A hybrid origin for the Martian atmosphere
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Abstract

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![]() Figure 1 The captured gas inventory (MH) as a function of the outgassed inventory (MCO2) for fully-mixed hybrid atmospheres. Curves correspond to different accretion rates in units of Mars masses per million years (M-m/Myr) and therefore to different planetary luminosities. “Pure nebular capture” (dotted lines) refers to nebular atmospheres with no outgassed component (MCO2 = 0) shown for reference and comparable to earlier calculations (Erkaev et al., 2014). Mixing with a high molecular weight component enhances nebular capture with the magnitude of the enhancement dependent on the mixed-in heavy gas inventory. The closeness of the solid line slopes to unity indicates the near constant proportion of nebular to chondritic gases in the model atmospheres. The four data points along each curve correspond to a range of mean molecular weights characterising fully-mixed hybrid atmospheres. | ![]() Figure 2 Mixtures of chondritic and solar composition gases make specific predictions for the provenance of elements deriving from each component. The krypton isotopic composition of the Martian atmosphere – like solar and distinct from chondrites (Pepin, 1991; Conrad et al., 2016) – suggests the nebular contribution to the primordial Martian atmosphere was >10 % counting atoms. Upper limits on the contribution of the nebular component to Martian volatiles derive from the physics of nebular capture into fully-mixed hybrid atmospheres and are <46–77 % (see Fig. 1). Neon is not plotted for clarity but like Ar is derived almost entirely from the nebular component in fully-mixed hybrid atmospheres. Data used to make this plot are given in Table S-1. | ![]() Figure 3 Relative abundances of volatile elements in mixtures of chondritic and solar composition gases normalised to krypton and to solar composition. Percentages refer to the fraction of total atoms in the mixture contributed by the solar component. Mixtures with varying proportions of the nebular component can be compared to the composition of the present day Martian atmosphere and differences between the two compositions used to infer the imprint of loss processes. The similarity of cyan, blue, and magenta curves attests to a well-constrained initial composition for the hybrid atmosphere. | ![]() Figure 4 Mass-dependent fractionation accompanying argon loss from the hybrid Mars atmosphere. The solid lines show the isotopic composition of an atmosphere after Rayleigh distillation leading to 98 % Ar loss driven by hydrodynamic escape, for various nebular to chondritic proportions (H2/CO2), starting with solar Ar (36Ar/38Ar = 5.5). The efficiency factor is a proxy for mass loss rate. Preservation of solar-like isotopic Kr requires krypton non-participation in the mass fractionating outflow and sets upper limits on the efficiency factor. The existence of solutions sufficiently vigorous to produce 50x reductions in Ar/Kr (see Fig. 3) without excessive Ar (and no Kr) isotopic fractionation indicates the viability of a hybrid mixture as the initial composition of the Martian atmosphere. |
Figure 1 | Figure 2 | Figure 3 | Figure 4 |
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Introduction
Mars has recently emerged as a natural laboratory for studying the acquisition and processing of volatile elements on the terrestrial planets. Because undifferentiated building blocks of terrestrial planets were likely volatile-bearing (Schaefer and Fegley, 2017
Schaefer, L., Fegley Jr., B. (2017) Redox States of Initial Atmospheres Outgassed on Rocky Planets and Planetesimals. The Astrophysical Journal 843, 120. https://doi.org/10.3847/1538-4357/aa784f
) and Martian accretion likely occurred in the presence of the solar nebula (Dauphas and Pourmand, 2011Dauphas, N., Pourmand, A. (2011) Hf-W-Th evidence for rapid growth of Mars and its status as a planetary embryo. Nature 473, 489–U227. https://doi.org/10.1038/nature10077
), questions about different volatile sources and formation processes for the primordial Martian atmosphere can now be addressed (Saito and Kuramoto, 2018Saito, H., Kuramoto, K. (2018) Formation of a hybrid-type proto-atmosphere on Mars accreting in the solar nebula. Monthly Notices of the Royal Astronomical Society 475, 1274–1287. https://doi.org/10.1093/mnras/stx3176
; Péron and Mukhopadhyay, 2022Péron, S., Mukhopadhyay, S. (2022) Krypton in the Chassigny meteorite shows Mars accreted chondritic volatiles before nebular gases. Science 377, 320–324. https://doi.org/10.1126/science.abk1175
). High precision isotopic measurements display a dichotomy in the sources of Martian volatiles. Volatiles dissolved in melts derived from the Martian mantle are observed to have an isotopic composition akin to chondrites for hydrogen, nitrogen, krypton and xenon (Usui, 2019Usui, T. (2019) Hydrogen reservoirs in Mars as revealed by martian meteorites, Volatiles in the Martian Crust. Elsevier, 71–88. https://doi.org/10.1016/B978-0-12-804191-8.00004-0
; Péron and Mukhopadhyay, 2022Péron, S., Mukhopadhyay, S. (2022) Krypton in the Chassigny meteorite shows Mars accreted chondritic volatiles before nebular gases. Science 377, 320–324. https://doi.org/10.1126/science.abk1175
; Deligny et al., 2023Deligny, C., Füri, E., Deloule, E., Peslier, A., Faure, F., Marrocchi, Y. (2023) Origin of nitrogen on Mars: First in situ N isotope analyses of martian meteorites. Geochimica et Cosmochimica Acta 344, 134–145. https://doi.org/10.1016/j.gca.2023.01.017
) whereas the isotopic composition of krypton and xenon in the Martian atmosphere – which do not currently experience escape – record a solar-like source (Pepin, 1991Pepin, R.O. (1991) On the origin and early evolution of terrestrial planet atmospheres and meteoritic volatiles. Icarus 92, 2–79. https://doi.org/10.1016/0019-1035(91)90036-S
