Volatile Delivery Research Articles

New Evidence for Wet Accretion of Inner Solar System Planetesimals from Meteorites Chelyabinsk and Benenitra

Abstract We investigated the hydrogen isotopic compositions and water contents of pyroxenes in two recent ordinary chondrite falls, namely, Chelyabinsk (2013 fall) and Benenitra (2018 fall), and compared them to three ordinary chondrite Antarctic finds, namely, Graves Nunataks GRA 06179, Larkman Nunatak LAR 12241, and Dominion Range DOM 10035. The pyroxene minerals in Benenitra and Chelyabinsk are hydrated (∼0.018–0.087 wt.% H2O) and show D-poor isotopic signatures (δDSMOW from −444‰ to −49‰). On the contrary, the ordinary chondrite finds exhibit evidence of terrestrial contamination with elevated water contents (∼0.039–0.174 wt.%) and δDSMOW values (from −199‰ to −14‰). We evaluated several small parent-body processes that are likely to alter the measured compositions in Benenitra and Chelyabinsk and inferred that water loss in S-type planetesimals is minimal during thermal metamorphism. Benenitra and Chelyabinsk hydrogen compositions reflect a mixed component of D-poor nebular hydrogen and water from the D-rich mesostases. A total of 45%–95% of water in the minerals characterized by low δDSMOW values was contributed by nebular hydrogen. S-type asteroids dominantly composed of nominally anhydrous minerals can hold 254–518 ppm of water. Addition of a nebular water component to nominally dry inner solar system bodies during accretion suggests a reduced need of volatile delivery to the terrestrial planets during late accretion.

The role of impacts on the atmospheres on the moons of outer giants

ABSTRACTWe investigate the comparative effect of impacts by trans-Neptunian Objects on the atmospheres of the moons Ganymede, Callisto, Europa, and Titan. We derive an analytic prescription for the ‘stalling mass’ (i.e. the atmosphere mass at which equilibrium between erosion and volatile delivery occurs), which is tested against a numerical model, demonstrating that the behaviour of the atmosphere matches the analytic prediction, albeit with stochastic events causing orders of magnitude variability. We find that bombardment, neglecting other effects, predicts atmosphere erosion on Ganymede, Callisto, and Europa leading to masses in quantitative agreement with the observed atmospheres. The predicted masses are relatively insensitive to the impactor size and velocity distributions, but sensitive to impactor density and volatile content. Crucially, we find that in this model the frequent arrival of 1–20 km-sized objects sets the quiescent atmosphere masses of the different moons, with atmospheres returning to these levels on ∼100 Myr time-scales at current bombardment levels, and larger impactors causing stochastic excursions to larger atmosphere masses. This quiescent level is higher on Titan than the Jovian moons due to the typically slower impact velocities, but to recreate Titan’s massive current atmosphere an additional volatiles contribution is needed, which may be provided by impact-triggered outgassing. If so, the predicted mass is then dependent on the outgassing efficiency and the volatile mass contained in the crust, both of which are uncertain. This work highlights the role that impacts may have played in shaping the atmosphere evolution of outer Solar system moons, and the importance of stochastic effects.

Tracing Earth's Volatile Delivery With Tin

AbstractEarth's accretion history for volatile elements, and the origin of their depletions with respect to the Sun and primitive meteorites, continue to be debated. Two end‐member scenarios propose either that volatile elements were delivered during the main phases of accretion and differentiation, or that the Earth accreted from materials largely devoid of volatiles with late addition of volatile‐rich materials. Experiments evaluating the effect of metal–silicate equilibrium on elemental and isotopic distribution of volatile and siderophile elements such as Sn can help to distinguish between these scenarios. In this study, we have systematically investigated the relative influence of temperature, pressure, oxygen fugacity, and metal and silicate composition on the metal–silicate partioning behavior of Sn, from 2 to 20 GPa and 1,700 to 2,573 K, indicating that Sn siderophility noticeably decreases with temperature and S content of the metal but increases dramatically with pressure. A resolvable isotopic fractionation factor between metal and silicate suggests that core–mantle equilibrium temperatures (∼3,000 K) could potentially generate a Sn isotopic composition of the mantle lighter than the core by 150–200 ppm/amu. Core formation modeling shows that the volatiles were added during the last 10% of the accretion history. A final core containing 2.5 to 3.5 wt.% S is required. Furthermore, modeling of the BSE isotopic composition argues for a late Sn delivery on Earth with carbonaceous chondrite‐like material as the most likely source of volatiles. Therefore, both elemental and isotopic approaches converge toward an identical volatile accretion scenario, involving a late volatile delivery.

