<table><caption>**Table 5** Isotopic ratios in the martian atmosphere (see text for references)</caption><thead><tr><th>Isotopic ratio</th><th>Comparison standard</th><th>Atmosphere Viking</th><th>Atmosphere Curiosity</th></tr></thead><tbody><tr><td>D/H</td><td>%-terrestrial</td><td>450</td><td>495</td></tr><tr><td><sup>14</sup>N/<sup>15</sup>N</td><td>ratio</td><td>168 ± 17</td><td>173 ± 11</td></tr><tr><td><sup>13</sup>C/<sup>12</sup>C</td><td>%-terrestrial</td><td>2.3 ± 4.3</td><td>4.6 ± 0.4</td></tr><tr><td><sup>17</sup>O/<sup>18</sup>O</td><td>%-terrestrial</td><td></td><td>2.4 ± 0.5</td></tr><tr><td><sup>18</sup>O/<sup>16</sup>O</td><td>%-terrestrial</td><td>0.7 ± 4.4</td><td>4.8 ± 0.5</td></tr><tr><td><sup>13</sup>C<sup>18</sup>O/<sup>12</sup>C<sup>16</sup>O</td><td>%-terrestrial</td><td></td><td>10.9 ± 3.1</td></tr><tr><td><sup>20</sup>N/<sup>22</sup>N</td><td>Ratio</td><td></td><td></td></tr><tr><td><sup>36</sup>Ar/<sup>38</sup>Ar</td><td>Ratio</td><td>5.5 ± 1.5</td><td>4.2 ± 0.1</td></tr><tr><td><sup>40</sup>Ar/<sup>36</sup>Ar</td><td>Ratio</td><td>3000 ± 500</td><td></td></tr><tr><td><sup>86</sup>Kr/<sup>84</sup>Kr</td><td></td><td></td><td>Conrad et al. (2015)</td></tr><tr><td><sup>129</sup>Xe/<sup>130</sup>Xe</td><td>Ratio</td><td>2.5</td><td>Conrad et al. (2015)</td></tr><tr><td><sup>136</sup>Xe/<sup>130</sup>Xe</td><td></td><td></td><td>Conrad et al. (2015)</td></tr></tbody></table>

### 4.4.2 Atmospheric escape: physical processes and exospheric observations

Atmospheric escape processes are thought to have played a major role in the evolution of the atmosphere and of the climate of Mars, because of its low gravity. In particular, the presence of geological features and mineralogical signatures in the infrared, indicative of the influence of liquid water, would be consistent with a denser atmosphere in the early history of the planet and with a strong atmospheric escape (e.g., Chassefière and Leblanc 2004; Bibring et al. 2005). Chamberlain (1962) mentioned the possibility for oxygen to escape Mars (and Venus), and escape rates were first estimated by Chamberlain (1969). Many theoretical studies have been carried out to explore the different processes that lead to the loss of an atmosphere, which have been supported by measurements performed by Phobos-2, Mars Express, and more recently the MAVEN spacecraft.

The erosion of the Mars' atmosphere can be, in general terms, explained by the lack of an intrinsic magnetic field, which lead to a direct interaction between the atmosphere and the solar wind, and by the low gravity of the planet. Part of the past atmospheric loss could have been due to asteroid and comet impacts, although this process is not believed to be significant (Melosh and Vickery 1989; Binh San Pham and Karatekin 2013). In general, escape processes can be divided into thermal and non-thermal mechanisms (e.g., Chassefière and Leblanc 2004). In thermal escape, light neutral components (like Hydrogen) from the far tail of their energy distribution function may reach escape velocity and leave the atmosphere, above the exobase. The escape of heavier species is due to non-thermal processes, resulting from the interaction of the upper atmosphere with solar photons and charged particles. Four types of non-thermal escape can occur: (1) dissociative recombination, which produces 2 neutrals from an ion and an electron. The best example is $O^2 + e^- \rightarrow O + O$, where oxygen atoms acquire energy above the escape threshold. (2) Ionospheric escape, where ions
<figure><img src="image_60.png" /><figcaption>**Fig. 38** Map of D/H on Mars inferred by near-infrared ground-based measurements of HDO and H₂O (from Villanueva et al. 2015)</figcaption></figure>

are created in the atmosphere and leave it along the solar wind magnetic field lines or by solar wind electric field acceleration. (3) Ion sputtering, where the atmosphere is impacted by part of pick-up ions that transfer their energy to the neutral species, leading to neutral escape. (4) Energetic Neutral Atoms escape, which is the escape of hot neutral atoms produced by charge exchange between pick-up or solar wind ions and the neutral exosphere (Fig. 38).