; Conrad et al., 2016Conrad, P.G., Malespin, C.A., Franz, H.B., Pepin, R.O., Trainer, M.G., Schwenzer, S.P., Atreya, S., Freissinet, C., Jones, J., Manning, H. (2016) In situ measurement of atmospheric krypton and xenon on Mars with Mars Science Laboratory. Earth and Planetary Science Letters 454, 1–9. https://doi.org/10.1016/j.epsl.2016.08.028
). These observations prompt questions about the relationship between Martian interior and atmospheric volatiles.The volatile dichotomy between a chondrite-like mantle and a solar-like atmosphere has recently been interpreted to mean that the Martian atmosphere cannot be the result of magma ocean outgassing and must be the result of nebular capture (Péron and Mukhopadhyay, 2022
Péron, S., Mukhopadhyay, S. (2022) Krypton in the Chassigny meteorite shows Mars accreted chondritic volatiles before nebular gases. Science 377, 320–324. https://doi.org/10.1126/science.abk1175
). There is, however, empirical evidence that silicate Mars experienced outgassing during the lifetime of the short-lived and volatile radionuclide 129I (τ1/2 = 16 Myr), resulting in the observed 129Xe depletion in Martian interior reservoirs (Marty and Marti, 2002Marty, B., Marti, K. (2002) Signatures of early differentiation of Mars. Earth and Planetary Science Letters 196, 251–263. https://doi.org/10.1016/S0012-821X(01)00612-4
). Early selective removal of volatile elements from silicate Mars – for example via outgassing from a molten state (Elkins-Tanton, 2008Elkins-Tanton, L.T. (2008) Linked magma ocean solidification and atmospheric growth for Earth and Mars. Earth and Planetary Science Letters 271, 181–191. https://doi.org/10.1016/j.epsl.2008.03.062
) – points towards transport of chondritic volatiles into the primordial atmosphere. Although this episode of primordial outgassing is empirically supported, it has yet to be reconciled with the observed dichotomy between the Martian interior and atmospheric volatiles (Péron and Mukhopadhyay, 2022Péron, S., Mukhopadhyay, S. (2022) Krypton in the Chassigny meteorite shows Mars accreted chondritic volatiles before nebular gases. Science 377, 320–324. https://doi.org/10.1126/science.abk1175
). Here, we consider hybrid accretionary atmospheres (Saito and Kuramoto, 2018Saito, H., Kuramoto, K. (2018) Formation of a hybrid-type proto-atmosphere on Mars accreting in the solar nebula. Monthly Notices of the Royal Astronomical Society 475, 1274–1287. https://doi.org/10.1093/mnras/stx3176
) in which an outgassed high molecular weight gas is mixed into the distended low molecular weight nebular atmosphere. We show that such mixing can reconcile primordial outgassing of chondritic volatiles with nebular capture of solar-like gases into the Martian atmosphere, that mixing before dissipation of the solar nebula strongly enhances the mass of nebular captured gas, and that comparison of hybrid-source compositions with that of the present day atmosphere can yield new insights into the history of Martian atmospheric evolution. As an example, the hybrid origin model implies that most Martian argon loss occurred primordially rather than during subsequent geologic epochs as commonly assumed. We show that a hybrid initial composition is a viable initial condition for understanding Martian atmospheric history.top
Model and Results
Enhancement of nebular capture via mixing. We calculate structures for dusty (Eq. S-4) captured Martian atmospheres present during accretion in hydrostatic equilibrium and thermal steady state with the solar nebula. We consider atmospheres both with and without mixing of an outgassed high mean molecular weight layer (see Supplementary Information for discussion of the energetics of mixing via thermal convection). Atmospheres without a high molecular weight component are called “pure” and are presented as a reference. The atmospheres are convective at depth and radiative at altitude, and are assumed to blend into the solar nebula at the Hill radius at ≈320 Mars radii. Because the mass (and heat capacity) of these atmospheres is relatively small, a heat source other than secular cooling is needed to calculate quasi-static structures. An absolute lower limit on the heat flow derives from long-lived radioactive decay and is equivalent to accretion rates ≈10−4 Mars masses/Myr (Erkaev et al., 2014
Erkaev, N., Lammer, H., Elkins-Tanton, L., Stökl, A., Odert, P., Marcq, E., Dorfi, E., Kislyakova, K., Kulikov, Y.N., Leitzinger, M. (2014) Escape of the martian protoatmosphere and initial water inventory. Planetary and Space Science 98, 106–119. https://doi.org/10.1016/j.pss.2013.09.008
). More likely heat flows relevant to the first few million years of Martian history derive from ongoing planetesimal accretion – which also delivers high molecular weight volatiles – and/or 26Al decay. We consider heat flows at the base of the atmosphere equivalent to planetesimal accretion rates of 0.01–1 Mars masses/Myr (Eq. S-1), covering the range from energetic accretion consistent with large-scale melting (Dauphas and Pourmand, 2011Dauphas, N., Pourmand, A. (2011) Hf-W-Th evidence for rapid growth of Mars and its status as a planetary embryo. Nature 473, 489–U227. https://doi.org/10.1038/nature10077
) down to reduced heat flows unable to maintain a magma ocean (Saito and Kuramoto, 2018Saito, H., Kuramoto, K. (2018) Formation of a hybrid-type proto-atmosphere on Mars accreting in the solar nebula. Monthly Notices of the Royal Astronomical Society 475, 1274–1287. https://doi.org/10.1093/mnras/stx3176
) and more consistent with sweep-up of planetesimals during the waning stages of accretion. For heat flows equivalent to accretion rates of 0.01–1 Mars masses/Myr, the mass (MH) of a “pure” nebular captured atmosphere is ≈0.2–3.1 x 1018 kg and equivalent to ≈0.05–0.8 bars of H2 at the Mars surface (Fig. 1). Lower accretion rates produce cooler, denser atmospheres that are more massive, a behaviour summarised with the maxim: “to cool is to accrete” (Lee and Chiang, 2015Lee, E.J., Chiang, E. (2015) To cool is to accrete: analytic scalings for nebular accretion of planetary atmospheres. The Astrophysical Journal 811, 41. https://doi.org/10.1088/0004-637X/811/1/41
).
