Planetary and Space Science 166 (2019) 70–89

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Planetary and Space Science

journal homepage: www.elsevier.com/locate/pss

Water in the history of Mars: An assessment

H. Rickman a, b, M.I. Błęcka a, J. Gurgurewicz a, *, U.G. Jørgensen c, E. Słaby d, S. Szutowicz a,
N. Zalewska a
a
Space Research Centre, Polish Academy of Sciences, Bartycka 18A, PL-00716, Warsaw, Poland
b
Dept. of Physics and Astronomy, Uppsala University, Box 516, SE-75120, Uppsala, Sweden
c
Centre for Star and Planet Formation, Niels Bohr Institute, University of Copenhagen, Øster Voldgade 5, DK-1350, Copenhagen, Denmark
d
Institute of Geological Sciences, Polish Academy of Sciences, Research Centre in Warsaw, Twarda 51/55, PL-00818, Warsaw, Poland

A R T I C L E I N F O A B S T R A C T

Keywords: This paper presents a review of recent literature concerning issues related to the origin of water in planet Mars
Mars and its role in the geologic evolution of that planet. The baseline case of our discussion is the Grand Tack model of
Planet formation planetary migration in the solar nebula and an early planetary orbital instability according to the Nice Model. This
Martian meteorites discussion also benefits from a comparison with the Earth's accretional history. Recent observations are used to
D/H ratios check the results of planetary accretion models, leading to a new picture of the early history of water on planet
Martian ocean
Mars. The embryo forming the basis of the planet is found to have been very deficient in water. During the
Impact craters
following period, predating the formation of the Earth's Moon, the accreted water may have been as high as
~5 km Global Equivalent Layer (GEL) while the amount accreted at later times may have been as low as ~10 m
GEL according to recent studies. In particular, the trans-planetary source was insignificant, at whatever time it
was active. The proposed resurfacing event creating the Borealis basin could have been important for the loss of a
significant part of the early Martian water inventory.

1. Introduction
This review will deal with the role of water in the history of Mars. In
most regards, this will mean the time up to and including the Noachian.
Our main emphasis will be placed on the issue of how and when the
planet acquired its H2O inventory. Since impacts play a major role in this
discussion (up to and including the Late Heavy Bombardment), we will
pay special attention to the main impact features on Mars and their
relation to the evolution of Martian near-surface water. We will use the
Introduction to briefly set the stage by highlighting the different ideas
and models of relevance. In the following sections, we will discuss the
geochemistry and isotopic signatures of Mars, the evolution of the
Martian atmosphere and hydrosphere including impact-related pro-
cesses, and geomorphologic and mineralogical evidence for water on the
Martian surface including the origin and distribution of phyllosilicates. In
the Conclusions, we will come back to the fundamental issue of the origin
of the Martian water, summarizing the implications of recent findings
and identifying open issues. We note here that, not very long ago,
excellent papers have been published containing reviews of topics close
to the current one (e.g., Lammer et al., 2013; Brasser, 2013). However, so
much progress has been achieved since then that we believe a new review
is called for.
Let us start from the study of Dauphas and Pourmand (2011), which,
by means of Hf-W dating using Martian meteorites, settled the issue of
the accretion time scale of Mars by showing this to have been only a few
Myr. This is consistent with the planet being a stranded embryo and thus
different from Earth and Venus, which resulted from a series of giant
impacts lasting for more than 50 Myr (Raymond et al., 2009; Jacobson
et al., 2014). One possible consequence of such a rapid accretion is 26Al
induced global melting (Dauphas and Pourmand, 2011), leading to a
magma ocean that might have taken a considerable time to cool and
solidify. Whether or not such an evolutionary stage took place, as well as
its duration, will influence to what degree the infant planet could have
picked up volatiles from impacting, water-rich planetesimals.
In any case, the embryo that is here identified as the new-born planet
Mars – at a time a few Myr after CAI1 formation – was made of locally

* Corresponding author.
E-mail address: jgur@cbk.waw.pl (J. Gurgurewicz).
1
CAI stands for Calcium-Aluminum rich Inclusions, which are abundant in many chondritic meteorites. These are formed by extremely refractory minerals.
Together with the first chondrules, they mark the oldest radiometric age determined in any solar system material, 4.567 Gyr (Connelly et al., 2012), and is therefore
interpreted as the time when the first solid materials condensed in the protosolar disk, often referred to as the age of the solar system.

https://doi.org/10.1016/j.pss.2018.08.003
Received 9 April 2018; Received in revised form 27 July 2018; Accepted 13 August 2018
Available online 15 August 2018
0032-0633/© 2018 Elsevier Ltd. All rights reserved.
H. Rickman et al.
accreted building blocks (see Morbidelli et al., 2012a), and these are
usually inferred to have been extremely deficient in water because of the
expected, high temperatures in the innermost part of the solar nebula and
the existence of anhydrous chondrites apparently originating in the inner
parts of the asteroid belt. Mars might thus have formed dry or, at most,
with a very small water content. But it would not take long, until
water-rich projectiles started to invade its surroundings. The nature of
these projectiles will be discussed below.
There are several scenarios of relevance in this regard. The classical
model envisages a situation, where Jupiter stays far away from the ac-
cretion zone of the terrestrial planets. Here the most important phe-
nomenon is the dispersal of the solar nebula and the ensuing
gravitational perturbations causing resonant pumping of orbital eccen-
tricities in all regions of the asteroid belt as well as, to a lesser degree, in
the regions closer to the Sun (Morbidelli et al., 2012a). This triggers the
giant impact phase of planet formation and brings water-rich material
from the outer part of the asteroid belt into the terrestrial planet zone.
The time at which the dispersal happened is not firmly established but is
generally believed to be a few Myr after CAI formation – thus more or less
coeval with or slightly postdating the formation of Mars.
Within this picture, Mars would have been bombarded by all kinds of
planetesimals, both water-poor and water-rich, but avoided being hit by
other embryos. The amount of water that Mars would thus have accreted
during the giant impact phase is not well determined, but if the common
view that the Earth acquired its water mainly from CI- or CM-type, distal
embryos (Morbidelli et al., 2000; Raymond et al., 2009) is correct, the
absence of this source in the case of Mars may imply that it left its infancy
with less water than the Earth or Venus would have at their later time of
formation. Lunine et al. (2003) made an estimate of about 0.01–0.06%
for the relative mass of the water accreted by Mars, based on dynamical
simulations.
However, this classical model suffers from a problem to explain the
survival of Mars as a stranded embryo – the so-called “small Mars
problem”. Most simulations (e.g., Chambers, 2001; Kokubo et al., 2006;
Raymond et al., 2006) have produced a full-grown planet – less massive
than Earth or Venus but much more massive than Mars – near the place of
Mars' orbit. As summarized by Brasser (2013), alternative scenarios that
succeed better have tended to assume a narrow annulus of embryos at
about 0.7–1 AU (Hansen, 2009) instead of the extended disk-like distri-
bution of the classical model. Walsh et al. (2011) provided an explana-
tion for such a structure in the so-called Grand Tack model of planet
formation.
Here something dramatic happens before the dispersal of the solar
nebula. The growth of Jupiter to near its final mass triggered a sunward,
Type II migration that would bring the planet all the way to 1.5 AU from
the Sun during a two-planet migration caused by a resonant locking with
Saturn (Masset and Snellgrove, 2001), before the two gas giants “tacked”
and migrated outward together. This would have compressed the
terrestrial planet embryo population into a narrow annulus, as hypoth-
esized above, and also brought a large population of planetesimals, both
rich and poor in water, into high-eccentricity orbits penetrating this
region.