Amongst all these non-thermal mechanisms, the ionospheric escape has been studied with Phobos-2 and Mars Express data. These space probes provide in situ measurements of ion fluxes as a function of energy, from which an escape rate is calculated. Many assumptions are behind this computation, such as observation geometry and interpolation between data, which lead to overall uncertainties of a factor of 2–3 (Barabash 2013). Figure 39 shows different estimations of the ion escape rate (Dubinin et al. 2011) from several of these assumptions. The ion escape rate typically ranges from $10^{22}$ to $10^{25}$ s⁻¹, which corresponds to a few grams per second (Barabash et al. 2007). These rates can be propagated backward over a period of 3.5 billion years, resulting in the total removal of 0.2–4 hPa of carbon dioxide and a few centimeters of GEL or water. Clearly, ion escape is not a significant escape channel. Moreover, solar cycle effects on the heavy ion escape rate have been quantified by Lundin et al. (2013). They found that the average escape rate was increased by a factor of ≈10, from ≈$10^{24}$ ions s⁻¹ at the solar minimum to ≈$10^{25}$ ion s⁻¹ at the solar maximum, as illustrated in Fig. 40. The authors also derived an empirical expression for the Martian escape rate versus solar activity F10.7 index and the sunspot number, which is a useful tool to derive the accumulated ion escape rate from Mars based on historical records of solar activity, with big potentials to back to the young Sun epoch. More recently, Ramstad et al. (2015) have further quantified the ion escape rate with respect to upstream solar wind density, velocity, and EUV conditions. The most interesting trend is the decrease
<figure><img src="image_61.png" /><figcaption>**Fig. 39** Summary of ion loss fluxes at Mars evaluated by different authors on the base of Mars Express ASPERA-3 observations at different energies. The figures are taken from Dubinin et al. (2011)</figcaption></figure>

of the atmospheric erosion with increasing solar wind density, in particular during low solar EUV intensity conditions. It is also important to mention the direct effect of co-rotating interaction regions and coronal mass ejections that increase the ion escape up to a factor of 2.5 (Edberg 2010).

When the escape rate data from Mars Express are compared with Earth and Venus, the ion escape at Earth is found to be similar or even higher than in the Venus and Mars cases (Barabash et al. 2009; Luhmann 2009). A possible reason for this could be the size of the Earth’s magnetosphere, which is larger, and, therefore, intercepts more energy from the solar wind than Mars and Venus (Barabash et al. 2009). This observation could lead to a possible paradigm shift: Are non-magnetized bodies better protected against solar wind? Could the escape rates at Mars be much higher in the distant past, when Mars’ internal dynamo was active, and there was a larger solar forcing from the early Sun?

It is obvious that to understand the evolution of Mars, we need information on the atmospheric escape over time. At this stage, it must be understood that the estimation of this quantity with the current data is still carried out with large uncertainties. First, there is not yet a clear picture of which processes are the drivers. Recent data show that the ion escape channel is not very efficient. The escape rate is low, and thus, one has to continue searching for water reservoirs and carbon dioxide stores on or beneath the planetary surface and also to investigate other escape channels (e.g. Barabash et al. 2007). Furthermore, large uncertainties are associated with the measurements and computation. The next steps are in the line of better understanding all the processes to minimize the corresponding uncertainties. The ion escape rate variability is also

<figure><img src="image_62.png" /></figure>
<figure><img src="image_63.png" /><figcaption>**Fig. 40** From Lundin et al. (2013). Ion fluxes as function of time, illustrating the effect of the solar cycle activity. The average escape rate increased by at least a factor of ≈10 from solar minimum to solar maximum</figcaption></figure>

a critical parameter to assess, and studies over a complete solar cycle are needed to assess the full range of fluctuations. Then, the challenging exercise of extrapolating previous estimations over a few billion years, from a current larger time dataset, may be improved. It is also necessary to link these results with the D/H measurements and interpretation (e.g., Chassefière and Leblanc 2004; Mahaffy et al. 2015) for consistency. Certainly, MAVEN (Jakosky et al. 2015a, b) will bring much more information and constraints to the atmospheric escape, and thus on the evolution of the red planet. MAVEN observations have recently shown a major impact of interplanetary coronal mass ejections on atmospheric erosion (Jakosky et al. 2015a, b). The effects through the entire upper atmosphere system produced substantially disturbed conditions and appeared to have a major impact on the instantaneous rates of loss of ions to space. Given the likely prevalence of interplanetary coronal mass ejections like conditions earlier in solar system history, it is possible that ion escape rates at that time were dominated by storm events. As these early periods may have been the dominant times at which the martian atmosphere experienced loss, the inferred climate change on Mars may have been driven to a large extent by these solar storms (Jakosky et al. 2015a, b).