Figure 1 The captured gas inventory (MH) as a function of the outgassed inventory (MCO2) for fully-mixed hybrid atmospheres. Curves correspond to different accretion rates in units of Mars masses per million years (M-m/Myr) and therefore to different planetary luminosities. “Pure nebular capture” (dotted lines) refers to nebular atmospheres with no outgassed component (MCO2 = 0) shown for reference and comparable to earlier calculations (Erkaev et al., 2014
Erkaev, N., Lammer, H., Elkins-Tanton, L., Stökl, A., Odert, P., Marcq, E., Dorfi, E., Kislyakova, K., Kulikov, Y.N., Leitzinger, M. (2014) Escape of the martian protoatmosphere and initial water inventory. Planetary and Space Science 98, 106–119. https://doi.org/10.1016/j.pss.2013.09.008
). Mixing with a high molecular weight component enhances nebular capture with the magnitude of the enhancement dependent on the mixed-in heavy gas inventory. The closeness of the solid line slopes to unity indicates the near constant proportion of nebular to chondritic gases in the model atmospheres. The four data points along each curve correspond to a range of mean molecular weights characterising fully-mixed hybrid atmospheres.Mixing of the nebular atmosphere with an outgassed high molecular weight gas – for which there is sufficient energy (Eq. S-13) – sharply enhances the mass of the captured gas inventory. To illustrate the magnitude of this effect, we calculate the structure of hybrid-source atmospheres in which the outgassed component (μCO2 = 44 amu with an inventory size characterised by MCO2) and the nebular component (μH = 2.4 amu with an inventory size characterised by MH) are assumed to be fully-mixed into a homogenous atmosphere (see equations S-1 to S-3 and S-7 to S-12 in the Supplementary Information). To find solutions, we take the mean molecular weight of the mixture as a free parameter, varying it across a range (μ = 6.6–19 amu) that allows sampling of the solution space. When a well-mixed hybrid atmosphere hydrostatically equilibrates with the solar nebula and achieves thermal steady state, the mass of the captured inventory (MH) strongly depends on the inventory of the high molecular weight gas (MCO2) with which it is mixed (see Gas-assisted capture; Fig. 1). For planetesimal accretion rates of 0.01–1 Mars masses/Myr and heavy gas inventories (MCO2 = 3.9–390 x 1019 kg) equivalent to 10–1000 bars of CO2 at the planetary surface (Elkins-Tanton, 2008
Elkins-Tanton, L.T. (2008) Linked magma ocean solidification and atmospheric growth for Earth and Mars. Earth and Planetary Science Letters 271, 181–191. https://doi.org/10.1016/j.epsl.2008.03.062
), the captured nebular inventory (MH) is in the range of 1.2–120 x 1019 kg, equivalent to ≈3–300 bars of H2 at the surface (Fig. 1). The strong enhancement of nebular capture via mixing an outgassed component is mainly due to an increase in mean molecular weight, which increases the gravitational coupling between the atmosphere and planet and decreases the atmospheric scale height, which – like cooling – causes contraction and an increase in the hydrogen density of the lower atmosphere where most of the atmospheric mass resides. This behaviour can be summarised with another maxim: “to mix is to accrete.”The dependence of the nebular captured inventory (MH) on the outgassed inventory (MCO2) in fully-mixed hybrid-source atmospheres (Fig. 1, and Eqs. S-11 and S-12) sets upper limits on the contribution of the nebular component to the Martian atmosphere. A measure of the relative contribution of captured and outgassed inventories is the mean molecular weight of the mixture, which only varies by a factor of ∼three for the full range of conditions that we consider (Fig. 1). Although the mass of the outgassed component is dominated by carbon species (e.g., CO2), other outgassed volatiles (H, N, and noble gases) were also present and the elemental abundances and isotopic composition of the hybrid mixture can be used – in comparison with observed abundances – to further constrain the nebular contribution to Martian volatiles. Whereas the physics of nebular capture into fully-mixed hybrid atmospheres yields upper limits on the nebular contribution, lower limits can be derived from the cosmochemistry of chondritic-nebular gas mixtures, as we show in the following section.
Chondritic-nebular gas mixtures. To describe cosmochemical consequences of mixing a nebular component into an outgassed atmosphere, we calculate two-component mixtures including major volatiles (H, C, N) and noble gases (Ne, Ar, Kr, Xe) with chondritic and nebular end members. We neglect He because – like He in Earth’s atmosphere – the lifetime of this noble gas with respect to escape from the Martian atmosphere is extremely short relative to geological time scales and its present day abundance simply reflects a balance between recent supply and loss (Krasnopolsky et al., 1994
Krasnopolsky, V., Bowyer, S., Chakrabarti, S., Gladstone, G., Mcdonald, J. (1994) First measurement of helium on Mars: Implications for the problem of radiogenic gases on the terrestrial planets. Icarus 109, 337–351. https://doi.org/10.1006/icar.1994.1098
). For the chondritic end member, we adopt the 55 % H chondrite, 45 % EH chondrite model for Mars (Sanloup et al., 1999Sanloup, C., Jambon, A., Gillet, P. (1999) A simple chondritic model of Mars. Physics of the Earth and Planetary Interiors 112, 43–54. https://doi.org/10.1016/S0031-9201(98)00175-7
). For the purposes of the mixing calculations, we include all chondritic volatiles (interior and outgassed), although a substantial fraction of chondritic H (or “water”) is expected to remain sequestered in the interior (Sim et al., 2024Sim, S.J., Hirschmann, M.M., Hier‐Majumder, S. (2024) Volatile and trace element storage in a crystallizing martian magma ocean. Journal of Geophysical Research: Planets 129, e2024JE008346. https://doi.org/10.1029/2024JE008346
). The assumption of complete outgassing may be more accurate for C, N, and the noble gases. With end member compositions specified, the composition of the mixture can be described with one parameter, the relative contribution of the two components.The compositional characteristics of a nebular-chondritic mixture can be calculated for comparison with the observed atmospheric abundances. For “Gas-assisted capture” (Fig. 1), representing fully-mixed hybrid-sourced atmospheres in hydrostatic equilibrium with the solar nebula, the nebular contribution to the total volatile budget of Mars, counting atoms, is ≈46–77 %, depending on the accretion rate and outgassed volatile inventory. The total volatile budget is dominated by H and He from the nebular component and H and C from the chondritic component. For these relative proportions of the nebular component to the hybrid mixture, the neon (>99 %), argon (>99 %) and krypton (>90 %) inventories are dominated by the nebular component, whereas carbon (<1 %) and nitrogen (<2 %) inventories experience negligible nebular additions and continue to be dominated by the outgassed component (Fig. 2). Hydrogen and xenon are intermediate cases in which the inventories in the mixture are derived from comparable contributions from the two sources. In summary, nebular capture via complete mixing into a hybrid-source atmosphere produces Martian Ne, Ar and Kr with solar heritage, C and N with chondritic heritage, and H and Xe with mixed heritage.