Brasser et al. (2016a) revisited the Grand Tack modeling of terrestrial
planet formation, aiming to improve the realism of the model, with the
result that the best fit to the masses of these planets is obtained for a
tacking distance of 2 AU instead of 1.5 AU. It is not likely that this change
would significantly reduce the amount of water-bearing planetesimals
holding the potential to be accreted by the Earth or Mars.
The chronology of the Grand Tack scenario is worth a comment.
Before the migration can start, Jupiter's core of about 10 Earth masses or
more (Wahl et al., 2017) must be formed. The growth of terrestrial planet
embryos should be finished within a comparable time and for Mars the
default estimate by Dauphas and Pourmand (2011) is about 2 Myr. This
supports the above conjecture that the growth of Mars started from
material that predated the Grand Tack migration and thus contained little
if any water.
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Planetary and Space Science 166 (2019) 70–89
Meanwhile, the narrow annulus picture resulting from the Grand
Tack model is not the only proposed solution to the small Mars problem.
Levison et al. (2015) applied a model introduced by Lambrechts and
Johansen (2012) for the growth of planetary embryos by accretion of
pebbles remaining after planetesimal formation – the so-called Viscously
Stirred Pebble Accretion (VSPA) model
to study the ensuing system of
terrestrial planets. As a result, the small mass of Mars relative to the Earth
or Venus comes out as a natural consequence.
In the framework of the VSPA model, the Grand Tack is not needed as
a way to solve the small Mars problem. Mars could have been formed by
local accretion at its current distance from the Sun, and the classical
model might still apply. Moreover, the classical model is very flexible as
regards the preferred heliocentric distance for the early formation of
planetesimals. According to recent models of planetesimal formation
involving the streaming instability (Johansen et al., 2014), an enhance-
ment of the local dust density in the disk is necessary, and this was shown
via dust evolution models by Drą_zkowska et al. (2016) to have prefer-
entially occurred in a narrow annulus at 1 AU in the solar system. This
scenario, which does not rely on pebble accretion, also circumvents the
small Mars problem. However, the Grand Tack is much more than just a
solution to the small Mars problem. It is a likely scenario for giant planet
migration in the solar nebula whether or not it is needed to explain the
mass of Mars, and it has frequently been used in recent papers on the
formation of Mars. We shall therefore treat it as a baseline case in the
following discussions.
The Nice Model (Tsiganis et al., 2005) is also of crucial importance.
This forms the basic framework, within which the Grand Tack model was
developed. Its salient feature is the concept that the giant planets formed
within the solar nebula in a much tighter configuration than the present
one, and that this configuration broke down at some later time, leading to
the scattering of icy planetesimals around the whole solar system.
The Nice Model does not prescribe the timing of the planetary
instability. This has often been assumed to connect to the Late Heavy
Bombardment (LHB), i.e., the intense lunar cratering that occurred almost
4 Gyr ago (Tera et al., 1974). Evidence suggesting an episodic peak in the
lunar cratering rate at that time was interpreted to mean that the insta-
bility occurred at that time (Gomes et al., 2005). Meanwhile, Kaib and
Chambers (2016) preferred a very early instability that occurred before
the terrestrial planets were formed.
Morbidelli et al. (2018) have recently revisited the case for a late peak
in the cratering rate as based on highly siderophile element (HSE)
abundances in the lunar mantle. These authors found it likely that the
HSEs brought by impacting bodies of chondritic composition were not
retained in the lunar mantle until a time more than 100 Myr later than
that of the Earth. This would explain the relative dearth of HSEs in the
lunar mantle without the need to assume a low chondritic impact rate.
We note that another way to achieve this may be to assume a slightly
higher value for the impactor velocity than that used by Morbidelli et al.
(2018). Thus, there are new arguments supporting the interpretation of
the LHB as a late accretion tail (Hartmann, 1975) rather than as an
episodic peak, which brings new fuel to this long-standing debate. If the
LHB was not an impact peak but an impact tail, then the instability could
indeed have occurred very early – long before the Earth and Moon were
formed. We shall take such an early instability as the baseline case for our
discussion but keep in mind that the issue is not settled and thus consider
also the alternative of a late instability.
As argued above, in both the Grand Tack, classical and pebble ac-
cretion scenarios, the bulk of Mars likely formed quite dry, and the
acquisition of water was due to later arriving planetesimals. Some in-
dications come from results on the Earth's accretion of water. Morbidelli
et al. (2012a) state that at least 50% of the Earth's water was accreted
after our planet had reached 60–70% of its final mass, according to
simulations within both the classical and Grand Tack scenarios. Among
relevant geochemical evidence, we note that the oxidation state of the
Earth increased while the planet was growing so that the first 60–70% of
its mass should have been highly reduced (Wood et al., 2008; Rubie et al.,
H. Rickman et al.
2011).
From the point of view of dynamics, it can be argued that the time
scale for water-bearing objects to hit the Earth should be the same,
whether these are big embryos or small planetesimals. The same should
in principle hold for Mars, although in reality, no embryo collided with
Mars. But the late arrival of water onto the Earth seems to imply that at
least one big embryo arriving late in the accretion process brought a large
part of our planet's water (see below for further evidence), so the absence
of such a collision for Mars might imply a lesser total amount of accreted
volatiles relative to the mass of the planet.
Brasser (2013) mentioned some preliminary results about the accre-
tion of water by Mars in the Grand Tack model, based on simulations by
Walsh et al. (2011) and O’Brien et al. (2010). Indeed, he found the planet
to be made of one embryo and lots of accreted planetesimals – the latter
contributing about 20% of the mass. Since several percent of the total
would originate beyond the snow line and thus be water bearing, he
could estimate the amount of accreted water. Using a H2O content of 5%
(Morbidelli et al., 2000) for the icy objects, Brasser estimated that Mars
could have incorporated 0.1–0.2% water, i.e., comparable to the Earth's
fractional water content if the latter is assumed to be dominated by
mantle water. However, this estimate naturally comes with a large error
bar, and Brasser explicitly regarded it as a likely upper limit.
O’Brien et al. (2014) again addressed the issue of the water delivery
to the Earth within the Grand Tack model in a detailed modeling study of
several aspects of planet formation. These authors argued that Earth's
fractional water content resulting from accretion (not counting associ-
ated or subsequent loss processes) is expected to be ~0.1%, assuming
that planetesimals formed beyond Jupiter's initial orbit contained on the
average 10% water by mass. According to the predictions of the Grand
Tack model, these correspond to the C-type asteroids populating the
outer part of the main belt, from which the carbonaceous chondrites are
thought to originate.
However, the actual amount of this water content is currently a major,
unresolved issue. The value used by O’Brien et al. (2014) was based on
the average for water-rich carbonaceous chondrites (mainly, the CI and
CM classes). But those meteorites might come from parent bodies with a
higher water content (Raymond and Morbidelli, 2014) as suggested by
the icy surface of (24) Themis (Rivkin and Emery, 2010; Campins et al.,
2010) or the low-density, likely icy mantle of (1) Ceres (Park et al.,
2016). On the other hand, Rosetta observations of coma grains in comet
67P/Churyumov-Gerasimenko have led to an estimated ratio of about 6
between the average dust and gas production rates (Fulle et al., 2016),
indicating that the bulk composition of this comet may be dominated by
refractories instead of ice. The planetesimals considered in the Grand
Tack model were formed closer to the Sun and would hence be even more
depleted in water.