Origin and timing of volatile delivery (N, H) to the angrite parent body: Constraints from in situ analyses of melt inclusions

Angrites are derived from the earliest generation of differentiated planetesimals that accreted sunward of Jupiter’s orbit, and are, thus, key to constraining the timing and source(s) of volatile delivery to planetary bodies in the inner solar system. Here we investigate the nitrogen and hydrogen isotopic signatures of angrite melts by in situ secondary ion mass spectrometry (SIMS) analyses of mineral-hosted melt inclusions and interstitial glass in two of the oldest volcanic angrites: D’Orbigny and Sahara 99555. The most primitive melt trapped in Mg-rich olivines in D'Orbigny is characterized by δ15N values ranging from 0 ± 25 to +56 ± 29‰ and δD values between −348 ± 53 and −118 ± 31‰. This shows that the angrite mantle source sampled by D'Orbigny has a N-H isotopic composition that is similar to that of CM carbonaceous chondrites, whose parent bodies are thought to have accreted in the outer solar system. The low nitrogen and water contents measured in Sahara 99555 possibly indicate that its parental melt underwent a higher degree of degassing compared to D’Orbigny or, alternatively, that the two angrites do not sample the same volatile reservoir within the angrite parent body. Given the very old crystallisation age of D’Orbigny, our findings imply that nitrogen- and water-rich objects, presumably formed beyond the orbit of Jupiter, must have been present in the terrestrial planet-forming region within the first ~4 Ma after the formation of Ca-Al-rich inclusions (CAIs, the oldest materials in the solar system).

Thermal Desorption of Astrophysically Relevant Ice Mixtures of Acetaldehyde and Acetonitrile from Olivine Dust*

Abstract Millimeter and centimeter observations are discovering an increasing number of interstellar complex organic molecules (iCOMs) in a large variety of star-forming sites, from the earliest stages of star formation to protoplanetary disks and in comets. In this context it is pivotal to understand how the solid-phase interactions between iCOMs and grain surfaces influence the thermal desorption process and, therefore, the presence of molecular species in the gas phase. In the laboratory, it is possible to simulate the thermal desorption process, deriving important parameters such as the desorption temperatures and energies. We report new laboratory results on temperature-programmed desorption from olivine dust of astrophysical relevant ice mixtures of water, acetonitrile, and acetaldehyde. We found that in the presence of grains, only a fraction of acetaldehyde and acetonitrile desorb at about 100 K and 120 K, respectively, while 40% of the molecules are retained by fluffy grains of the order of 100 μm up to temperatures of 190–210 K. In contrast with the typical assumption that all molecules are desorbed in regions with temperatures higher than 100 K, this result implies that about 40% of the molecules can survive on the grains enabling the delivery of volatiles toward regions with temperatures as high as 200 K and shifting inwards the position of the snow lines in protoplanetary disks. These studies offer a necessary support to interpret observational data and may help our understanding of iCOM formation, providing an estimate of the fraction of molecules released at various temperatures.

On the Probability That a Rocky Planet’s Composition Reflects Its Host Star

Abstract The bulk density of a planet, as measured by mass and radius, is a result of planet structure and composition. Relative proportions of iron core, rocky mantle, and gaseous envelopes are degenerate for a given density. This degeneracy is reduced for rocky planets without significant gaseous envelopes when the structure is assumed to be a differentiated iron core and rocky mantle, in which the core mass fraction (CMF) is a first-order description of a planet’s bulk composition. A rocky planet’s CMF may be derived both from bulk density and by assuming the planet reflects the host star’s major rock-building elemental abundances (Fe, Mg, and Si). Contrasting CMF measures, therefore, shed light on the outcome diversity of planet formation from processes including mantle stripping, out-gassing, and/or late-stage volatile delivery. We present a statistically rigorous analysis of the consistency of these two CMF measures accounting for observational uncertainties of planet mass and radius and host-star chemical abundances. We find that these two measures are unlikely to be resolvable as statistically different unless the bulk density CMF is at least 40% greater than or 50% less than the CMF as inferred from the host star. Applied to 11 probable rocky exoplanets, Kepler-107 c has a CMF as inferred from bulk density that is significantly greater than the inferred CMF from its host star (2σ) and is therefore likely an iron-enriched super-Mercury. K2-229b, previously described as a super-Mercury, however, does not meet the threshold for a super-Mercury at a 1σ or 2σ level.