Figure 2 Mixtures of chondritic and solar composition gases make specific predictions for the provenance of elements deriving from each component. The krypton isotopic composition of the Martian atmosphere – like solar and distinct from chondrites (Pepin, 1991
Pepin, R.O. (1991) On the origin and early evolution of terrestrial planet atmospheres and meteoritic volatiles. Icarus 92, 2–79. https://doi.org/10.1016/0019-1035(91)90036-S
; Conrad et al., 2016Conrad, P.G., Malespin, C.A., Franz, H.B., Pepin, R.O., Trainer, M.G., Schwenzer, S.P., Atreya, S., Freissinet, C., Jones, J., Manning, H. (2016) In situ measurement of atmospheric krypton and xenon on Mars with Mars Science Laboratory. Earth and Planetary Science Letters 454, 1–9. https://doi.org/10.1016/j.epsl.2016.08.028
) – suggests the nebular contribution to the primordial Martian atmosphere was >10 % counting atoms. Upper limits on the contribution of the nebular component to Martian volatiles derive from the physics of nebular capture into fully-mixed hybrid atmospheres and are <46–77 % (see Fig. 1). Neon is not plotted for clarity but like Ar is derived almost entirely from the nebular component in fully-mixed hybrid atmospheres. Data used to make this plot are given in Table S-1.A hybrid primordial mixture is consistent with the observed isotopic composition of the Martian atmosphere. Mass-selective loss has fractionated stable Ar isotopes (36Ar from 38Ar) but a solar-like source is a viable starting composition for atmospheric argon (Atreya et al., 2013
Atreya, S.K., Trainer, M.G., Franz, H.B., Wong, M.H., Manning, H.L., Malespin, C.A., Mahaffy, P.R., Conrad, P.G., Brunner, A.E., Leshin, L.A. (2013) Primordial argon isotope fractionation in the atmosphere of Mars measured by the SAM instrument on Curiosity and implications for atmospheric loss. Geophysical Research Letters 40, 5605–5609. https://doi.org/10.1002/2013GL057763
). Krypton in the atmosphere is distinct from chondrites but nearly indistinguishable from solar (Pepin, 1991Pepin, R.O. (1991) On the origin and early evolution of terrestrial planet atmospheres and meteoritic volatiles. Icarus 92, 2–79. https://doi.org/10.1016/0019-1035(91)90036-S
; Conrad et al., 2016Conrad, P.G., Malespin, C.A., Franz, H.B., Pepin, R.O., Trainer, M.G., Schwenzer, S.P., Atreya, S., Freissinet, C., Jones, J., Manning, H. (2016) In situ measurement of atmospheric krypton and xenon on Mars with Mars Science Laboratory. Earth and Planetary Science Letters 454, 1–9. https://doi.org/10.1016/j.epsl.2016.08.028
). Atmospheric xenon can be modelled either as mass-fractionated solar or mass-fractionated chondritic gas (Swindle, 2002Swindle, T.D. (2002) Martian noble gases. Reviews in Mineralogy and Geochemistry 47, 171–190. https://doi.org/10.2138/rmg.2002.47.6
). Although the physics of nebular capture into fully-mixed hybrid atmospheres sets upper limits on the nebular contribution (<46–77 %), partial mixing could yield a lower nebular contribution. The requirement that Martian Kr be nearly indistinguishable from solar but distinct from chondrites constrains the nebular contribution to the total Martian volatile budget to >10 %, counting atoms (Fig. 2). Next, we consider the consequences of primordial hybrid mixtures for inferring Martian atmospheric history.Elemental abundances elucidate escape processes. Of all the major volatiles (H, C, N) and noble gases (Ne, Ar, Kr, Xe) we consider, krypton is most nearly isotopically unfractionated in Mars’s atmosphere relative to its apparent source, the solar nebula. Accordingly, to gain insight into the nature of evolutionary processes, we consider elemental abundances normalised to krypton and relative to solar abundances. Hybrid-source elemental abundances have some affinity to modern Mars (Fig. 3), with important differences. Relative to hybrid-source mixtures, the modern Martian atmosphere is depleted in H, C, N, Ne, Ar, and Xe, each of which is also enriched in the heavy isotopes in the Martian atmosphere (Bogard et al., 2001
Bogard, D., Clayton, R., Marti, K., Owen, T., Turner, G. (2001) Martian volatiles: Isotopic composition, origin, and evolution. Chronology and Evolution of Mars: Proceedings of an ISSI Workshop, 10–14 April 2000, Bern, Switzerland. Springer. https://doi.org/10.1007/978-94-017-1035-0_17
). Such coupled elemental and isotopic fractionation suggests the viability of a hybrid-source mixture as a precursor to the modern Martian atmosphere, the two being linked via compositional evolutionary processes, among which mass-selective losses to space looms large.
Figure 3 Relative abundances of volatile elements in mixtures of chondritic and solar composition gases normalised to krypton and to solar composition. Percentages refer to the fraction of total atoms in the mixture contributed by the solar component. Mixtures with varying proportions of the nebular component can be compared to the composition of the present day Martian atmosphere and differences between the two compositions used to infer the imprint of loss processes. The similarity of cyan, blue, and magenta curves attests to a well-constrained initial composition for the hybrid atmosphere.