The fractional water content (fw) can be translated into the thickness
(hw) of a global equivalent water layer (GEL) by the relation:
hw ¼ fwRpρp/3ρw, where Rp is the planetary radius, and ρp and ρw are the
mean density of the planet and the density of water, respectively. For the
case of Mars this yields: hw ¼ fw  4.42  103 km. The lower end of the
above interval thus corresponds to 4 km GEL of water, so we may regard
several km GEL as a rough upper limit to the total initial inventory, of
which some fraction currently exists as near-surface water. This may be
compared with estimates of the amount of water existing in Mars at later
times during its history. The presently known polar ice Martian H2O
deposits hold a total of 20–30 m GEL (Christensen, 2006; see also
Chassefiere et al., 2013). In addition, up to 1 km GEL of water may be
trapped in the cryosphere and underlying groundwater (Clifford et al.,
2010). Observational verification of this comes from the MARSIS radar
sounding of Mars on board the ESA Mars Express mission (Mouginot
et al., 2012). A low dielectric constant found in the Vastitas Borealis
region was shown to indicate low-density sedimentary deposits and/or
massive deposits of ground ice. Recently, Dundas et al. (2018) investi-
gated erosional scarps in the Martian mid-latitudes and found exposed
deposits of water ice up to more than 100 m thick. From studies of the
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Planetary and Space Science 166 (2019) 70–89
water content in the parental magma of SNC meteorites (Gross et al.,
2013; Slaby et al. 2016; Weis et al., 2017), it has been concluded that the
Martian mantle of recent times may be similar to or somewhat dryer than
the Earth's Mid-Oceanic Ridge Basalts (MORB).
In addition, the morphologic evidence for liquid surface water during
the Noachian, especially the outflow channels, indicates a near-surface
reservoir of water at that time, amounting to about 500 m GEL (Carr,
1987). Furthermore, the water content of the northern palaeo-ocean on
Mars, based on estimates of shoreline elevations, may imply a GEL of
130–1500 m (Carr and Head, 2003), while estimates based on the
development of the D/H ratio up to the present time point at the lower
end of this range (Villanueva et al., 2015). Further evidence will be
discussed below.
2. Geochemistry of volatiles in terrestrial planets
We find it convenient to discuss the issues of Martian water by
comparing with the evidence gathered for the case of the Earth. Let us
thus start by discussing the Earth's water contents. How much water does
our planet contain now, and how much did it receive during its accre-
tion? The answer to the first question is surprisingly uncertain in itself,
since the amount of mantle water cannot be estimated accurately. We
will use a standard estimate of 0.1% of the Earth's mass for the total,
supported by the finding that the transition layer in the Earth's mantle
contains about three ocean masses of water dissolved in wadsleyite and
ringwoodite (Pearson et al., 2014; Schmandt et al., 2014). In absolute
terms, this means about 6  1021 kg.
The answer to the second question also suffers from an important
uncertainty. It is often thought that the water accreted by the Earth
during its formation dominates over all later sources (Morbidelli et al.,
2012a). However, the end of the Earth's formation is marked by the
Moon-forming impact, which has recently been dated to about 60–130
Myr after CAI formation by Jacobson et al. (2014) and to 140–150 Myr by
Connelly and Bizzarro (2016). One crucial question is how much water
was lost due to both this extremely violent event and the preceding ones
that were likely very violent too.
Before coming to this discussion, let us outline the major issues
around the accretion of volatiles by the Earth and Mars. We separate two
phases of such accretion, which occurred in chronological order. First,
there was the interval, during which the planets formed. This would
leave behind what we call formation water. For the Earth, the phase ended
with the Moon-forming impact and its direct aftermaths, after which our
planet was ready to receive additional water. For Mars we include, first,
the time of formation of the planet, and then a brief era, during which
only a limited amount of water could be retained because of atmospheric
erosion by hydrodynamic escape (Lammer et al., 2013). As mentioned,
this time span for Mars was much shorter than the corresponding interval
for the Earth.
Second, there was a period extending over several hundred Myr,
when both planets were able to accrete water via impacts by water-
bearing projectiles. The latter would have included both comets and C-
type asteroids containing chondritic material of water-rich composition.
This will be referred to as the late veneer. It was characterized by an
impact flux, which was initially very high and tapered off with a time
constant of about one hundred Myr (Brasser et al., 2016a) until the time
of the Late Heavy Bombardment. There might be a subsequent, third
contribution by icy projectiles coming from the trans-planetary zone,
corresponding to the LHB in the hypothetical case of a late planetary
instability. Even if this is not our baseline case, we will consider the
possibility. The water currently present in the Earth and Mars may in
each case be a combination of formation water, late veneer water and
LHB water.
2.1. Formation water
Let us first summarize the current knowledge about this source for the
H. Rickman et al.
case of the Earth, based on a recent paper by Schlichting and Mukho-
padhyay (2018). These authors discuss in particular the non-radiogenic
isotope ratio 20Ne/22Ne in mid-ocean ridge basalts versus deep mantle
plume rocks
the latter clustering around a value close to that of the
solar nebula. They interpreted this to mean that our planet may still
retain nebular volatiles in its deep interior. They conclude that some of
the Earth's embryos did accrete such volatiles without losing all of them
during the following collisional evolution. Partial loss is, however, sug-
gested by the fact that the deep plume source has a ratio lower than the
nebular value and is thus affected by an admixture of chondritic volatiles
within the embryos.
The loss of volatiles from the Earth's embryos seems related to the
giant impacts (Schlichting and Mukhopadhyay, 2018). According to
dynamical simulations, these started to occur right after Jupiter's inward
Grand Tack migration (Morbidelli, pers. comm.). Basically, the mecha-
nism would be the creation of magma oceans by the giant impacts, which
tended to drive the volatiles into the atmospheres, after which the
bombardment by smaller planetesimals eroded these atmospheres away.
It is not clear, to what extent the most effective, km-sized projectiles
existed as a function of time, because recent models of planetesimal
formation (Johansen et al., 2014) predict initial sizes in excess of 100 km
(see below), so that the km-sized projectiles would have to result from a
collisional cascade. The time scale of this process still needs to be
established.
Further evidence for the loss of early volatiles comes from several
elemental abundance ratios characterizing the Earth. According to Hal-
liday (2013), the low C/H and N/H ratios of the Earth relative to chon-
drites are best explained, if both water and more volatile species were
mainly accreted before the Moon-forming impact, and the C- and
N-bearing volatiles were largely lost through the early impacts while
water was more easily retained. Thus, from our perspective, the
conclusion is that the early impacts including the one that formed the
Moon may not have completely driven off the oceanic or mantle water.
The circumstances around the Moon's formation are plagued by large
uncertainties (Asphaug 2014) as evidenced by the “isotopic crisis”
(Melosh, 2009), i.e., the difficulty of explaining the similarity of Earth
and Moon in isotope ratios of many elements. While the Moon accreted
an important quantity of water (Hauri et al., 2011; Hui et al., 2013), there
is a deficit of heavy halogens in the Earth that is best explained by their
affinity for aqueous solutions and a loss of water during the Earth's ac-
cretion (Sharp and Draper, 2013). From modeling of the Earth's early Pb
inventory, Connelly and Bizzarro (2016) found that the Moon-forming
impact should have left the Earth practically devoid of water. At one
end of the scale recent studies therefore conclude that major amounts of
formation water survived the Moon forming impact, while at the other
end of the scale other recent studies find that all the Earth's water was lost
during the Moon formation.