Did Mars Possess a Dense Atmosphere During the First $\sim400$ Million Years?

It is not yet entirely clear whether Mars began as a warm and wet planet that evolved towards the present-day cold and dry body or if it always was cold and dry with just some sporadic episodes of liquid water on its surface. An important clue into this question can be gained by studying the earliest evolution of the Martian atmosphere and whether it was dense and stable to maintain a warm and wet climate or tenuous and susceptible to strong atmospheric escape. We discuss relevant aspects for the evolution and stability of a potential early Martian atmosphere. This contains the solar EUV flux evolution, the formation timescale and volatile inventory of the planet including volcanic degassing, impact delivery and removal, the loss of a catastrophically outgassed steam atmosphere, atmosphere-surface interactions, and thermal and non-thermal escape processes affecting any secondary atmosphere. While early non-thermal escape at Mars before 4 billion years ago (Ga) is poorly understood, particularly in view of its ancient intrinsic magnetic field, research on thermal escape processes indicate that volatile delivery and volcanic degassing cannot counterbalance the strong thermal escape. Therefore, a catastrophically outgassed steam atmosphere of several bars of CO2 and H2O, or CO and H2 for reduced conditions, could have been lost within just a few million years (Myr). Thereafter, Mars likely could not build up a dense secondary atmosphere during its first ~400 Myr but might only have possessed an atmosphere sporadically during events of strong volcanic degassing, potentially also including SO2. This indicates that before ~4.1 Ga Mars indeed might have been cold and dry. A denser CO2- or CO-dominated atmosphere, however, might have built up afterwards but must have been lost later-on due to non-thermal escape processes and sequestration into the ground.

In vitro performance evaluation of AnaConDaTM-100 and AnaConDaTM-50 compared to a circle breathing system for control and consumption of volatile anaesthetics

To identify the better volatile anaesthetic delivery system in an intensive care setting, we compared the circle breathing system and two models of reflection systems (AnaConDa™ with a dead space of 100 ml (ACD-100) or 50 ml (ACD-50)). These systems were analysed for the parameters like wash-in, consumption, and wash-out of isoflurane and sevoflurane utilising a test lung model. The test lung was connected to a respirator (circle breathing system: Aisys CS™; ACD-100/50: Puriton Bennett 840). Set parameters were volume-controlled mode, tidal volume-500 ml, respiratory rate-10/min, inspiration time-2 sec, PEEP-5 mbar, and oxygen-21%. Wash-in, consumption, and wash-out were investigated at fresh gas flows of 0.5, 1.0, 2.5, and 5.0 l/min. Anaesthetic target concentrations were 0.5, 1.0, 1.5, 2.0, and 2.5%. Wash-in was slower in ACD-100/-50 compared to the circle breathing system, except for fresh gas flows of 0.5 and 1.0 l/min. The consumption of isoflurane and sevoflurane in ACD-100 and ACD-50 corresponded to the fresh gas flow of 0.5-1.0 l/min in the circle breathing system. Consumption with ACD-50 was higher in comparison to ACD-100, especially at gas concentrations > 1.5%. Wash-out was quicker in ACD-100/-50 than in the circle breathing system at a fresh gas flow of 0.5 l/min, however, it was longer at all the other flow rates. Wash-out was comparable in ACD-100 and ACD-50. Wash-in and wash-out were generally quicker with the circle breathing system than in ACD-100/-50. However, consumption at 0.5 minimum alveolar concentration was comparable at flows of 0.5 and 1.0 l/min.

