 013: Unusual CBa‐like chondrite

AbstractThe new metal‐enriched anomalous chondrite Sierra Gorda 013 (SG 013) contains two different lithologies. Lithology 1 (L1) is represented by anomalous CBa‐like chondrite material containing ~80 vol% of Fe,Ni‐metal particles and globules up to 6 mm in size; chondrules and clasts of types POP, BO, and SO (up to 5 mm in diameter); rare sulfides; and shock melted silicate–metal areas. It does not contain any fine‐grained matrix. Several chondrules contain chromite–pyroxene symplectites. Lithology 2 (L2) has a recrystallized texture with evenly distributed olivine, pyroxene and plagioclase. L2 does not have any chondrules or sulfides, and contains less Fe,Ni‐ metal (~25 vol%) than L1. Both lithologies contain reduced olivine (Fa2–4) and pyroxene (Fs3.5), similar to CBa chondrites. Similar to CBa, there is no Ni‐Co correlation in the SG 013 metal. Rare sulfides in L1 are enriched in V. Chromite was observed in both lithologies. Oxygen isotope compositions of both lithologies are different but in the range of CBa chondrites. Bulk major and trace element geochemistry of nonporphyritic chondrules and bulk siderophile compositions in metal globules of L1 indicate elemental fractionation during formation of metallic and silicate objects with records of the evaporation process: depletion in moderate and volatile elements with the exception of Cr. Bulk geochemistry of porphyritic chondrules of L1 and the silicate portion of L2 is similar and also indicates evaporation processes. The rare Earth element (REE) distribution of L1 chondrules records a very fractionated signature corresponding to possible differentiated precursor material, while the REE pattern of L2 is primitive chondritic. The formation of SG 013 could be explained by collisions of planetesimals producing an impact plume, the precursor material of which could be chondritic and possibly differentiated. Both lithologies were affected by secondary processes: L1 preserved the traces of shock events and partial melting resulting in formation of symplectites in chondrules, melt pockets, and metal–silicate melt between the metal globules; L2 was affected by shock thermal metamorphism (up to 900 °C) resulting in recrystallization.

The origin of volatile elements in the Earth–Moon system

The origin of volatile species such as water in the Earth-Moon system is a subject of intense debate but is obfuscated by the potential for volatile loss during the Giant Impact that resulted in the formation of these bodies. One way to address these topics and place constraints on the temporal evolution of volatile components in planetary bodies is by using the observed decay of 87Rb to 87Sr because Rb is a moderately volatile element, whereas Sr is much more refractory. Here, we show that lunar highland rocks that crystallized ∼4.35 billion years ago exhibit very limited ingrowth of 87Sr, indicating that prior to the Moon-forming impact, the impactor commonly referred to as "Theia" and the proto-Earth both must have already been strongly depleted in volatile elements relative to primitive meteorites. These results imply that 1) the volatile element depletion of the Moon did not arise from the Giant Impact, 2) volatile element distributions on the Moon and Earth were principally inherited from their precursors, 3) both Theia and the proto-Earth probably formed in the inner solar system, and 4) the Giant Impact occurred relatively late in solar system history.

Collisional mixing between inner and outer solar system planetesimals inferred from the Nedagolla iron meteorite

AbstractThe ungrouped iron meteorite Nedagolla is the first meteorite with bulk Mo, Ru, and Ni isotopic compositions that are intermediate between those of the noncarbonaceous (NC) and carbonaceous (CC) meteorite reservoirs. The Hf‐W chronology of Nedagolla indicates that this mixed NC–CC isotopic composition was established relatively late, more than 7 Myr after solar system formation. The mixed NC–CC isotopic composition is consistent with the chemical composition of Nedagolla, which combines signatures of metal segregation under more oxidizing conditions (relative depletions in Mo and W), characteristic for CC bodies, and more reducing conditions (high Si and Cr contents), characteristic for some NC bodies, in a single sample. These data combined suggest that Nedagolla formed as the result of collisional mixing of NC and CC core material, which partially re‐equilibrated with silicate mantle material that predominantly derives from the NC body. These mixing processes might have occurred during a hit‐and‐run collision between two differentiated bodies, which also provides a possible pathway for Nedagolla's extreme volatile element depletion. As such, Nedagolla provides the first isotopic evidence for early collisional mixing of NC and CC bodies that is expected as a result of Jupiter's growth.