We consider elemental (36Ar/84Kr) and isotopic (36Ar/38Ar) fractionation accompanying argon loss. Argon is suitable for examining ancient processes because the inventory of atmospheric 36Ar is primordial meaning it cannot be accounted for by volcanic outgassing over time (Jakosky and Treiman, 2023
Jakosky, B.M., Treiman, A.H. (2023) Mars volatile inventory and outgassing history. Icarus 402, 115627. https://doi.org/10.1016/j.icarus.2023.115627
). The non-radiogenic Ar/Kr ratio in the modern Martian atmosphere is lower than that of a hybrid mixture by a factor of ≈50 (Fig. 3) whereas the 36Ar/38Ar is lower than plausible sources by ≈25 % (Atreya et al., 2013Atreya, S.K., Trainer, M.G., Franz, H.B., Wong, M.H., Manning, H.L., Malespin, C.A., Mahaffy, P.R., Conrad, P.G., Brunner, A.E., Leshin, L.A. (2013) Primordial argon isotope fractionation in the atmosphere of Mars measured by the SAM instrument on Curiosity and implications for atmospheric loss. Geophysical Research Letters 40, 5605–5609. https://doi.org/10.1002/2013GL057763
). A loss process that strongly separates Ar from Kr but weakly discriminates 36Ar from 38Ar is indicated. We consider an episode of extreme ultraviolet (EUV) powered hydrodynamic escape in which an outflow of H2 and CO2 entrains trace gases via frequent collisions (Zahnle et al., 1990Zahnle, K., Kasting, J.F., Pollack, J.B. (1990) Mass fractionation of noble gases in diffusion-limited hydrodynamic hydrogen escape. Icarus 84, 502–527. https://doi.org/10.1016/0019-1035(90)90050-J
). Entrainment involves all trace gases up to a maximum molecular mass whose value depends on the strength of the flow (See Eq. S-16 for details). Results reveal the existence of a hydrodynamic outflow sufficiently strong to reproduce the chemical (Ar/Kr) and isotopic (36Ar/38Ar) fractionation observed in the Martian atmosphere starting from a hybrid mixture while remaining sufficiently weak to allow Kr to be retained and its solar isotopic heritage to be preserved (Fig. 4). Of course, mass-selective argon loss from Mars via other mechanisms (e.g., solar wind sputtering) occurs and is ongoing (Jakosky et al., 2017Jakosky, B.M., Slipski, M., Benna, M., Mahaffy, P., Elrod, M., Yelle, R., Stone, S., Alsaeed, N. (2017) Mars’ atmospheric history derived from upper-atmosphere measurements of 38Ar/36Ar. Science 355, 1408–1410. https://doi.org/10.1126/science.aai7721
). The hybrid mixture model provides a framework for assessing the relative importance of various mechanisms of atmospheric loss over the entire history of the planet.
Figure 4 Mass-dependent fractionation accompanying argon loss from the hybrid Mars atmosphere. The solid lines show the isotopic composition of an atmosphere after Rayleigh distillation leading to 98 % Ar loss driven by hydrodynamic escape, for various nebular to chondritic proportions (H2/CO2), starting with solar Ar (36Ar/38Ar = 5.5). The efficiency factor is a proxy for mass loss rate. Preservation of solar-like isotopic Kr requires krypton non-participation in the mass fractionating outflow and sets upper limits on the efficiency factor. The existence of solutions sufficiently vigorous to produce 50x reductions in Ar/Kr (see Fig. 3) without excessive Ar (and no Kr) isotopic fractionation indicates the viability of a hybrid mixture as the initial composition of the Martian atmosphere.
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Discussion
The origin of the Martian hydrosphere. A significant feature of the Martian volatile record is that the surface hydrosphere inferred by geomorphology – like the atmospheric 36Ar reservoir – cannot be generated via volcanic outgassing over time (Jakosky and Treiman, 2023
Jakosky, B.M., Treiman, A.H. (2023) Mars volatile inventory and outgassing history. Icarus 402, 115627. https://doi.org/10.1016/j.icarus.2023.115627
). The hydrosphere was apparently placed on the Martian surface early in planetary history. Independent evidence for the existence of a Martian surface hydrosphere in the first 100 Myr comes from an excess of 129Xe in the atmosphere from the decay of water soluble and short-lived 129I (Musselwhite et al., 1991Musselwhite, D.S., Drake, M.J., Swindle, T.D. (1991) Early outgassing of Mars supported by differential water solubility of iodine and xenon. Nature 352, 697–699. https://doi.org/10.1038/352697a0
). The hybrid origin model suggests a new mechanism for the formation of a Martian hydrosphere, similar to the generic scenario recently explored in Kimura and Ikoma (2020)Kimura, T., Ikoma, M. (2020) Formation of aqua planets with water of nebular origin: effects of water enrichment on the structure and mass of captured atmospheres of terrestrial planets. Monthly Notices of the Royal Astronomical Society 496, 3755–3766. https://doi.org/10.1093/mnras/staa1778
. Although we have considered the nebular and chondritic gases to be chemically inert, the nebular gas can react with outgassed oxides to produce new water (H2 + CO2 →H2O + CO). If the CO thus produced escapes as CO, there is a net gain of water at the Martian surface. Both the strong D/H enrichment of the early hydrosphere (Greenwood et al., 2008Greenwood, J.P., Itoh, S., Sakamoto, N., Vicenzi, E.P., Yurimoto, H. (2008) Hydrogen isotope evidence for loss of water from Mars through time. Geophysical Research Letters 35. https://doi.org/10.1029/2007GL032721
) and the anomalous oxygen recorded in ∼4.43 billion year old zircons (Nemchin et al., 2014Nemchin, A., Humayun, M., Whitehouse, M., Hewins, R., Lorand, J., Kennedy, A., Grange, M., Zanda, B., Fieni, C., Deldicque, D. (2014) Record of the ancient martian hydrosphere and atmosphere preserved in zircon from a martian meteorite. Nature Geoscience 7, 638–642. https://doi.org/10.1038/ngeo2231
) may result from isotopic exchange between a hydrosphere and an escaping H2-dominated atmosphere (Pahlevan et al., 2022Pahlevan, K., Schaefer, L., Elkins-Tanton, L.T., Desch, S.J., Buseck, P.R. (2022) A primordial atmospheric origin of hydrospheric deuterium enrichment on Mars. Earth and Planetary Science Letters 595, 117772. https://doi.org/10.1016/j.epsl.2022.117772