## 4.5 The fate of volatiles and their link to climate evolution

### *The carbon cycle*

The current carbon cycle is strongly related to the seasonal CO₂ frost deposition, inducing strong seasonal flux. While current variations of climate were thought to be related mainly to astronomical parameters (eccentricity, obliquity), recent observations from the SHARAD radar have shown the presence of a buried deposit of CO₂ ice within the south-polar layered deposits which could have enhanced the total atmosphere
pressure by almost a factor of two in recent high obliquity phases (Phillips et al. 2011). In addition, clathrates/hydrates are theoretically stable at depth and could contribute to the carbon cycle (Prieto-Ballesteros et al. 2006; Chastain and Chevrier 2007; Gainey and Elwood Madden 2012; Mousis et al. 2013; Chassefière et al. 2013), including the sporadic presence of methane in the atmosphere. These examples show how the poor knowledge of the deep cryosphere is a limitation to current understanding of the current carbon cycle.

In parallel to the current reservoir of CO₂, carbonates could have trapped part of the potentially thicker early atmosphere. Recent studies concluded that carbonates observed at Nili Fossae represent a limited CO₂ reservoir unable to explain a thicker atmosphere (Edwards and Ehlmann 2015). Nevertheless, more carbonates exhumed by craters are progressively found by orbital data (Wray et al. 2016) linking to estimation of several 100 ppm of equivalent CO₂ gas trapped in these carbonates (Hu et al. 2015). An unavoidable problem is that the detection of possible buried reservoirs remains limited by the local role of impact craters which excavate these carbonates only locally. Therefore, it is currently difficult to conclude definitively regarding the total amount of carbon stored as sub-surface carbonates.

*The “early Mars paradox”*

As discussed above, the deuterium enrichment and other isotopic ratios, such as ³⁶Ar/³⁸Ar, strongly suggest the presence of a large proportion of water (100s m of global equivalent layer) and a thicker atmosphere in the Noachian (above 100 mbar, but likely below 1 bar). This diagnostic comes in addition with many other geological and spectroscopic signatures (see Sect. 4.1), so there seems to be converging evidence for a warmer and wetter early Mars. However, recent attempts to model this early Mars using global climate models have failed to reproduce warm and wet conditions. Forget et al. (2013) and Wordsworth et al. (2013) have performed 3D simulations of the early martian climate assuming a faint young sun (consistent with stellar evolution models), under a wide range of surface pressures and various conditions of obliquity, orbital parameters, and atmospheric and surface properties. In most of the cases, CO₂ ice was found to cover a major part of the planet, implying a high surface albedo. As a consequence, a cold early Mars model was favored: the mean surface temperature could not have risen above 0 °C anywhere on the planet (implying no possibility for liquid water to flow). To explain observations, episodic melting of ice might have occurred following meteoritic impacts or volcanic activity. However, those conditions are currently not able to explain the lack of U-shaped glacial valleys that would form as a consequence cold and wet conditions neither to reproduce the widespread signature of surface alteration (e.g., Carter et al. 2013, 2015). The early Mars history illustrates the need for understanding Mars evolution as a whole from multiple disciplines.

# 5 Conclusions, outstanding questions, and future missions

## 5.1 Major questions

Although Mars has been the target of multiple space missions in the two last decades, many questions remain unsolved, and several have been raised after new observations

<figure><img src="image_64.png" /></figure>
from these missions. This situation is due to the fact that Mars is probably as complex
as the Earth system, with a rich and prolonged geological history, which is itself
a fascinating result and a statement that can be made after these two decades of
exploration.

The sub-surface structure of Mars is underconstrained due to the lack of seismo-
logical data, as is the thermal budget from the lack of knowledge of the heat flow.
However, both are keys to the understanding of the energy budget of the planet, and
the volcano-tectonic evolution through time, just as knowing the size of the core is
important to understand of past dynamo(s) and its cessation.

The age of the surface of Mars is constrained relatively by crater densities, but
retrieval of absolute ages requires isotopic dating of well-characterized surface units,
for instance, by dating a well-defined surface unit by isotopic chronometers, as it was
done for the Moon with the Apollo program.