Constraints on early Earth's water budget from the evolution of the lunar hydrogen cycle

During the Hadean, Earth recovered from the Moon-forming giant impact, became covered with liquid water oceans, and witnessed the onset of plate tectonics and life. Quantifying the abundances, distribution, and chemical states of water in the atmosphere, on the surface, and in the interior of the early Earth is essential to constrain the early evolution of System Earth. Assessing these parameters is hampered by the general dearth of early Earth samples, the difficulty of distinguishing primary signatures from later alteration processes in such samples, leading to large uncertainties on the influx and outflux of water to and from the early Earth. Given the close proximity of Earth and Moon, constraints on the early hydrogen cycle in the Moon may reflect coeval aspects of the water cycle on early Earth. Here, we assess constraints on the lunar water cycle from the time the Moon formed until the end of late accretion at ~3.8 Ga, and implications of these constraints for the early Earth water budget. Dynamic accretion models suggest the Moon initially contained ~455 ppm of water. Recent experimental studies of lunar magma ocean crystallization suggest similarly substantial initial lunar water contents. Hydrogen concentration measurements in lunar plagioclase crystals derived from the magma ocean illustrate that the Moon experienced significant degassing during the solidification of the lunar magma ocean (thought to have occurred between 4.5 and ~ 4.3 Ga). Hydrogen and chlorine systematics in lunar magmatic apatite grains formed between ~4.1 Ga and ~ 3 Ga indicate that lunar hydrogen reservoirs were replenished by volatile delivery during late accretion (~4.1–3.8 Ga), after which the water abundance of the Moon stabilized. Using this knowledge of the lunar water cycle to model Earth's early water budget leads to two scenarios that are consistent with the observed present-day terrestrial water content of 1000–3000 ppm: (1) Earth contained significantly more water than the Moon-forming material immediately after the giant impact, suggesting hydrogen heterogeneity in the initial Earth-Moon system; (2) Earth did not experience significant degassing in the aftermath of the giant impact, and the late accretion mass added to Earth was large and water-rich

Evolution of the Earth’s atmosphere during Late Veneer accretion

ABSTRACT Recent advances in our understanding of the dynamical history of the Solar system have altered the inferred bombardment history of the Earth during accretion of the Late Veneer, after the Moon-forming impact. We investigate how the bombardment by planetesimals left-over from the terrestrial planet region after terrestrial planet formation, as well as asteroids and comets, affects the evolution of Earth’s early atmosphere. We develop a new statistical code of stochastic bombardment for atmosphere evolution, combining prescriptions for atmosphere loss and volatile delivery derived from hydrodynamic simulations and theory with results from dynamical modelling of realistic populations of impactors. We find that for an initially Earth-like atmosphere, impacts cause moderate atmospheric erosion with stochastic delivery of large asteroids, giving substantial growth (× 10) in a few ${{\ \rm per\ cent}}$ of cases. The exact change in atmosphere mass is inherently stochastic and dependent on the dynamics of the left-over planetesimals. We also consider the dependence on unknowns including the impactor volatile content, finding that the atmosphere is typically completely stripped by especially dry left-over planetesimals ($\lt 0.02 ~ {{\ \rm per\ cent}}$ volatiles). Remarkably, for a wide range of initial atmosphere masses and compositions, the atmosphere converges towards similar final masses and compositions, i.e. initially low-mass atmospheres grow, whereas massive atmospheres deplete. While the final properties are sensitive to the assumed impactor properties, the resulting atmosphere mass is close to that of current Earth. The exception to this is that a large initial atmosphere cannot be eroded to the current mass unless the atmosphere was initially primordial in composition.

Volcanically Induced Transient Atmospheres on the Moon: Assessment of Duration, Significance, and Contributions to Polar Volatile Traps

AbstractA transient lunar atmosphere formed during a peak period of volcanic outgassing and lasting up to about ~70 Ma was recently proposed. We utilize forward‐modeling of individual lunar basaltic eruptions and the observed geologic record to predict eruption frequency, magma volumes, and rates of volcanic volatile release. Typical lunar mare basalt eruptions have volumes of ~102–103 km3, last less than a year, and have a rapidly decreasing volatile release rate. The total volume of lunar mare basalts erupted is small, and the repose period between individual eruptions is predicted to range from 20,000 to 60,000 years. Only under very exceptional circumstances could sufficient volatiles be released in a single eruption to create a transient atmosphere with a pressure as large as ~0.5 Pa. The frequency of eruptions was likely too low to sustain any such atmosphere for more than a few thousand years. Transient, volcanically induced atmospheres were probably inefficient sources for volatile delivery to permanently shadowed lunar polar regions.