; Zahnle and Kasting, 2023Zahnle, K.J., Kasting, J.F. (2023) Elemental and isotopic fractionation as fossils of water escape from Venus. Geochimica et Cosmochimica Acta 361, 228–244. https://doi.org/10.1016/j.gca.2023.09.023
).Cometary contribution to the inner Solar System. The low C/36Ar and N/36Ar of the Martian atmosphere relative to chondrites (Fig. 3) has previously been attributed to a possible contribution from Ar-rich comets (Marty et al., 2016
Marty, B., Avice, G., Sano, Y., Altwegg, K., Balsiger, H., Hässig, M., Morbidelli, A., Mousis, O., Rubin, M. (2016) Origins of volatile elements (H, C, N, noble gases) on Earth and Mars in light of recent results from the ROSETTA cometary mission. Earth and Planetary Science Letters 441, 91–102. https://doi.org/10.1016/j.epsl.2016.02.031
). However, a cometary origin introduces some problems even as it solves others. Results from the Rosetta mission allowed the identification of cometary xenon as a likely source for terrestrial xenon, in particular the long hypothesised component called U-Xe that is apparent in the atmosphere of Earth but not Mars (Marty et al., 2017Marty, B., Altwegg, K., Balsiger, H., Bar-Nun, A., Bekaert, D.V., et al. (2017) Xenon isotopes in 67P/Churyumov-Gerasimenko show that comets contributed to Earth’s atmosphere. Science 356, 1069–1072. https://doi.org/10.1126/science.aal3496
). Assuming comet 67P/Churyumov-Gerasimenko – which Rosetta sampled – is representative of the cometary reservoir, the question arises as to why Martian atmospheric xenon does not record the cometary signature. The resolution to this dilemma may be the retention of volatiles during impacts onto Earth and Mars. Cometary impacts onto terrestrial planets are high velocity events sufficiently energetic to vapourise both icy and silicate components, producing vapour plumes. The fate of vapour plumes (retained or lost) depends on the ratio of impact to escape velocity, such that cometary vapour plumes on Earth tend to be gravitationally retained whereas those on Mars tend to disperse (Zahnle, 1993Zahnle, K.J. (1993) Xenological constraints on the impact erosion of the early Martian atmosphere. Journal of Geophysical Research: Planets 98, 10899–10913. https://doi.org/10.1029/92JE02941
). More work is needed to better understand the role of various escape processes in sculpting the volatile inventory of the terrestrial planets.top
Acknowledgements
The authors acknowledge discussions with Sujoy Mukhopadhyay, comments on an early draft from Alessandro Morbidelli and James Lyons, and extensive reviews by Kevin Zahnle and an anonymous referee, which improved the manuscript. KP acknowledges support from NASA’s Solar System Workings Program (80NSSC21K1833).
Editor: Helen Williams
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References
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Mass-selective loss has fractionated stable Ar isotopes (36Ar from 38Ar) but a solar-like source is a viable starting composition for atmospheric argon (Atreya et al., 2013).
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The non-radiogenic Ar/Kr ratio in the modern Martian atmosphere is lower than that of a hybrid mixture by a factor of ≈50 (Fig. 3) whereas the 36Ar/38Ar is lower than plausible sources by ≈25 % (Atreya et al., 2013).
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Relative to hybrid-source mixtures, the modern Martian atmosphere is depleted in H, C, N, Ne, Ar, and Xe, each of which is also enriched in the heavy isotopes in the Martian atmosphere (Bogard et al., 2001).
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Volatiles dissolved in melts derived from the Martian mantle are observed to have an isotopic composition akin to chondrites for hydrogen, nitrogen, krypton and xenon (Usui, 2019; Péron and Mukhopadhyay, 2022; Deligny et al., 2023) whereas the isotopic composition of krypton and xenon in the Martian atmosphere – which do not currently experience escape – record a solar-like source (Pepin, 1991; Conrad et al., 2016).
View in article
The krypton isotopic composition of the Martian atmosphere – like solar and distinct from chondrites (Pepin, 1991; Conrad et al., 2016) – suggests the nebular contribution to the primordial Martian atmosphere was >10 % counting atoms.
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Krypton in the atmosphere is distinct from chondrites but nearly indistinguishable from solar (Pepin, 1991; Conrad et al., 2016).
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Volatiles dissolved in melts derived from the Martian mantle are observed to have an isotopic composition akin to chondrites for hydrogen, nitrogen, krypton and xenon (Usui, 2019; Péron and Mukhopadhyay, 2022; Deligny et al., 2023) whereas the isotopic composition of krypton and xenon in the Martian atmosphere – which do not currently experience escape – record a solar-like source (Pepin, 1991; Conrad et al., 2016).
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View in article
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An absolute lower limit on the heat flow derives from long-lived radioactive decay and is equivalent to accretion rates ≈10−4 Mars masses/Myr (Erkaev et al., 2014).
View in article
“Pure nebular capture” (dotted lines) refers to nebular atmospheres with no outgassed component (MCO2 = 0) shown for reference and comparable to earlier calculations (Erkaev et al., 2014).
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Both the strong D/H enrichment of the early hydrosphere (Greenwood et al., 2008) and the anomalous oxygen recorded in ∼4.43 billion year old zircons (Nemchin et al., 2014) may result from isotopic exchange between a hydrosphere and an escaping H2-dominated atmosphere (Pahlevan et al., 2022; Zahnle and Kasting, 2023).