The case of Mars may have been similar. The proposed early forma-
tion of the Borelis basin (see Section 4.2.1) by a major impact would have
been an event that in relative terms was comparable in size to the Moon-
forming impact. As we shall argue in Section 4.2.1, a considerable loss of
water is to be expected, but there is no reason to a priori suppose this to
have brought the planet close to desiccation. Defining the formation
water as we did for Mars, we find that its amount must have been very
small. On the other hand, the late veneer started very early and – as
mentioned above
could possibly have brought ~0.1% of the planet's
mass in the form of H2O (Brasser, 2013; O’Brien et al. 2014). As
mentioned, this water may have been partially lost as a consequence of
the Borealis-forming impact.
Note that all the early impacts under consideration would also be
potential sources of water and other volatiles. There was hence interplay
between gains and losses, and the gains were due to accretion of ice- or
water-bearing planetesimals (for the Earth, also embryos). The rate of
such impacts was higher than at any later time in solar system history.
In view of the uncertainties around the early accretion of water by
Mars, any observational evidence would be extremely valuable. In the
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Planetary and Space Science 166 (2019) 70–89
search for such evidence, one may look for water in the oldest Martian
meteorites. Unfortunately, this method remained elusive for a long time.
The oldest specimen on record was ALH 84001, which is known to
contain the water-bearing mineral apatite in the form of chlorapatite and
merrillite (Cooney et al., 1999). Lapen et al. (2010) determined the age of
this meteorite as 4.091  0.030 Gyr. Chlorapatite is considered an
alteration product of primary fluorapatite due to aqueous activity (Bel-
lucci et al., 2017). Merrillite may have originally been Hþ-bearing
whitlockite, which changes our view on water-limited late-stage Martian
melts (Adcock et al., 2017). Indeed, during melt differentiation, the
incorporation of volatiles into minerals is delayed because most of them
do not need volatiles. Only at the end of the differentiation, the volatile
concentration is sufficient for crystallization of volatile-bearing phases.
Mafic melts are not considered very rich in volatile components. How-
ever, Adcock et al. (2017) indicated that these can be much richer than
previously thought, rich enough to crystallize not only one, but several
volatile-bearing phases.
The situation also recently changed due to the retrieval of Northwest
Africa meteorites NWA 7034 and NWA 7533. These are regolith breccias
containing clasts, which contain zircons with crystallization ages of about
4.4 Gyr (Humayun et al., 2013; Yin et al., 2014; Bouvier et al., 2018). The
detection of Δ17O with respect to the Mars fractionation line shows
fractional crystallization from water- or volatile-rich magma as well as
hydrous alteration to have occurred by that time (Ziegler et al., 2013;
Nemchin et al., 2014). Thus, we can now state with certainty that there
was water in the early, mafic crustal rocks of Mars and hence the early
Martian mantle was wet (Balta and McSween, 2013). Wade et al. (2017)
found evidence that Martian lavas hold more structurally bound water
and can retain it to greater depths than corresponding terrestrial basalts,
and thus can have contributed to a considerable removal of water from
the early surface of Mars into the mantle. Such silicate-mantle hydration
reactions could also form a natural explanation of the presence of for
example the oxidized magnetite identified in NWA 7034. We also have
evidence of very early aqueous activity on the Martian surface and in the
Martian crust. This water would likely represent the oldest part of the
Martian late veneer.
There is an extensive literature dealing with interpretations of both
Earth and Mars as two-component mixtures of different chondrite types
(Ringwood, 1979). W€anke (1981) applied this modeling to Mars, finding
a best fit for 60% highly reduced material like enstatite chondrites and
40% oxidized and volatile-bearing CI material. According to this homo-
geneous accretion model, Mars would thus have formed with a sub-
stantial amount of formation water. Brasser et al. (2017) summarized
recent work in this field. Based on variations in the abundances of several
isotopes (for instance, isotopes of O, Ti, Ni and Mo), a good fit for the
Earth was found to be 90% enstatite, 7% ordinary and 2% carbonaceous
chondrites (Dauphas et al., 2014), while for Mars the result was 45%
enstatite and 55% ordinary chondrites (Tang and Dauphas, 2014).
Brasser et al. (2017) pointed out that this hints at different formation
sites for the two planets, the latter being farther from the Sun. Hence,
Mars should not be considered as an embryo scattered out from the
narrow annulus of the Grand Tack model but rather as one that formed
far outside this annulus. They showed by extensive simulations that this
is dynamically viable while not a priori likely. Clearly, this would mean
some difference in the amount of formation water picked up by Earth and
Mars. However, putting this in quantitative terms is difficult, since large
variations of water content are found among different types of ordinary
as well as carbonaceous chondrites – L-type ordinary chondrites and
CI/CM-type carbonaceous chondrites carrying most of the water within
each class.
In summary, the low statistical likelihood of a scenario where Mars
was formed far outside its present location makes us focus on a formation
site close to the Sun. This means a very small amount of water acquired
during the rapid growth of the planet. However, there is evidence for wet
rocks in the Martian crust and mantle soon thereafter, possibly corre-
sponding to a global inventory of several km GEL as predicted by
H. Rickman et al.
dynamical models. This arrival marked the earliest part of the Martian
late veneer, largely predating the formation of the Moon.
2.2. The late veneer
We now focus on core formation and the accretion of volatiles by
impacts after this event. Core formation means the basic differentiation,
whereby reduced iron and siderophile elements settled into the inner-
most regions of a planetary object, and this should have happened to all
embryos due to the short time scale involved. The reason is both the
kinetic energy of impacting planetesimals and the heating by decay of
radionuclides. However, when embryos merged during the giant impact
phase, the cores should also merge, and it appears likely that material of
chondritic composition, which had been accreted previously, was molten
and differentiated too.
It is therefore natural to consider core formation as an ongoing pro-
cess that started very early and went on until the planet formation phase
was over. For the Earth it is thus tempting to regard the Moon-forming
event as the end of core formation, and the corresponding epoch for
Mars may be the end of the rapid formation of the embryo as dated by
Dauphas and Pourmand (2011).
The projectiles that hit the planets during the late veneer may be
called stray planetesimals. By this we mean all those planetesimals that
were still orbiting the Sun during the time in question. Clearly, since
planet formation was largely finished much earlier for Mars than for the
Earth, the stray planetesimal source must have been much richer for
Mars. However, there is a caveat. Classically, planetesimals are thought
of as km-sized objects, but this may not be accurate. There has been a
recent paradigm shift concerning planetesimal formation, and at least for
the inner planetary region the classical picture of hierarchical accretion
has been challenged by one of gas-grain instabilities in the solar nebula
(Johansen et al., 2014).
In the latter case, giant swarms of “pebbles” are subject to gravita-
tional collapse and may form objects 100–1000 km in size (Johansen
et al., 2007). Moreover, as argued by Morbidelli et al. (2009), the main
belt asteroids may derive from an initial population characterized by
sizes in excess of 100 km, consistent with being such large planetesimals.
Within this scenario, the stray planetesimals that hit the Earth and Mars
early on were also very big. This begs the question to what extent their
impacts onto the planets would have tended to mix their reduced iron to
large depths, even contributing to the planetary cores.
The usual assumption is that, after core formation, the impinging
planetesimals would dump their highly siderophile elements (HSE) into
the mantle, so that by measuring the amount of HSE currently residing in
the mantle, one can deduce the total mass of the late veneer contribution
from the HSE cosmic abundances, assuming the projectiles to be chon-
dritic. This has led to an estimate of about 0.5% of the Earth's mass from
the late veneer (Walker, 2009).