The Sn isotope composition of chondrites: Implications for volatile element depletion in the Solar System

The origin of volatile element depletion in terrestrial planets and meteorites relative to a solar composition represented by CI carbonaceous chondrites remains an unsolved problem. The isotope compositions of moderately volatile elements may offer the possibility to distinguish between the various processes that may have caused this depletion (e.g., partial condensation or partial evaporation). We report high precision Sn isotope measurements in carbonaceous chondrites and ordinary chondrites and the results are reported as δ124/116Sn. Four carbonaceous chondrites (Orgueil CI, Murchison CM2, NWA 5240 CV3 and Allende CV3) show a limited range in δ124/116Sn (–0.02‰ to 0.11‰) with an average value of 0.04 ± 0.11‰ (2 s.d.) for a wide range of Sn concentrations (0.63 ppm to 1.57 ppm). The absence of Sn isotope fractionation among carbonaceous chondrites suggests that volatile depletion may have taken place under thermodynamic equilibrium conditions between solid and vapor in the Solar Nebula. Alternatively, the mixing of two components, a volatile-free component containing no or little Sn and a volatile-rich component could explain this trend. This latter hypothesis is consistent with the overall trace element pattern found in carbonaceous chondrites, showing a constant relative abundance when normalized to CI chondrites for the most volatile elements. In contrast with carbonaceous chondrites, ordinary chondrites exhibit a larger range of Sn isotope compositions (δ124/116Sn from –2.02‰ to 0.64‰), but neither the degree of metamorphism (3–6) nor the group (H, L, LL) is correlated with Sn isotopic variations, or with the Sn contents (range 0.20 to 1.44 ppm). Nineteen out of twenty-one ordinary chondrites are enriched in light Sn isotopes compared with carbonaceous chondrites and the bulk silicate Earth. The trace element patterns of volatile elements in ordinary chondrites suggest that equilibrated ordinary chondrites have been disturbed by parent body processes related to metamorphic or shock overprinting but also inherited isotope fractionation found in unequilibrated ordinary chondrites. Last, the isotope composition of the bulk silicate Earth (BSE) indicates that the volatile element depletion observed in the Earth took place in conditions perhaps similar to those of carbonaceous chondrites, as a simple model describing the effect of Earth’s core formation on Sn isotopes shows that the Sn isotope composition of the bulk Earth is identical to that of the BSE and of carbonaceous chondrites.

Survival of presolar p-nuclide carriers in the nebula revealed by stepwise leaching of Allende refractory inclusions.

The 87Rb-87Sr radiochronometer provides key insights into the timing of volatile element depletion in planetary bodies, yet the unknown nucleosynthetic origin of Sr anomalies in Ca-Al-rich inclusions (CAIs, the oldest dated solar system solids) challenges the reliability of resulting chronological interpretations. To identify the nature of these Sr anomalies, we performed step-leaching experiments on nine unmelted CAIs from Allende. In six CAIs, the chemically resistant residues (0.06 to 9.7% total CAI Sr) show extreme positive μ84Sr (up to +80,655) and 87Sr variations that cannot be explained by decay of 87Rb. The extreme 84Sr but more subdued 87Sr anomalies are best explained by the presence of a presolar carrier enriched in the p-nuclide 84Sr. We argue that this unidentified carrier controls the isotopic anomalies in bulk CAIs and outer solar system materials, which reinstates the chronological significance of differences in initial 87Sr/86Sr between CAIs and volatile-depleted inner solar system materials.