Setting the Stage: Planet Formation and Volatile Delivery

The diversity in mass and composition of planetary atmospheres stems from the different building blocks present in protoplanetary discs and from the different physical and chemical processes that these experience during the planetary assembly and evolution. This review aims to summarise, in a nutshell, the key concepts and processes operating during planet formation, with a focus on the delivery of volatiles to the inner regions of the planetary system.

Earths in Other Solar Systems’ N-body Simulations: The Role of Orbital Damping in Reproducing the Kepler Planetary Systems

Abstract The population of exoplanetary systems detected by Kepler provides opportunities to refine our understanding of planet formation. Unraveling the conditions needed to produce the observed exoplanet systems will allow us to make informed predictions as to where habitable worlds exist within the galaxy. In this paper, we examine, using N-body simulations, how the properties of planetary systems are determined during the final stages of assembly, when planets accrete from embryos and planetesimals. While accretion is a chaotic process, trends emerge allowing certain features of an ensemble of planetary systems to provide a memory of the initial distribution of solid mass around a star prior to accretion. We also use epos, the Exoplanet Population Observation Simulator, to account for detection biases and show that different accretion scenarios can be distinguished from observations of the Kepler systems. We show that the period of the innermost planet, the ratio of orbital periods of adjacent planets, and masses of the planets are determined by the total mass and radial distribution of embryos and planetesimals at the beginning of accretion. In general, some amount of orbital damping, via either planetesimals or gas, during accretion is needed to match the whole population of exoplanets. Surprisingly, all simulated planetary systems have planets that are similar in size, showing that the “peas in a pod” pattern can be consistent with both a giant impact scenario and a planet migration scenario. The inclusion of material at distances larger than what Kepler observes (>1 au) has a profound impact on the observed planetary architectures and thus on the formation and delivery of volatiles to possible habitable worlds.

Key Atmospheric Signatures for Identifying the Source Reservoirs of Volatiles in Uranus and Neptune

We investigate the enrichment patterns of several delivery scenarios of the volatiles to the atmospheres of ice giants, having in mind that the only well constrained determination made remotely, i.e. the carbon abundance measurement, suggests that their envelopes possess highly supersolar metallicities, i.e. close to two orders of magnitude above that of the protosolar nebula. In the framework of the core accretion model, only the delivery of volatiles in solid forms (amorphous ice, clathrates, pure condensates) to these planets can account for the apparent supersolar metallicity of their envelopes. In contrast, because of the inward drift of icy particles through various snowlines, all mechanisms invoking the delivery of volatiles in vapor forms predict subsolar abundances in the envelopes of Uranus and Neptune. Alternatively, even if the disk instability mechanism remains questionable in our solar system, it might be consistent with the supersolar metallicities observed in Uranus and Neptune, assuming the two planets suffered subsequent erosion of their H-He envelopes. The enrichment patterns derived for each delivery scenario considered should be useful to interpret future in situ measurements by atmospheric entry probes.

Identification of chondritic krypton and xenon in Yellowstone gases and the timing of terrestrial volatile accretion

Identifying the origin of noble gases in Earth's mantle can provide crucial constraints on the source and timing of volatile (C, N, H2O, noble gases, etc.) delivery to Earth. It remains unclear whether the early Earth was able to directly capture and retain volatiles throughout accretion or whether it accreted anhydrously and subsequently acquired volatiles through later additions of chondritic material. Here, we report high-precision noble gas isotopic data from volcanic gases emanating from, in and around, the Yellowstone caldera (Wyoming, United States). We show that the He and Ne isotopic and elemental signatures of the Yellowstone gas requires an input from an undegassed mantle plume. Coupled with the distinct ratio of 129Xe to primordial Xe isotopes in Yellowstone compared with mid-ocean ridge basalt (MORB) samples, this confirms that the deep plume and shallow MORB mantles have remained distinct from one another for the majority of Earth's history. Krypton and xenon isotopes in the Yellowstone mantle plume are found to be chondritic in origin, similar to the MORB source mantle. This is in contrast with the origin of neon in the mantle, which exhibits an isotopic dichotomy between solar plume and chondritic MORB mantle sources. The co-occurrence of solar and chondritic noble gases in the deep mantle is thought to reflect the heterogeneous nature of Earth's volatile accretion during the lifetime of the protosolar nebula. It notably implies that the Earth was able to retain its chondritic volatiles since its earliest stages of accretion, and not only through late additions.