For the Moon the corresponding estimate is about 0.03 wt% (Day and
Walker, 2015; Kruijer et al., 2015). Such a low value caused concern,
because the ratio between the late veneer amounts of HSE in the Earth
and the Moon is then much larger than the ratio of the collisional cross
sections of the two bodies. Bottke et al. (2010) suggested that the reason
could be connected to the mass distribution of the large planetesimals. If
this were shallow enough, the total mass would be mostly bound up in
the largest objects. Since the Earth would accrete larger objects than the
Moon, a very large mass ratio could ensue (Sleep et al., 1989). However,
as mentioned above, Morbidelli et al. (2018) prefer a different explana-
tion for the large ratio of the mantle HSE abundances, relying on a sig-
nificant delay in the Moon's ability to retain the accreted HSE in the
mantle.
Brasser et al. (2016b) performed Monte Carlo simulations of the late
accretion of planetesimals by the Moon and all the terrestrial planets
considering the time after 4.5 Ga, which they took as the time of the
Moon-forming impact. The HSE concentration in the Martian mantle,
derived from Martian meteorites, may be explained by metal-silicate
74
Planetary and Space Science 166 (2019) 70–89
equilibration early in the planet's history (Righter et al., 2015) and
thus does not require any substantial accretion post-dating the formation
of the Moon. Brasser et al. indeed found that the preferred way to satisfy
both the constraint of a high Earth/Moon HSE ratio and that of avoiding
the re-melting of the Earth's crust by late, big impacts was to have only
one very big object providing the Earth's late veneer, while the plane-
tesimal population swept up by the Moon and Mars had a relatively low
mass. As a result, Mars would have accreted at most about 0.1 wt%.
We may estimate the corresponding amount of water by assuming a
certain composition and water abundance of the stray planetesimals. If
we use the average composition of the meteorites falling on the Earth
today, we can estimate about 6% of the objects being of CI chondrite type
and containing on the average 5% water. As a result, we obtain 0.3% of
the late veneer, or 0.0015% of the Earth's mass as late veneer water. This
is orders of magnitude below the Earth's water content and thus appears
negligible.
There is reason to think that the stray planetesimal bombardment had
an average chondritic composition similar to today's meteorite influx to
the Earth, but since we do not know this, we can also imagine an extreme
case, where all the planetesimals have a CI chondrite composition instead
of just 6%. The above exercise would then result in 0.024% of the Earth's
mass – still insufficient to deliver all the water in the Earth. On the other
hand, such a composition of the late veneer is in conflict with observa-
tions and thus has to be rejected.
Drake and Righter (2002) show the distribution of 187Os/188Os ratios
in chondrites compared to the average for the Earth's primitive upper
mantle. Since osmium is a HSE, and the HSE elemental abundance
pattern relative to the chondritic HSE composition is flat, this element
can be used as a tracer of the material accreted by the Earth after core
formation. The best isotopic agreement is found for ordinary chondrites.
Using the result of Brasser et al. (2016b), we may conclude that the very
big object delivering the Earth's mantle HSEs had a composition consis-
tent with ordinary chondrites. Since it was thus very poor in water, the
conclusion of a negligible amount of late veneer water in the Earth seems
verified.
Fischer-G€ odde and Kleine (2017) found independent support for this
conclusion by studying Ru isotope anomalies in the different chondrite
classes and comparing these with the ruthenium of the Earth's mantle –
the latter probing the late veneer. The result was that, in terms of Ru
isotopes, the Earth's late veneer stands out from all the chondrites. In
particular, the Ru isotopic signature of the water-bearing chondrites of
the formation water is not seen in the mantle, indicating that this
ruthenium was partitioned into the Earth's core during the differentiation
of our planet. By contrast, the late veneer did not originate in the outer
solar system and could not have been the primary source of water and
volatiles in the Earth.
For Mars it seems relevant to assume, like we did above for the Earth,
that the late veneer contained 0.3% water. Combined with the estimated
maximum of 0.1 wt% for the Martian planetesimal accretion after Moon
formation (Brasser et al., 2016b), we find a corresponding GEL of at most
about 15 m. However, as indicated above, the preceding period that
postdated the formation epoch would likely have brought a much larger
quantity of water to Mars.
There is an interesting issue dealing with the amount of CO2 that Mars
might have accreted along with the early water. Suppose that the icy
projectiles had a CO2/H2O mass ratio ~0.2, similar to some observed
comets. With an accreted amount of H2O of ~0.1% of the planetary mass,
an efficient outgassing of CO2 would create a surface partial pressure of
~30 bar. According to Amerstorfer et al. (2017), the loss of this amount
of gas by thermal escape (see Erkaev et al., 2014) would be very prob-
lematic, and as discussed in Section 3, a much more moderate loss by
sputtering was estimated by Jakosky et al. (2017) based on MAVEN data.
Then, why does Mars not show any trace of the remainders? The simplest
answer is that the early projectiles hitting Mars had a considerably lower
CO2/H2O ratio than typical comets. A’Hearn et al. (2012) summarized
observational results on CO and CO2 abundances in comets and
H. Rickman et al.
concluded that their origin is likely found between the CO2 and CO snow
lines. By contrast, the icy planetesimals considered in the Grand Tack
model originated much closer to the Sun and should thus have contained
much less CO2.
In summary, the amount of water acquired by Mars significantly after
the formation of the Moon is estimated to have been only ~1% of the
earlier inventory. We find that the water-bearing projectiles both before
and after Moon formation likely carried a much lower CO2/H2O mass
ratio than typical comets, having originated closer to the Sun. Thereby,
these impacts would not have created an excessively massive CO2
atmosphere.
2.3. The trans-planetary water
According to Morbidelli et al. (2012b), the LHB was an episodic peak
in the lunar bombardment rate that started abruptly about 4.1 Gyr ago
and decayed during the following several hundred Myr. It would thus
account for the mare basins on the Moon due to the large end of the
projectile size distribution but also for the plethora of smaller craters that
cover the lunar highlands due to the small impacting objects. In the Nice
Model scenario of Gomes et al. (2005), this would partly come from a
massive disk of icy planetesimals beyond the giant planet orbits and their
surroundings, which had been cleaned of stray planetesimals during the
growth of the giants. A sudden instability within the multi-resonant
system of giant planets would eject the icy giants into this disk, where
their orbits got circularized by dynamical friction and migrated outward
into their current locations (Morbidelli et al., 2010; Levison et al., 2011).
While the episodic peak of the impact rate has been taken as a fact in
much of the recent literature, there has also been a debate around this
issue, including the point of view that the saw-tooth shape of the cra-
tering curve claimed by Morbidelli et al. (2012b) is not securely estab-
lished owing to saturation of the highland surface. As mentioned above,
from the work of Morbidelli et al. (2018) the LHB should rather be
interpreted as the tail end of planetesimal bombardment than as an
episodic peak. This is why we take a very early instability of the planet
orbits in the Nice Model as a possibility in our baseline case and consider
the late instability only as a possible alternative. In each case, the
trans-planetary disk would have been dispersed by the migration of the
ice giants in essentially the same manner with the same consequences for
the delivery of water to the inner solar system by trans-planetary
planetesimals.
The main issue is about the amount of water that this could bring to
the Earth or Mars rather than the time at which the delivery occurred. Let
us first seek a rough estimate. The mass of the trans-planetary disk has
been inferred by dynamical arguments to be of order 30–50 Earth masses
(Gomes et al., 2005). Gravitational scattering is expected to transfer
about 10 Earth masses into orbits crossing the inner solar system, and if
these perform on average 103 Earth-crossing orbits with an impact
probability ~10
8 per orbit (Rickman et al., 2014), the mass accreted by
the Earth would be ~10
4 Earth masses or 6  1020 kg. This indicates
that the trans-planetary source should have been quite inefficient in
supplying the Earth's water.