Earth and Mars – Distinct inner solar system products

Composition of terrestrial planets records planetary accretion, core–mantle and crust–mantle differentiation, and surface processes. Here we compare the compositional models of Earth and Mars to reveal their characteristics and formation processes. Earth and Mars are equally enriched in refractory elements (1.9 × CI), although Earth is more volatile-depleted and less oxidized than Mars. Their chemical compositions were established by nebular fractionation, with negligible contributions from post-accretionary losses of moderately volatile elements. The degree of planetary volatile element depletion might correlate with the abundances of chondrules in the accreted materials, planetary size, and their accretion timescale, which provides insights into composition and origin of Mercury, Venus, the Moon-forming giant impactor, and the proto-Earth. During its formation before and after the nebular disk's lifetime, the Earth likely accreted more chondrules and less matrix-like materials than Mars and chondritic asteroids, establishing its marked volatile depletion. A giant impact of an oxidized, differentiated Mars-like (i.e., composition and mass) body into a volatile-depleted, reduced proto-Earth produced a Moon-forming debris ring with mostly a proto-Earth's mantle composition. Chalcophile and some siderophile elements in the silicate Earth added by the Mars-like impactor were extracted into the core by a sulfide melt (∼0.5% of the mass of the Earth's mantle). In contrast, the composition of Mars indicates its rapid accretion of lesser amounts of chondrules under nearly uniform oxidizing conditions. Mars’ rapid cooling and early loss of its dynamo likely led to the absence of plate tectonics and surface water, and the present-day low surface heat flux. These similarities and differences between the Earth and Mars made the former habitable and the other inhospitable to uninhabitable.

K/U of the MORB Source and Silicate Earth

AbstractPotassium (K) informs on the radiogenic heat production, atmospheric composition, and volatile element depletion of the Earth and other planetary systems. Constraints on the abundance of K in the Earth, Moon, and other rocky bodies have historically hinged on K/U values measured in planetary materials, particularly comparisons of the continental crust and mid‐ocean ridge basalts (MORBs), for developing compositional models of the bulk silicate Earth (BSE). However, a consensus on the most representative K/U value for global MORB remains elusive despite numerous studies. Here, we statistically analyze a critical compilation of MORB data to determine the K/U value of the MORB source. Covariations in the log‐normal abundances of K and U establish that K is 3–7 times less incompatible than U during melting and/or crystallization processes, enabling inverse modeling to infer the K/U of the MORB source region. These comprehensive data have a mean K/U for global MORB = 13,900 ± 200 (2σm; n = 4,646), and define a MORB source region with a K/U between 14,000 and 15,500, depending on the modeled melting regime. However, this range represents strictly a lower limit due to the undefined role of fractional crystallization in these samples and challenges preserving the signatures of depleted components in the MORB mantle source. This MORB source model, when combined with recent metadata analyses of ocean island basalt (OIB) and continental crust, suggests that the BSE has a K/U value >12,100 and contains >260 × 10−6 kg/kg K, resulting in a global production of ∼3.5 TW of radiogenic heat today and 1.5 × 1017 kg of 40Ar over the lifetime of the planet.

Determination of the refractory enrichment factor of the bulk silicate Earth from metal-silicate experiments on rare Earth elements

This study investigates the partitioning of rare earth elements (REE) from La to Gd between molten metal and silicate to evaluate potential fractionation occurring during core-mantle differentiation. We report molten metal-silicate liquid partition coefficients from 24 multi-anvil experiments, extending the range of pressure, previously ranging from 1 to 8 GPa, up to 14 GPa. Experiments were performed at temperatures of between 2300 and 2560 K, and for oxygen fugacities ranging from the IW (Iron-Wüstite buffer) to IW–4. Metal-silicate partition coefficients for the studied REE vary with the oxygen fugacity and S concentration in the metallic phase of the system. These elements were all lithophile during the Earth's accretion. By compiling all existing data on molten metal-silicate liquid partitioning, REE partitioning between the mantle and core during the Earth's accretion can be determined for a wide range of P, T and fo2 conditions representing the early evolution of planetary bodies from planetesimals to planets. REE concentrations of the bulk silicate Earth (BSE) are calculated from accretion scenarios using varying proportions and compositions of chondritic building blocks. The models selected are those that reproduce the Earth's nucleosynthetic isotope signature and the Ni/Co, Th/U and Nb/Ta ratios of the BSE. The BSE refractory element enrichment factor determined from REE data is equal to 2.88 (relative to CI chondrites). This calculation takes into account the depletion in volatile elements in the Earth compared to chondrites. This new estimate is in good agreement with previous determinations based on analysis of the upper mantle rocks, which supports the idea of a chemically homogeneous mantle. We also confirm that the formation of the core, with or without segregation of a sulfide phase, does not fractionate Sm/Nd and cannot be responsible for the 142Nd excess measured in modern terrestrial samples relative to chondrites.