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Of course, mass-selective argon loss from Mars via other mechanisms (e.g., solar wind sputtering) occurs and is ongoing (Jakosky et al., 2017).
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A significant feature of the Martian volatile record is that the surface hydrosphere inferred by geomorphology – like the atmospheric 36Ar reservoir – cannot be generated via volcanic outgassing over time (Jakosky and Treiman, 2023).
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The hybrid origin model suggests a new mechanism for the formation of a Martian hydrosphere, similar to the generic scenario recently explored in Kimura and Ikoma (2020).
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Lower accretion rates produce cooler, denser atmospheres that are more massive, a behaviour summarised with the maxim: “to cool is to accrete” (Lee and Chiang, 2015).
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Results from the Rosetta mission allowed the identification of cometary xenon as a likely source for terrestrial xenon, in particular the long hypothesised component called U-Xe that is apparent in the atmosphere of Earth but not Mars (Marty et al., 2017).
View in article
Marty, B., Avice, G., Sano, Y., Altwegg, K., Balsiger, H., Hässig, M., Morbidelli, A., Mousis, O., Rubin, M. (2016) Origins of volatile elements (H, C, N, noble gases) on Earth and Mars in light of recent results from the ROSETTA cometary mission. Earth and Planetary Science Letters 441, 91–102. https://doi.org/10.1016/j.epsl.2016.02.031

The low C/36Ar and N/36Ar of the Martian atmosphere relative to chondrites (Fig. 3) has previously been attributed to a possible contribution from Ar-rich comets (Marty et al., 2016).
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There is, however, empirical evidence that silicate Mars experienced outgassing during the lifetime of the short-lived and volatile radionuclide 129I (τ1/2 = 16 Myr), resulting in the observed 129Xe depletion in Martian interior reservoirs (Marty and Marti, 2002).
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The hydrosphere was apparently placed on the Martian surface early in planetary history. Independent evidence for the existence of a Martian surface hydrosphere in the first 100 Myr comes from an excess of 129Xe in the atmosphere from the decay of water soluble and short-lived 129I (Musselwhite et al., 1991).
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Both the strong D/H enrichment of the early hydrosphere (Greenwood et al., 2008) and the anomalous oxygen recorded in ∼4.43 billion year old zircons (Nemchin et al., 2014) may result from isotopic exchange between a hydrosphere and an escaping H2-dominated atmosphere (Pahlevan et al., 2022; Zahnle and Kasting, 2023).
View in article
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Volatiles dissolved in melts derived from the Martian mantle are observed to have an isotopic composition akin to chondrites for hydrogen, nitrogen, krypton and xenon (Usui, 2019; Péron and Mukhopadhyay, 2022; Deligny et al., 2023) whereas the isotopic composition of krypton and xenon in the Martian atmosphere – which do not currently experience escape – record a solar-like source (Pepin, 1991; Conrad et al., 2016).
View in article
The krypton isotopic composition of the Martian atmosphere – like solar and distinct from chondrites (Pepin, 1991; Conrad et al., 2016) – suggests the nebular contribution to the primordial Martian atmosphere was >10 % counting atoms.
View in article
Krypton in the atmosphere is distinct from chondrites but nearly indistinguishable from solar (Pepin, 1991; Conrad et al., 2016).
View in article
Péron, S., Mukhopadhyay, S. (2022) Krypton in the Chassigny meteorite shows Mars accreted chondritic volatiles before nebular gases. Science 377, 320–324. https://doi.org/10.1126/science.abk1175

Because undifferentiated building blocks of terrestrial planets were likely volatile-bearing (Schaefer and Fegley, 2017) and Martian accretion likely occurred in the presence of the solar nebula (Dauphas and Pourmand, 2011), questions about different volatile sources and formation processes for the primordial Martian atmosphere can now be addressed (Saito and Kuramoto, 2018; Péron and Mukhopadhyay, 2022).
View in article
Volatiles dissolved in melts derived from the Martian mantle are observed to have an isotopic composition akin to chondrites for hydrogen, nitrogen, krypton and xenon (Usui, 2019; Péron and Mukhopadhyay, 2022; Deligny et al., 2023) whereas the isotopic composition of krypton and xenon in the Martian atmosphere – which do not currently experience escape – record a solar-like source (Pepin, 1991; Conrad et al., 2016).
View in article
The volatile dichotomy between a chondrite-like mantle and a solar-like atmosphere has recently been interpreted to mean that the Martian atmosphere cannot be the result of magma ocean outgassing and must be the result of nebular capture (Péron and Mukhopadhyay, 2022).
View in article
Although this episode of primordial outgassing is empirically supported, it has yet to be reconciled with the observed dichotomy between the Martian interior and atmospheric volatiles (Péron and Mukhopadhyay, 2022).
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Because undifferentiated building blocks of terrestrial planets were likely volatile-bearing (Schaefer and Fegley, 2017) and Martian accretion likely occurred in the presence of the solar nebula (Dauphas and Pourmand, 2011), questions about different volatile sources and formation processes for the primordial Martian atmosphere can now be addressed (Saito and Kuramoto, 2018; Péron and Mukhopadhyay, 2022).
View in article
Here, we consider hybrid accretionary atmospheres (Saito and Kuramoto, 2018) in which an outgassed high molecular weight gas is mixed into the distended low molecular weight nebular atmosphere.
View in article
We consider heat flows at the base of the atmosphere equivalent to planetesimal accretion rates of 0.01–1 Mars masses/Myr (Eq. S-1), covering the range from energetic accretion consistent with large-scale melting (Dauphas and Pourmand, 2011) down to reduced heat flows unable to maintain a magma ocean (Saito and Kuramoto, 2018) and more consistent with sweep-up of planetesimals during the waning stages of accretion.
View in article
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For the chondritic end member, we adopt the 55 % H chondrite, 45 % EH chondrite model for Mars (Sanloup et al., 1999).