However, to make the case clear, we need a comprehensive analysis.
Rickman et al. (2017) recently performed this, considering the likely size
distribution of the projectiles, their individual impact probabilities with
respect to the individual targets, the physical lifetimes of the projectiles,
and the probability distribution of the number of actual impacts in the
size range where the expectancy is small. When considering different
masses of the primordial planetesimal disk and different transfer effi-
ciencies into the inner solar system, the conclusion was that the Earth
would likely have swept up, at the most, about 2  1020 kg of
trans-planetary projectiles. This is only about 3% of the Earth's water,
and allowing for a current estimate of about 20% water in comet nuclei
(Rotundi et al., 2015), the estimate is below 1%. For Mars, the corre-
sponding estimate was about 10 m GEL, which is way below the
above-mentioned estimates of the Martian water inventory.
75
Planetary and Space Science 166 (2019) 70–89
In our baseline case, this delivery occurred long before the Earth was
formed. Moreover, the Oort Cloud was formed early according to the
scenario proposed by Brasser and Morbidelli (2013). Let us now discuss
how these phenomena might have influenced the accretion of water by
the Earth and Mars.
Let us suppose the timing of the planetary instability to have been 10
Myr after CAI formation, just to fix the ideas. According to the Grand
Tack model, the embryos of the terrestrial planets were then confined
mostly within a narrow annulus located around the Earth's present orbit
(Walsh et al., 2011). One of these embryos was planet Mars before it had
accreted most of its supplement of planetesimals. Several of the others
were building blocks of the Earth.
For a rough estimate, we may scale the above estimates of the
amounts of projectiles colliding with the planets to the amounts colliding
with the corresponding numbers of embryos. The total collisional area of
the embryos is larger than that of the current planets, but the ratio is
reduced for the Earth because most of the gravitational focusing by the
full-size planet is lost when considering the much smaller embryos. At the
same time, the lower gravity prevents the efficient retention of water, so
we tentatively conclude that this source of trans-planetary formation
water cannot have been important for the Earth. For Mars, the case re-
mains the same as already discussed, because Mars was roughly the same
10 Myr after CAI formation as during the LHB.
Oort Cloud comets may provide an additional source of water-bearing
objects colliding with the Earth or Mars. The most interesting issue
concerning an early formation of the Oort Cloud is about the Sun's birth
cluster. It seems very unlikely that the Sun was born in isolation, and both
Lada and Lada (2003) and Adams (2010) discussed the probability dis-
tribution of cluster size. According to Nordlander et al. (2017), it is likely
that the Sun resided in its birth cluster for an extended period of time.
They hence investigated the consequences of this for the survival of
comets in a primordial Oort Cloud.
One result of this study is that about 1% of the Oort Cloud comets may
be driven into the inner solar system by the cluster tides, somewhat
dependent on the size of the birth cluster and the time the Sun was
ejected from it. This represents a very meager source of projectiles, and
its water supply would hardly be noticeable compared to the likely
amount of formation water.
Considering the possibility of a late, Nice Model instability explaining
the LHB, we note that this implies an additional source of water-bearing
projectiles before the LHB, i.e., during the late veneer. According to
Levison et al. (2011), viscous stirring within the planetesimal disk would
have delivered ordinary members from the innermost part into orbits
approaching the outermost ice giant. These would then have been flung
around due to a series of close encounters with the giants, until some of
them became terrestrial planet crossers and impacted upon the planets.
The process just outlined would have started just after the dissipation
of the solar nebula, but in case it went on
as generally imagined – for
several hundred Myr until the start of the LHB, it still was quite gentle.
The integrated amount of impacts was small compared to that of the LHB.
Thus, even if the projectiles were rich in volatiles, this bombardment is
not likely to have been important for the water budget of the terrestrial
planets.
In summary, based on detailed calculations, we find the probability of
a significant contribution by trans-planetary water to be very low in both
the Earth and Mars, independent of whether the Nice Model planetary
instability occurred early or late.
2.4. The origin of water
It therefore seems difficult to argue for a truly cometary origin of the
water on the Earth as well as on Mars. When we combine the conclusions
of the last three subsections, there is only one source that can reasonably
have provided the bulk of the Earth's water. This is what we called for-
mation water, i.e., the water contained in both embryos and planetesi-
mals that were accreted during the giant impact phase. The associated
H. Rickman et al.
amount of losses is hard to quantify accurately, but it likely was not
drastic.
The most energetic impacts suffered by Mars were likely smaller than
those of the Earth, so that Mars may have avoided some of the Earth's
losses. Nonetheless, impact erosion associated with the most outstanding
collisional events in Martian history has likely influenced the water
budget on that planet too. Concerning impacts of more normal size, nu-
merical and analytical modeling results indicate LHB erosion to be quite
inefficient (Lammer et al., 2013), but it is likely that much larger impacts
occurred in the early, pre-Noachian era (see Section 4.2.1).
The dating of the Moon forming impact is not yet very accurate. In
principle, pushing the formation of the Moon to earlier times would allow
a major increase of the amount of water that the Earth accreted after-
wards (Jacobson et al., 2014). However, their timing of the
Moon-forming impact is precisely due to a limit to the mentioned amount
set by the HSE abundances in the Earth's mantle. Walker (2009) found
that the Earth's primitive upper mantle (PUM) contains between 3.1 and
3.9 ppb iridium, which is to be compared with the chondritic Ir abun-
dance of 400–800 ppb. Assuming that the HSEs in the primitive upper
mantle derive from a chondritic late veneer, these ranges translate into a
0.4–1.0% contribution of this type to the PUM.
If we assume no mixing between the PUM and the lower mantle, we
find that the chondritic late veneer contributed 0.1–0.2% of the total
mass of the Earth. On the other hand, assuming full mixing, this range
changes into 0.3–0.7%, which brackets the value of 0.5% used by
Jacobson et al. (2014) and Connelly and Bizzarro (2016). Hence, the
formal uncertainty of that value is not dramatic, and the above conclu-
sion stands in that the Earth's entire supply of water cannot have an
origin in the late veneer – the absolute maximum would be about one
ocean mass, assuming 100% of the chondrites to be of CI type. However,
as mentioned above, the osmium isotope ratio of the PUM shows that this
was not the case, and the ruthenium isotopes tell the same story.
As to the LHB, the first question is if indeed there was an episode
involving icy projectiles. However, even if the answer would be yes, we
have found that such a source was by far insufficient to deliver the
necessary water to either Earth or Mars. While the asteroid E-belt has
been proposed to deliver many more projectiles (Bottke et al., 2012),
these would be practically devoid of water and hence would not solve the
problem.
The amount of iridium measured in the ISUA sediments by Jørgensen
et al. (2009) sets an upper limit to the amount of chondritic LHB pro-
jectiles, especially if these impacted onto the Earth at low speeds, typical
of asteroids. This might constrain the total amount of E-belt bombard-
ment. However, enough water could only have been brought by a very
rich source of comets. There is no such source known to exist, which
would have been able to provide an episodic surge of bombardment in
the inner solar system about 4 Gyr ago. In fact, the richest source of
comets that has ever existed – i.e., the trans-planetary planetesimal disk
of the young solar system – has been shown to be insufficient to deliver
the Earth's water.