Carbonaceous Chondrites and the Condensation of Elements from the Solar Nebula

Abstract Common features of all carbonaceous chondrite groups are invariant refractory element ratios, depletions of moderately volatile elements as a function of their condensation temperature (T C), and strongly depleted highly volatile element concentrations independent of T C. The depletion of volatile elements with respect to the bulk solar system composition requires a separation of gas from solids in the solar nebula. Several models have been proposed to explain the decoupling of gas and solids, but not all are compatible with astrophysical, chemical, and petrologic constraints. Here existing physical models are integrated with measured element concentrations, measured and modeled physical properties of protoplanetary disks, and planetary-scale nucleosynthetic and stable isotope variations to establish a conceptual model for the condensation and accretion of elements into planetesimals. In this model, the chemical composition of chondrites is established by element condensation in a cooling solar nebula that changed its surface density as a function of time and temperature. The model predicts peak temperatures at the condensation sites of about 1400 K that consequently decreased due to a diminishing heat source originating from viscous heating and radiation, accompanied by continuous removal of gas from the nebula surface by photoevaporation. The coupled evolution of condensing solids from a nebula of diminishing surface density resulted in a pattern of decreasing moderately volatile abundances with decreasing T C. The reduction of nebula opacity due to the chondrule-forming process significantly increased nebula cooling rates and led to the near-chondritic relative abundances of highly volatile elements observed in carbonaceous chondrites.

The selenium isotope composition of lunar rocks: Implications for the formation of the Moon and its volatile loss

The Moon and Earth share similar relative abundances and isotope compositions of refractory lithophile elements, indicating that the Moon formed from a silicate reservoir that is chemically indistinguishable from the Earth's primitive silicate mantle. In contrast, most volatile elements are depleted in lunar mare basalts compared to Earth's mantle and differ in their isotope composition. However, the depletion of volatile elements is not a simple function of their condensation temperature, indicating multiple mechanisms that established the lunar volatile element budget. Specifically, the chalcophile elements S, Se and Te are not depleted in lunar basalts compared to their terrestrial counterparts. In this study, the abundances and stable isotope compositions of the volatile and chalcophile element Se measured in three lunar mare basalts and seven soils are used to refine the processes that caused volatile element depletion on the Moon. The Se isotope composition of two lunar mare basalts (δ82/78Se = 1.08 and 0.8‰) is significantly heavier compared to chondrites (−0.20 ± 0.26‰; 2 s.d.) and terrestrial basalts (0.29 ± 0.24‰; 2 s.d.). The offset in the Se isotope composition is attributed to a volatility controlled loss of Se from the Moon. The lack of chalcophile element depletion in lunar mare basalts is then explained by sulphide segregation in the Earth's mantle after the Moon forming impact followed by a late veneer of chondritic material to the Earth. Seven lunar soils were found to have chondritic S/Se ratios, but have δ82/78Se values that are 6 to 13‰ heavier compared to mare basalts. This fractionation is likely the result of coupled and repeating processes of meteoritic material addition and concomitant partial evaporation. Results from numerical modelling indicate that isotope fractionation in lunar soils is due to partial evaporation of FeSe and FeS with evaporative loss of about 20% for both Se and S.