Enrichment of the HR 8799 planets by minor bodies and dust

Context. In the Solar System, minor bodies and dust deliver various materials to planetary surfaces. Several exoplanetary systems are known to host inner and outer belts, analogues of the main asteroid belt and the Kuiper belt, respectively. Aims. We study the possibility that exominor bodies and exodust deliver volatiles and refractories to the exoplanets in the well-characterised system HR 8799. Methods. We performed N-body simulations to study the impact rates of minor bodies in the system HR 8799. The model consists of the host star, four giant planets (HR 8799 e, d, c, and b), 650 000 test particles representing the inner belt, and 1 450 000 test particles representing the outer belt. Moreover we modelled dust populations that originate from both belts. Results. Within a million years, the two belts evolve towards the expected dynamical structure (also derived in other works), where mean-motion resonances with the planets carve the analogues of Kirkwood gaps. We find that, after this point, the planets suffer impacts by objects from the inner and outer belt at rates that are essentially constant with time, while dust populations do not contribute significantly to the delivery process. We convert the impact rates to volatile and refractory delivery rates using our best estimates of the total mass contained in the belts and their volatile and refractory content. Over their lifetime, the four giant planets receive between 10−4 and 10−3 M⊕ of material from both belts. Conclusions. The total amount of delivered volatiles and refractories, 5 × 10−3 M⊕, is small compared to the total mass of the planets, 11 × 103 M⊕. However, if the planets were formed to be volatile-rich, their exogenous enrichment in refractory material may well be significant and observable, for example with JWST-MIRI. If terrestrial planets exist within the snow line of the system, volatile delivery would be an important astrobiological mechanism and may be observable as atmospheric trace gases.

The Earth’s core as a reservoir of water

Current estimates of the budget and distribution of water in the Earth have large uncertainties, most of which are due to the lack of information about the deep Earth. Recent studies suggest that the Earth could have gained a considerable amount of water during the early stages of its evolution from the hydrogen-rich solar nebula, and that a large amount of the water in the Earth may have partitioned into the core. Here we calculate the partitioning of water between iron and silicate melts at 20–135 GPa and 2,800–5,000 K, using ab initio molecular dynamics and thermodynamic integration techniques. Our results indicate a siderophile nature of water at core–mantle differentiation and core–mantle boundary conditions, which weakens with increasing temperature; nevertheless, we found that water always partitions strongly into the iron liquid under core-formation conditions for both reducing and oxidizing scenarios. The siderophile nature of water was also verified by an empirical-counting method that calculates the distribution of hydrogen in an equilibrated iron and silicate melt. We therefore conclude that the Earth’s core may act as a large reservoir that contains most of the Earth’s water. In addition to constraining the accretion models of volatile delivery, the findings may partially account for the low density of the Earth’s core implied by measured seismic velocities. The Earth’s core may host most of the planet’s water inventory, according to calculations of the partitioning behaviour of water at conditions of core formation.

An experimental assessment of the chalcophile behavior of F, Cl, Br and I: Implications for the fate of halogens during planetary accretion and the formation of magmatic ore deposits