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Because undifferentiated building blocks of terrestrial planets were likely volatile-bearing (Schaefer and Fegley, 2017) and Martian accretion likely occurred in the presence of the solar nebula (Dauphas and Pourmand, 2011), questions about different volatile sources and formation processes for the primordial Martian atmosphere can now be addressed (Saito and Kuramoto, 2018; Péron and Mukhopadhyay, 2022).
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Volatiles dissolved in melts derived from the Martian mantle are observed to have an isotopic composition akin to chondrites for hydrogen, nitrogen, krypton and xenon (Usui, 2019; Péron and Mukhopadhyay, 2022; Deligny et al., 2023) whereas the isotopic composition of krypton and xenon in the Martian atmosphere – which do not currently experience escape – record a solar-like source (Pepin, 1991; Conrad et al., 2016).
View in article
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We consider an episode of extreme ultraviolet (EUV) powered hydrodynamic escape in which an outflow of H2 and CO2 entrains trace gases via frequent collisions (Zahnle et al., 1990).
View in article
Zahnle, K.J. (1993) Xenological constraints on the impact erosion of the early Martian atmosphere. Journal of Geophysical Research: Planets 98, 10899–10913. https://doi.org/10.1029/92JE02941

The fate of vapour plumes (retained or lost) depends on the ratio of impact to escape velocity, such that cometary vapour plumes on Earth tend to be gravitationally retained whereas those on Mars tend to disperse (Zahnle, 1993).
View in article
Zahnle, K.J., Kasting, J.F. (2023) Elemental and isotopic fractionation as fossils of water escape from Venus. Geochimica et Cosmochimica Acta 361, 228–244. https://doi.org/10.1016/j.gca.2023.09.023

Both the strong D/H enrichment of the early hydrosphere (Greenwood et al., 2008) and the anomalous oxygen recorded in ∼4.43 billion year old zircons (Nemchin et al., 2014) may result from isotopic exchange between a hydrosphere and an escaping H2-dominated atmosphere (Pahlevan et al., 2022; Zahnle and Kasting, 2023).
View in article
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Supplementary Information
The Supplementary Information includes:
- Enhancement of Nebular Capture
- Energetics, Mechanisms, and Extent of Mixing
- Fractionation via Hydrodynamic Escape
- Magnitude of Impact Erosion
- Supplementary Tables S-1 and S-2
- Data Availability Statement
- Supplementary Information References
Download the Supplementary Information (PDF)
Figures

Figure 1 The captured gas inventory (MH) as a function of the outgassed inventory (MCO2) for fully-mixed hybrid atmospheres. Curves correspond to different accretion rates in units of Mars masses per million years (M-m/Myr) and therefore to different planetary luminosities. “Pure nebular capture” (dotted lines) refers to nebular atmospheres with no outgassed component (MCO2 = 0) shown for reference and comparable to earlier calculations (Erkaev et al., 2014
Erkaev, N., Lammer, H., Elkins-Tanton, L., Stökl, A., Odert, P., Marcq, E., Dorfi, E., Kislyakova, K., Kulikov, Y.N., Leitzinger, M. (2014) Escape of the martian protoatmosphere and initial water inventory. Planetary and Space Science 98, 106–119. https://doi.org/10.1016/j.pss.2013.09.008
). Mixing with a high molecular weight component enhances nebular capture with the magnitude of the enhancement dependent on the mixed-in heavy gas inventory. The closeness of the solid line slopes to unity indicates the near constant proportion of nebular to chondritic gases in the model atmospheres. The four data points along each curve correspond to a range of mean molecular weights characterising fully-mixed hybrid atmospheres.
Figure 2 Mixtures of chondritic and solar composition gases make specific predictions for the provenance of elements deriving from each component. The krypton isotopic composition of the Martian atmosphere – like solar and distinct from chondrites (Pepin, 1991
Pepin, R.O. (1991) On the origin and early evolution of terrestrial planet atmospheres and meteoritic volatiles. Icarus 92, 2–79. https://doi.org/10.1016/0019-1035(91)90036-S
; Conrad et al., 2016Conrad, P.G., Malespin, C.A., Franz, H.B., Pepin, R.O., Trainer, M.G., Schwenzer, S.P., Atreya, S., Freissinet, C., Jones, J., Manning, H. (2016) In situ measurement of atmospheric krypton and xenon on Mars with Mars Science Laboratory. Earth and Planetary Science Letters 454, 1–9. https://doi.org/10.1016/j.epsl.2016.08.028
) – suggests the nebular contribution to the primordial Martian atmosphere was >10 % counting atoms. Upper limits on the contribution of the nebular component to Martian volatiles derive from the physics of nebular capture into fully-mixed hybrid atmospheres and are <46–77 % (see Fig. 1). Neon is not plotted for clarity but like Ar is derived almost entirely from the nebular component in fully-mixed hybrid atmospheres. Data used to make this plot are given in Table S-1.
Figure 3 Relative abundances of volatile elements in mixtures of chondritic and solar composition gases normalised to krypton and to solar composition. Percentages refer to the fraction of total atoms in the mixture contributed by the solar component. Mixtures with varying proportions of the nebular component can be compared to the composition of the present day Martian atmosphere and differences between the two compositions used to infer the imprint of loss processes. The similarity of cyan, blue, and magenta curves attests to a well-constrained initial composition for the hybrid atmosphere.

Figure 4 Mass-dependent fractionation accompanying argon loss from the hybrid Mars atmosphere. The solid lines show the isotopic composition of an atmosphere after Rayleigh distillation leading to 98 % Ar loss driven by hydrodynamic escape, for various nebular to chondritic proportions (H2/CO2), starting with solar Ar (36Ar/38Ar = 5.5). The efficiency factor is a proxy for mass loss rate. Preservation of solar-like isotopic Kr requires krypton non-participation in the mass fractionating outflow and sets upper limits on the efficiency factor. The existence of solutions sufficiently vigorous to produce 50x reductions in Ar/Kr (see Fig. 3) without excessive Ar (and no Kr) isotopic fractionation indicates the viability of a hybrid mixture as the initial composition of the Martian atmosphere.