Potassium isotopic composition of the Moon

The Moon is depleted in water and other volatiles compared to Earth and the bulk solar composition. Such depletion of volatile elements and the stable isotope fractionations of these elements can be used to better understand the origin and early differentiation history of the Moon. In this study, we focus on the moderately volatile element, potassium, and we report the K elemental abundances and isotopic compositions (δ41K relative to NIST SRM 3141a) for nineteen Apollo lunar rocks and lunar meteorites (twenty-two subsamples), spanning all major geochemical and petrologic types of lunar materials. The K isotopic compositions of low-Ti and high-Ti basalts are indistinguishable, providing a lunar basalt average δ41K of –0.07 ± 0.09‰ (2SD), which we also consider to be the best estimate of the lunar mantle and the bulk silicate Moon. The significant enrichment of K in its heavier isotopes in the bulk silicate Moon, compared with the bulk silicate Earth (δ41K = –0.48 ± 0.03‰), is consistent with previous analyses of K isotopes and other moderately volatile elements (e.g., Cl, Cu, Zn, Ga, and Rb). We also report analyses of K isotopes for lunar nonmare samples, which show large variations of K isotopic ratios compared to lunar basalts. We interpret this large K isotopic fractionation as the result of late-stage magma ocean degassing during urKREEP formation, which is also coupled with Cl isotope fractionation. Degassing of urKREEP likely triggered redistribution of K isotopes in the Moon, enriching the urKREEP reservoir in heavy K isotopes while implanting the light K isotopic signatures onto the lunar surface. This scenario suggests a heterogeneous distribution of K isotopes in the Moon as a consequence of its magmatic evolution.

Vapor Drainage in the Protolunar Disk as the Cause for the Depletion in Volatile Elements of the Moon

Abstract Lunar rocks are severely depleted in moderately volatile elements (MVEs) such as Rb, K, and Zn relative to Earth. Identifying the cause of this depletion is important for understanding how the Earth–Moon system evolved in the aftermath of the Moon-forming giant impact. We measured the Rb isotopic compositions of lunar and terrestrial rocks to understand why MVEs are depleted in the Moon. Combining our new measurements with previous data reveals that the Moon has an 87Rb/85Rb ratio higher than Earth by +0.16 ± 0.04‰. This isotopic composition is consistent with evaporation of Rb into a vapor medium that was ∼99% saturated. Evaporation under this saturation can also explain the previously documented isotopic fractionations of K, Ga, Cu, and Zn of lunar rocks relative to Earth. We show that a possible setting for achieving the same saturation upon evaporation of elements with such diverse volatilities is through viscous drainage of a partially vaporized protolunar disk onto Earth. In the framework of an α-disk model, the α-viscosity needed to explain the ∼99% saturation calculated here is 10−3–10−2, which is consistent with a vapor disk where viscosity is controlled by magnetorotational instability.

An experimental assessment of the potential of sulfide saturation of the source regions of eucrites and angrites: Implications for asteroidal models of core formation, late accretion and volatile element depletions

The geochemistry of asteroidal magmas provides fundamental clues to the processes involved in the origin and early evolution of planetary bodies. Although sulfides are important reservoirs for a diverse suite of major and trace elements, it is currently unclear whether the interiors of asteroid Vesta and the Angrite Parent Body were sulfide liquid saturated during petrogenesis of non-cumulate eucrites and volcanic angrites. To assess the potential of sulfide liquid saturation in the interiors of these bodies, high pressure (P) – temperature (T) experiments were used to quantify the sulfur concentrations at sulfide saturation (SCSS) for volcanic angrites and non-cumulate eucrites. The sulfide-silicate partitioning behavior of various trace elements was simultaneously quantified to study their geochemical behavior at sulfide liquid saturation.It was found that the measured SCSS values agree well with the SCSS values predicted from a previous thermodynamic model for high-FeO* melts. To assess the possibility of sulfide liquid saturation of the source regions of non-cumulate eucrites and angrites, their S abundances were compared with the calculated SCSS values for their source regions. Results show that if eucritic and angritic source regions were saturated with FeS liquid, significant degassing (>50–80%) of S must have occurred during or following their magmatic emplacement. Such loss is inconsistent with the S, Cl, Zn and Rb isotopic compositions of non-cumulate eucrites. Sulfide liquid saturation of eucrite and angrite source regions is also excluded from the strongly incompatible behavior of Cu and HSE in non-cumulate eucrites and angrites (Riches et al., 2012).Additional calculations were performed to further explore the timing and extent of S loss during crystallization of the Vestan magma ocean. The assumption of chondritic bulk S abundances of bulk Vesta would correspond with extremely high S contents of the eucrite source region(s), even after consideration of depletion of S due to core formation. In light of the S, Cl, Zn and Rb stable isotopic compositions of eucrites, the S abundances in eucrites are most consistent with the hypothesis that the Vestan mantle was already strongly depleted in S (>70–80%) by the time of Vestan magma ocean crystallization, resulting in more realistic S contents of the eucrite source region(s). The depletion of S could have been established during initial accretion of Vesta or it could simply reflect accretion of volatile depleted components that experienced incomplete condensation (Wu et al., 2018). Modeling of the new experimentally determined sulfide-silicate partition coefficients and previously reported Vestan mantle depletions of the various chalcophile and siderophile elements suggests that sulfide liquid segregation during early Vestan magma ocean crystallization is also unlikely. The lack of sulfide liquid saturation in the source regions of non-cumulate eucrites and angrites, as well as during early Vestan magma ocean solidification, shows that current geochemical models of core formation and late accretion remain valid for these bodies.