Since the history of the Earth's water accretion is somewhat uncertain,
it would seem preposterous to claim a detailed knowledge of the source
for water on Mars. Empirical evidence relevant to Mars exists in the
above-mentioned Northwest Africa meteorites. In particular, NWA 7533
is enhanced in nickel and HSE with respect to the igneous rocks of usual
SNC meteorites at a level corresponding to about 5% admixture of
chondritic input into the early Martian crust (Humayun et al., 2013) – see
Fig. 1. If the crustal depth of Mars is about 50 km (Zuber et al., 2000),
then 5% of the crustal mass corresponds to 1  1021 kg or 0.15% of the
planetary mass, corresponding to about 6 km GEL. This might be a lower
limit to the late veneer accretion of water to Mars during the giant impact
phase (predating the formation of the Moon), since water deriving from
chondritic planetesimals would also have been present in the mantle.
However, if correct, it is in rough agreement with the predictions by
dynamical accretion models.
76
Planetary and Space Science 166 (2019) 70–89
Fig. 1. Siderophile-element abundances measured in the North African, Martian
meteorite NWA 7533. Panel a shows nickel and panel b shows iridium, both
against the magnesium abundance. The symbols refer to different samples as
explained in the legend to the right. Domains occupied by lunar breccias and
SNC meteorites are identified. Reprinted by permission from Springer Nature:
Nature, Origin and age of the earliest Martian crust from meteorite NWA 7533,
Humayun et al. (2013).
3. The Martian atmosphere
As part of the accretion of terrestrial planets, the embryos that built
up Venus and the Earth, and the one that may have survived as planet
Mars, were certainly formed within the solar nebula. Even though the
lifetime of the latter is not accurately known, it is clear that the ~10 Earth
mass cores of Jupiter and Saturn were able to form before the gas disk
dissipated, and thus, one has to conclude that the terrestrial planet em-
bryos – with a shorter accretion time scale – also formed in a gas-rich
environment. This is supported by the short time-scale for the forma-
tion of Mars as well as theoretical planetary accretion models (Brasser,
2013).
One consequence of this is the formation of massive, primordial at-
mospheres due to the gravitational capture of nebula gas (see Rafikov,
2006). Based on the estimates by Hayashi et al. (1979), Mars could then
have been surrounded by a gas envelope of mass ~1022 kg, whereof the
expected H2O mass from cosmic abundances would be ~1020 kg. There
would also have been noble gases including non-radiogenic argon in
accordance with their solar abundances.
Clearly, this primary atmosphere did not survive. Lammer et al.
(2013) have reviewed this topic. From observations of its present-day
counterparts (young G stars), the early Sun is expected to have bathed
the newly born terrestrial planets in very large fluxes of X-rays and EUV
photons. These caused hydrodynamic escape of the dominant hydrogen
gas as well as photo-dissociation of molecular species like H2O within
~10 Myr or less (Lammer et al., 2013). Moreover, the noble gas abun-
dances in the current terrestrial planet atmospheres (Fig. 2) are several
orders of magnitude below those of rock-forming elements, this depletion
decreases with atomic mass, and the different planets differ markedly
from each other with Mars being the most depleted (Pepin, 1991).
We may thus consider the short-lived, primary Martian atmosphere a
closed chapter with very small implications for the planet's current,
secondary atmosphere. According to the evidence for retention of some
fraction of the primordial volatiles in the Earth (Schlichting and
H. Rickman et al.
Fig. 2. Measured abundances of non-radiogenic isotopes of noble gases in the
atmospheres of Venus, Earth and Mars, and in CI chondrites (the latter being
considered as the most primitive type). The quantity plotted is the number of
isotopes per million Si atoms in the respective planet, divided by the corre-
sponding ratio in the solar atmosphere. The xenon isotopic abundance in the
Venus atmosphere is only an upper limit. Reprinted by permission from Springer
Nature: Space Science Reviews, Outgassing history and escape of the Martian
atmosphere and water inventory, Lammer et al. (2013).
Mukhopadhyay, 2018), it is reasonable to expect the same for Mars.
However, its volatiles were mainly brought by planetesimals and later
projectiles, as sketched in Section 2. This accretion, along with volcanic
outgassing of the volatiles and a variety of loss processes, has thus pro-
duced the current Martian atmosphere. There are close links between the
Martian water and the secondary atmosphere. For instance, the atmo-
spheric gases stem from the same projectiles that also brought the water
to the planet. They also provide the surface pressure that may stabilize
liquid water, which in turn sculpts the surface and leaves its imprints on
the mineralogy of the surface rocks. Moreover, the presence of H2O in the
Martian atmosphere leads to a deuterium enrichment that can be used to
trace the history of water on Mars. This motivates the following discus-
sion of the Martian atmospheric evolution.
In order to trace the atmospheric losses, the noble gases are consid-
ered important in view of their chemically inert nature. Marty et al.
(2016) discussed the origin of the atmospheric noble gases for the case of
the Earth. Their conclusion, based on the argon abundance in the coma of
comet 67P/Churyumov-Gerasimenko (Balsiger et al., 2015), was that,
while comets of this type were likely unimportant for the Earth's accre-
tion of volatiles at large, they would have been a natural source for the
noble gases. They mentioned in particular a cometary late veneer or the
trans-Neptunian part of the LHB in order to limit the giant-impact driven
losses. In our baseline case of an early planetary instability, to have this
episode occur after the majority of the giant impacts is not unlikely given
that such impacts tended to occur very early (O’Brien et al. 2014).
However, it is not yet clear, if a sufficient amount of noble gases could
still be retained.
For Mars, an early shower of trans-Neptunian projectiles would have
brought a large part of their noble gases directly into the atmosphere.
Hence, judging from the results of Schlichting and Mukhopadhyay
(2018), it is likely that atmospheric erosion due to impacts by km-sized
77
Planetary and Space Science 166 (2019) 70–89
objects would have caused an important loss of these gases indepen-
dent of atomic mass. A quantitative estimate will be mentioned below.
Due to the recent measurements of the non-radiogenic isotope ratio
36
Ar/38Ar using the SAM-QMS instrument on board the NASA Curiosity
rover (Mahaffy et al., 2013; Atreya et al., 2013), Mars' atmospheric argon
has come into focus. The mentioned ratio was found to be 4.2  0.1
(Atreya et al., 2013), consistent with the range thought to characterize
SNC meteorites (Bogard, 1997) but lower than all other values measured
in the solar system, which are near 5.4. This means a fractionation in
favor of the heavier isotope, which is explained by a preferential loss of
the lighter one into space. In the present case, the mechanism relies on
solar wind induced pickup-ion sputtering causing escape of Ar from near
the exobase, where the lighter isotope is overrepresented due to diffusive
separation above the homopause (Luhmann et al., 1992; Jakosky et al.,
1994).
The total amount of the loss of atmospheric argon on Mars estimated
by Atreya et al. (2013) is at least 50%, and possibly as large as 85–95%,
during the last 4 Gyr. This time interval comes from modeling of the
escape processes acting at earlier times (e.g., Pepin, 1994), which in-
dicates the remaining abundance of atmospheric argon ~4 Gyr ago on
Mars to have been well below the current argon abundance. Thus, the
current isotope ratio can be modeled as a result of a balance between Ar
outgassing with a ratio near 5.4 and the above-described mass-dependent
loss during the last 4 Gyr. The mentioned Ar loss fractions were estimated
from such models.
Even more recently, Jakosky et al. (2017) reported measurements by
the NASA MAVEN (Mars Atmosphere and Volatile Evolution) spacecraft,
pertaining to the same isotope ratio and related atmospheric modeling.