The composition of the upper crust has been largely documented and relatively well
understood, but the origin, proportion, and significance of felsic rocks such as those
identified at Gale crater and in recently found martian meteorites remain unclear. The
diversity of the composition and the structure of the crust need to be better understood:
first, to be able to identify if remnants of magma ocean crystallization phase have
survived until present time and, second, to understand the various processes of crustal
growth after the initial differentiation.

The presence, distribution, and nature of volatile species (including H₂O, CO₂,
CH₄, and various types of clathrates, and hydrates) in the upper crust remain also
an unsolved question. Such a reservoir could contribute significantly to the volatile
budget. Buried methane (in clathrate or other geological reservoirs) remains central
in questions related to its detection in the atmosphere (Lyons et al. 2005; Atreya et al.
2007; Chassefière et al. 2013). Whether the origin of Mars' methane is biotic or not,
its presence will play a central role in future science and exploration efforts, and is
also of relevance to the carbon cycle.

Studies of the carbon cycle are generally related to the fundamental question of
the “missing carbonates”. Indeed, if the past atmosphere was denser, how would the
atmosphere lost carbon, i.e., by atmospheric escape, or by the formation of carbonates
at depth, or another process?

While the early Mars conditions were clearly different from the present, as deduced
from various observations (aqueous mineralogy and fluvial landforms, D/H ratio, and
Ar isotopes), the exact conditions under which liquid water was stable at the surface
are still controversial. Was water liquid seasonally, or episodically over short periods
geologically speaking? Only detailed investigations in situ as performed by rovers
can help to further decipher the paleoclimate of the first billion years recorded in the
ancient sediments. The precise timing and causes for the climatic transition are not
well-established, but there is a general consensus that the loss of the magnetic field
has strongly influenced surface conditions.

This synthesis did not focus on organics and related chemistry, but we cannot end
this section without highlighting that the question of life is still the main fundamental
interest for Mars researches and is the predominant question driving mission selection
and design. The present dry and cold conditions are relatively uninhabitable for ter-
restrial life, but the presence of local niches with transient liquid water such, as RSLs
(although these landforms are also an ongoing topic of research) or sub-surface contexts, is potential habitats that may be investigated in situ in the future. Traces of past life have a higher probability than present biological activity explaining that the rover missions are focused on the analysis of >3.5 Gy old aqueous sediments. While various domains of Mars science have been greatly improved, the fundamental question of life on Mars is still far from being solved from in situ observations. Curiosity main objective is “follow the carbon”, but it is not able to detect life directly, although it could do so from macroscopic observations (e.g., stromatolites). Even with samples returned on Earth and with detailed analyses by the most sophisticated laboratory instruments, we may not be able to detect or discard a past life form in rocks, as evidenced by the controversy surrounding the observation of putative bacteria fossils in the meteorite ALH84001 (McKay 1996). Nevertheless, if we can once prove that life never started on Mars, trying to understand why Mars evolved differently than the Earth may be of great interest to understand the necessary conditions for the emergence of life, a knowledge that can be applied to the increasing amount of observations that constrain surface conditions on exoplanets.

## 5.2 Future missions

To address some of the issues described above, several missions have been scheduled by national agencies, including two rovers. After the successful Mars Express mission launched in 2004, ExoMars is ESA's next step in Mars scientific exploration. ExoMars consists of two missions (Vago et al. 2015). The first includes two elements: the Trace Gas Orbiter (TGO) and the Entry, Descent, and Landing Demonstrator Module (EDM). The orbiter will investigate atmospheric trace gases and their sources, and serve as a communication relay orbiter, while the EDM will test new key landing technologies and will study the environment at the landing site. The second mission will deliver a rover to the surface of Mars, to search for signs of life, past and present. These two missions are being conducted as a collaboration between ESA and the Russian space agency, Roscosmos.

The orbiter and EDM were launched together on March 14th 2016 on a Proton rocket. The TGO orbiter was successfully inserted into orbit on October 19th 2016 and will start in March 2017 an aerobraking phase to reach its final circular ~400-km altitude orbit, leading to a start of the nominal science phase scheduled for March 2018. The spacecraft carries four instruments from Europe and Russia that are expected to perform during at least one Martian year detailed and remote observations of the martian atmosphere, searching for evidence of gases of possible biological or geological importance. The location of sources that produce these gases will be studied by an imager. Three days before TGO orbit insertion, the EDM was ejected from the Orbiter towards the red planet, in a location named Meridiani Planum. Unfortunately, the contact with the EDM was lost shortly before the expected touchdown, suggesting a major failure during the last steps of its descent. At the time of writing of this article, there is no explanation about this failure. The goal of the EDM was to enhance Europe's expertise and enable the testing of key technologies which could be used in subsequent missions to Mars. A science package (called DREAMS) would have