Trace element partitioning between sulfide-, metal- and silicate melts at highly reduced conditions: Insights into the distribution of volatile elements during core formation in reduced bodies

Chalcophile and siderophile element abundances are used to provide important constraints on the interior compositions of planetary bodies as well as the pressure (P) - temperature (T) conditions that prevailed during core formation. The oxygen fugacity (fO2) during core formation varied considerably between the various terrestrial planets and asteroidal bodies in our solar system. Mercury, the aubrite parent body (AuPB) and some terrestrial precursor bodies may have differentiated at highly reduced conditions.At present knowledge about how the metal liquid-silicate melt and sulfide liquid-silicate melt partitioning behavior of major and trace elements are affected by high S concentrations in the silicate melt at highly reducing conditions is incomplete. Here, we experimentally study the metal-silicate and sulfide-silicate partitioning behavior of trace elements in reduced silicate melts over a wide range of S contents as a function of redox state at 1 GPa and 1833–1883 K. Silicate melt S contents ranged between ~0.5 and ~20 wt%, with a corresponding silicate FeO range of ~0.4 to ~17.5 wt%, in a fO2 range between 1 and 9 log units below the iron-wüstite buffer. Our results reproduce the decrease of the S concentration at sulfide saturation (SCSS) with decreasing FeO contents down to ~3 wt%, as well as its strong increase at <3 wt% FeO. At S contents exceeding >6–9 wt% S, the FeO contents increase again.Results show that most elements (Mg, Ti, V, Cr, Mn, Cu, Zn, Se, Nb, Cd, Sb, Te, Ta, Tl, Pb and Bi) are more chalcophile than siderophile at reducing conditions, whereas Si, Co, Ni, Ga, Ge, Mo and W preferentially partition into Fe-rich melts instead of sulfide liquids. Silicon, Ti, Se, and Te preferentially partition into Fe-S over (Fe,Mg,Ca)-S liquids, whereas Mn, Zn and Cd are more compatible in the latter. As proposed by Wood and Kiseeva (2015), chalcophile elements such as Cu, Se and Te behave less chalcophile with increasing S concentrations of the silicate melt, whereas the opposite is observed for nominally lithophile elements such as Mg, Ca and Ti.The results can be used to improve interpretations of the observed trace element systematics of aubrites and other reduced achondrites. All of the volatile elements considered here behave chalcophile at the reducing conditions inferred for differentiation of the AuPB. A significant degree of the observed volatile element depletions in aubrites may therefore reflect their preferential partitioning into sulfide liquids, rather than degassing during or after differentiation of the AuPB. These results suggest that, depending of the extent of core merging, precursor body differentiation and the efficiency of sulfide liquid segregation, reduced precursor bodies that were incorporated in the early Earth were likely more rich in volatile elements than currently assumed.

Earth's volatile element depletion pattern inherited from a carbonaceous chondrite-like source.