The elemental and isotopic abundances of halogens (F, Cl, Br, I) are used to constrain planetary volatile loss and volatile delivery processes, but their behavior during magmatic differentiation in general, and sulfide liquid segregation in particular, is currently not well constrained. To test whether sulfide liquid segregation could affect halogen behavior during magmatic processes, we performed high-pressure experiments to systematically quantify the sulfide liquid – silicate melt partition coefficients (Dsulliq-silmelt values, defined as the ratio between the wt.% concentration of the halogen in the sulfide liquid and silicate melt, respectively) of F, Cl, Br and I at a pressure of 1 GPa and temperatures of 1683–1883 K.Results show that dry-polishing target surfaces is crucial for obtaining representative halogen concentrations of sulfide liquids. The results also show that no appreciable amounts of F partition into sulfide liquids, whereas Cl, Br and I behave increasingly chalcophile with increasing atomic radius (i.e., DFsulliq-silmelt <DClsulliq-silmelt <DBrsulliq-silmelt < DIsulliq-silmelt), presumably as a result of an increasingly covalent nature of Fe-halogen bonds with increasing radius. This results in I behaving chalcophile (DIsulliq-silmelt > 1) in several experiments. In contrast to previous observations, DCl/Brsulliq-silmelt was found to be <1. The DCl,Br,Isulliq-silmelt predominantly vary with sulfide liquid melt composition, showing an increase with increasing O in the sulfide liquid, which itself is correlated with more oxidizing conditions (i.e., higher fO2) or silicate melt FeO contents. The DCl,Br,Isulliq-silmelt values remain constant and/or potentially decrease again at the highest O concentrations of the sulfide liquids in this study (∼2.5 wt.% O).Results indicate that the magnitude of halogen depletions in the terrestrial, martian and lunar mantle are not strongly affected by segregation of sulfide liquids during their accretion, given the expected low modal abundance of sulfide liquids and/or relatively low DCl,Br,Isulliq-silmelt values. Core formation remains the most important process in establishing iodine depletion in the terrestrial mantle, whereas volatility-related loss seems most likely for F, Cl, Br and I, in case of the martian mantle. However, segregation of sulfide liquids during accretion could have resulted in a relative increase of the offset between the mantle depletions of the lighter and heavier halogens. The experimental results confirm the previously proposed feasibility of sulfide liquids as reservoirs for halogens in magmatic sulfide ore environments. As proposed by Mungall and Brenan (2003), fractional crystallization of these sulfide liquids in the absence of a silicate melt can lead to the formation of halide melts or fluids, consistent with the association between halide minerals and magmatic sulfide ores in some localities.

Measuring the D/H Ratios of Exoplanets and Brown Dwarfs

Abstract The relative abundance of deuterium and hydrogen is a potent tracer of planet formation and evolution. Jupiter and Saturn have protosolar atmospheric D/H ratios, a relic of substantial gas accretion from the nebula, while the atmospheres of Neptune and Uranus are enhanced in D by accretion of ices into their envelopes. For terrestrial planets, D/H ratios are used to determine the mechanisms of volatile delivery and subsequent atmosphere loss over the lifetime of the planet. Planets and brown dwarfs more massive than ∼13 M J quickly fuse their initial D reservoir. Here, we simulate spectra for giant exoplanets and brown dwarfs (2 M Neptune to ∼10 M Jupiter) from T eff = 200–1800 K including both CH3D and HDO to determine the observability of these dominant deuterium isotopologues in mid-infrared thermal emission spectra. Colder objects have stronger molecular features in their spectra, due to the temperature dependence of molecular cross sections. CH3D is easier to observe than HDO at all temperatures considered, due to the strength of its absorption bands and locations of features at wavelengths with few other strong absorption features. We predict that for nearby cool brown dwarfs, the CH3D abundance can be measured at high signal to noise with the James Webb Space Telescope (JWST); for objects from 200 to 800 K closer than 10 pc, a protosolar D/H ratio would be readily observable in 2.5 hr. Moderately young Jupiter-mass planets (100–300 Myr) and young Neptunes (10 Myr) may be discovered with JWST and provide the best targets for detecting deuterium on an exoplanet in the coming decade. Future telescope designs should consider the importance of isotopes for understanding the formation and evolution of planetary atmospheres.

Selenium isotopes as tracers of a late volatile contribution to Earth from the outer Solar System.

The origin of Earth’s volatiles has been attributed to a late addition of meteoritic material after core-mantle differentiation. The nature and consequences of this 'late veneer' are debated, but may be traced by isotopes of the highly siderophile, or iron-loving, and volatile element selenium. Here we present high-precision selenium isotope data for mantle peridotites, from double spike and hydride generation multi-collector inductively coupled plasma mass spectrometry. These data indicate that the selenium isotopic composition of peridotites is unaffected by petrological processes, such as melt depletion and melt-rock reaction, and thus a narrow range is preserved that is representative of the silicate Earth. We show that selenium isotopes record a signature of late accretion after core formation and that this signature overlaps only with that of the CI-type carbonaceous chondrites. We conclude that these isotopic constraints indicate the late veneer originated from the outer Solar System and was of lower mass than previously estimated. Thus, we suggest a late and highly concentrated delivery of volatiles enabled Earth to become habitable.