<figure><img src="image_65.png" /></figure>
operated on the surface of Mars for a few days. DREAMS would have conducted atmospheric measurements at the landing site and provided measurements of electric fields on the surface. An investigation called AMELIA (Atmospheric Mars Entry and Landing Investigation and Analysis) was also set up to study the atmosphere during the entry and descent by using the probe engineering sensors and the tracking data, recorded by Mars orbiters and by the Giant Metrewave Radio Telescope (GMRT) near Pune, India. Fortunately, most of the data of this experience were collected on time; they will enable scientists to improve atmospheric models.

The ExoMars rover mission is planned to be launched in August 2020 on a Proton rocket, with a landing on Mars in April 2021. The rover will carry a comprehensive suite of instruments dedicated to exobiology and geology research named after Louis Pasteur. It will be able to travel several kilometers searching for traces of past and present signs of life. The rover will collect and analyze samples from within rocky outcrops, and from the sub-surface, down to 2-m depth. The very powerful combination of mobility with the ability to access locations where organic molecules can be well preserved is unique to this mission. It is also planned to include instruments on the landing platform with the goal to study the surface environment. At the time of writing, three possible landing sites are being studied: Oxia Planum, Mawrth Vallis, and Aram Dorsum. For the mission to achieve high-quality scientific results regarding the possible existence of biosignatures, the rover must be delivered safely to a scientifically appropriate setting: ancient (older than 3.6 billion years), having abundant morphological and mineral evidence for long-term water activity, including numerous outcrop targets distributed in the landing ellipse (to make sure that the rover can get at least to some of them), and with a little dust coverage.

Following the success of the two Mars Exploration Rovers Opportunity and Spirit and Mars Science Laboratory Curiosity rover, the next step for NASA's robotic exploration of Mars is the Mars 2020 rover, which is planned to be launched in 2020. Within the current science theme "Seek Signs of Life", the mission would explore a site likely to have been habitable, seek signs of past life, fill a returnable cache with the most compelling samples, and demonstrate technology needed for the future human and robotic exploration of Mars. The rover will carry seven scientific projects, including an exploration technology investigation, that will produce oxygen from atmospheric carbon dioxide. The caching system will be used to store samples for potential return to Earth by a future mission not currently planned. Despite the huge technology of martian rovers, ancient sediments would be better analyzed using sophisticated terrestrial laboratories, especially looking for traces of life.

The NASA Discovery program has selected the InSight mission as the 12th Discovery mission. This mission, which is not part of the NASA Mars Program, will be the first to explore the interior of a planet by means of seismology and heat-flow probes. The evolution of the seismometers in the last 10 years allowed the InSight team to convince the scientific panels that one state-of-the-art broadband seismometer will provide information on the interior structure and the tectonics at least as good, if not better, than a network of three seismometers as it has been proposed in the past by the MESURE and NETLANDER projects. The broadband seismometer will be carried onto the Martian surface by a Phoenix-type lander. A robotic arm will delicately put the seismometer on the surface in the vicinity of the lander. The lander will also carry
a heat-flow probe that will measure the temperature gradient and the thermal conduc-
tivity of the Martian sub-surface down to 5 m. This value will bring key information
on the amount of heat flux being expelled from the Martian interior, a key parameter
to understand the thermal evolution of the red planet. After a delay due to technical
issues, the InSight mission has been postponed to mid-2018.

While the current NASA orbiters (MRO, Mars Odyssey, MAVEN) may become
old in the next decade, NASA also aims to launch another orbiter in the next decade
with several instruments, including high-resolution cameras intended to track rover
activities at the surface. These upcoming missions to Mars demonstrate the constant
interest of this planet for the scientific community. These missions pave the way for
future sample return missions and possibly crewed missions for which there is an
increasing interest, although no firm schedule has been defined yet.

**Acknowledgements** We greatly appreciated detailed reviews from Mike Carr and anonymous reviewer. We wish to warmly thank Elliott Sefton-Nash for his detailed comments. Authors are funded by the Centre National d'Etudes Spatiales (CNES).

**Open Access** This article is distributed under the terms of the Creative Commons Attribution 4.0 International License (http://creativecommons.org/licenses/by/4.0/), which permits unrestricted use, distribution, and reproduction in any medium, provided you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons license, and indicate if changes were made.

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