Earth's volatile element abundances (e.g., sulfur, zinc, indium and lead) provide constraints on fundamental processes such as planetary accretion, differentiation, and the delivery of volatile species, like water, which contributed to Earth becoming a habitable planet. The composition of the silicate Earth suggests chemical affinity but isotopic disparity to carbonaceous chondrites, meteorites that record the earliest element fractionations in the protoplanetary disk. However, the volatile element depletion pattern of the silicate Earth is obscured by core formation. Another key problem is the overabundance of indium, which could not be reconciled with any known chondrite group. Here we complement recently published volatile element abundances for carbonaceous chondrites with high precision sulfur, selenium, and tellurium data. We show that both Earth and carbonaceous chondrites exhibit a unique hockey stick volatile element depletion pattern where volatile elements with low condensation temperatures (750 - 500 K) are unfractionated from each other. This abundance plateau accounts for the apparent overabundance of indium in the silicate Earth without the need of exotic building materials or vaporization from precursors or during the Moon-forming impact and suggests the accretion of 10-15 % CI-like material before core formation ceased. Finally, more accurate estimates of volatile element abundances in the core and bulk Earth can now be provided.

Effect of silicon on activity coefficients of Bi, Cd, Sn, and Ag in liquid Fe‐Si, and implications for differentiation and core formation

AbstractThe depletion of volatile siderophile elements (VSE) Sn, Ag, Bi, Cd, and P in mantles of differentiated planetary bodies can be attributed to volatile‐depleted precursor materials (building blocks), fractionation during core formation, fractionation into and retention in sulfide minerals, and/or volatile loss associated with magmatism. Quantitative models to constrain the fractionation due to core formation have not been possible due to the lack of activity and partitioning data. Interaction parameters in Fe‐Si liquids have been measured at 1 GPa, 1600 °C and increase in the order Cd (~6), Ag (~10), Sn (~28), Bi (~46), and P (~58). These large and positive values contrast with smaller and negative values in Fe‐S liquids indicating that any chalcophile behavior exhibited by these elements will be erased by dissolution of a small amount of Si in the metallic liquid. A newly updated activity model is applied to Earth, Mars, and Vesta. Five elements (P, Zn, Sn, Cd, and In) in Earth's primitive upper mantle can largely be explained by metal‐silicate equilibrium at high PT conditions where the core‐forming metal is a Fe‐Ni‐S‐Si‐C metallic liquid, but two other—Ag and Bi—become overabundant during core formation and require a removal mechanism such as late sulfide segregation. All of the VSE in the mantle of Mars are consistent with core formation in a volatile element depleted body, and do not require any additional processes. Only P and Ag in Vesta's mantle are consistent with combined core formation and volatile‐depleted precursors, whereas the rest require accretion of chondritic or volatile‐bearing material after core formation. The concentrations of Zn, Ag, and Cd modeled for Vesta's core are similar to the concentration range measured in magmatic iron meteorites indicating that these volatile elements were already depleted in Vesta's precursor materials.

Volatile element depletion of the Moon-The roles of precursors, post-impact disk dynamics, and core formation.

The compositional and isotopic similarity of Earth's primitive upper mantle (PUM) and the Moon supports the derivation of the Moon from proto-Earth, but the Moon's inventory of volatile lithophile elements-Na, K, Rb, and Cs-is lower than Earth's PUM by factors of 4 to 5. The abundances of 14 other volatile elements exhibit siderophile behavior [volatile siderophile elements (VSEs); i.e., P, As, Cu, Ag, Sb, Ga, Ge, Bi, Pb, Zn, Sn, Cd, In, and Tl] that can be used to evaluate whether the Moon was derived from proto-Earth and if core formation or volatility controlled their depletion. At lunar core formation conditions, As, Sb, Ag, Ge, Bi, and Sn are siderophile, whereas P, Cu, Ga, Pb, Zn, Cd, In, and Tl are weakly siderophile or lithophile. VSEs may help to discriminate between physical and chemical processes that formed the Moon such as low- versus high-energy impacts and gas-melt interactions.