According to these authors, about 66% of the argon in the Martian at-
mosphere has been eroded away by solar wind sputtering during the
same time interval. This would imply the loss of a major fraction of the
entire atmosphere. In particular, Jakosky et al. (2017) estimated the
sputtering loss of CO2 using their results for argon. In this case the
sputtering is preceded by photodissociation of CO2 into atomic carbon
and oxygen, which are present near the exobase. According to their
model, as much as ~0.5 bar of CO2 may thus have been lost over time.
Kurokawa et al. (2018) modeled the evolution of the Martian atmo-
sphere, including most of the gain and loss processes thought to be of
relevance. They found that the rate of isotopic fractionation of nitrogen
and argon (15N/14N and 38Ar/36Ar ratios) due to solar wind sputtering
decreases with the thickness of the atmosphere, i.e., the surface pressure.
To be consistent with the relatively small amounts of fractionation
measured in the 4.1 Gyr old Martian meteorite ALH 84001 (Mathew and
Marti, 2001), they concluded that a surface pressure of at least 0.5 bar is
needed at the time, when this meteorite was formed.
Such a pressure would likely have prevented the collapse of the at-
mosphere by freezing out of the CO2 at the poles according to the climate
modeling of Forget et al. (2013). It would also have allowed atmospheric
circulation, such that H2O could be transported to topographic highs,
thus creating fluvial terrains by episodic ice melting (Kurokawa et al.
2018).
In fact, there is a ~4–5% enrichment of 13C in Martian atmospheric
CO2 (Webster et al., 2013; Mahaffy et al., 2013), which is likely due to a
significant loss of CO2 into space during the same time. Note, however,
that in addition to the atmospheric loss mechanisms that cause isotope
fractionation, there are other losses that leave the isotope ratios unaf-
fected. Hence, the global loss rates could have been even larger than the
ones just mentioned.
Atmospheric impact erosion would not cause appreciable fraction-
ation, in case the impacting projectiles are large enough to remove an
atmospheric cap tangent to the surface at the point of impact (Melosh and
Vickery, 1989), or at least cause ejection of an atmospheric mass domi-
nated by the homosphere. In most models of atmospheric erosion and
replenishment (de Niem et al., 2012; Pham et al., 2011), the projectiles
are assumed to contain a non-zero fraction of volatiles, so that each
eroding impact is accompanied by some fresh supply of atmospheric
H. Rickman et al.
gases. However, it is not clear if this was always the case. Even with a late
planetary instability, as mentioned above, Bottke et al. (2012) argued
that the LHB projectiles mainly originated in the E-belt and were hence
very poor in water or other volatiles.
Among loss mechanisms for atmospheric CO2, impacts and sputtering
have to be supplemented by surface reactions involving carbonate for-
mation. These were suggested long ago (e.g., O’Connor 1968) but
appeared somewhat doubtful in the light of the failure to detect resulting
carbonates by the Mars Express OMEGA instrument (Bibring et al.,
2005). Bristow et al. (2017) also reported on a non-detection of car-
bonate phases by the Curiosity rover at Gale crater. However, carbonates
do exist on the Martian surface in Noachian outcrops often associated
with phyllosilicates, as found from Mars Reconnaissance Orbiter CRISM
spectra (Wray et al., 2016). This indicates that some CO2 was indeed lost
from the atmosphere by carbonate formation.
The extent of this loss remains difficult to specify. Thus, it is not clear
how the total loss was partitioned between sputtering, impact plumes
and carbonate formation or how this balance may have shifted with time.
In any case, the Mars Express ASPERA-3 observations (Barabash et al.,
2007) placed significant upper limits to the past, cumulative loss of CO2
by solar wind caused COþ 2 escape. While this does not conflict with the
removal of large quantities of CO2 by the above-mentioned sputtering,
we note that Jakosky et al. (2017) considered 0.5 bar as an upper limit to
the CO2 loss by sputtering, while Kurokawa et al. (2018) found 0.5 bar to
be a lower limit to the surface pressure 4.1 Gyr ago. This indicates that
impact erosion and, possibly, carbonate formation have been important
been important.
The main source of atmospheric gases, acting at all times though
principally when the planet was young and active, was large-scale
volcanism (seen, for example, in the Tharsis uplift). Lammer et al.
(2013) provided an in-depth discussion of Martian volcanism and its
associated volatile outgassing. In their model, the growth of a volcani-
cally formed, secondary atmosphere may have started 4.3–4.0 Gyr ago,
after the input rate started to exceed the loss rate caused by solar EUV
(Tian et al., 2009).
Thus, given that Martian volcanism extended to times beyond the
LHB, a substantial atmosphere seems a likely outcome during the late
Noachian. The actual sequence of events that occurred during this time in
Martian history remains an unsettled problem of utmost importance. In
addition to explaining the intriguing traces seen on the surface of Mars, to
be discussed in Section 4, it couples to the already discussed issue of the
origin of Martian volatiles.
3.1. The D/H ratio
The history of surface water in Mars is reflected in the current at-
mospheric deuterium/hydrogen ratio (D/H) as well as those found in
Martian meteorites and in ground deposits of clay minerals. For conve-
nience, let us express D/H in units of the VSMOW (Vienna Standard Mean
Ocean Water) ratio, which equals 1.56  10
4. This atomic D/H abun-
dance ratio characterizes the Earth's oceanic water.
Photodissociation of H2O and HDO in the Martian atmosphere pro-
duces H and D atoms, of which some fraction is lost by exospheric escape.
This fraction is larger for the lighter H atoms. Hence, the surviving atomic
hydrogen gets enriched in deuterium, and the atmospheric water vapor
gets enriched in its deuterated variant. Water on and immediately below
the planetary surface is subject to continuous exchange with the atmo-
sphere and thus tends to adapt to the atmospheric D/H ratio, while the
Martian mantle water keeps its original value. From planetary formation
models, this value is expected to be not far from that of the Earth. Lunine
et al. (2003) estimated D/H  1.2–1.6 referred to VSMOW.
The Martian atmosphere has a general D/H of about 5–6 (Owen et al.,
1988; Leshin et al., 1996). Local variations, caused by isotopic fraction-
ation during ice sublimation and condensation (Montmessin et al., 2005),
have been detected spectroscopically (Novak et al., 2011). Using an
empirical value for the isotopic fractionation efficiency related to the
78
Planetary and Space Science 166 (2019) 70–89
exospheric loss process and an estimate of the global amount of
exchangeable surface water, one may derive the cumulative amount of
surface water that has been lost from Mars (Kurokawa et al., 2014).
The question when this loss took place can be tackled using D/H
measurements in Martian meteorites of various ages and in clay minerals
deposited on the Martian surface very long ago. While the interpretation
of the latter is relatively straightforward (Mahaffy et al., 2015), the
meteorites require special attention, since these may contain both ele-
ments of parental magma including mantle water and assimilated crustal
rocks including the exchangeable water of the time of crystallization.
By means of the Sample Analysis at Mars (SAM) experiment on the
NASA Curiosity rover, Mahaffy et al. (2015) were able to determine D/H
in the clay mineral smectite found in the Gale crater, dating from the
Hesperian era. The value measured was close to 3, which indicates that
the Martian atmosphere about 3 Gyr ago had already undergone an
important loss of water, while much more was still to occur.
The oldest Martian meteoritic specimens for which D/H has been
measured are mantle melt inclusions in Yamato 980459. The age of these
has been estimated as 4.5 Gyr, and their D/H is found to be 1.275 or
smaller (Usui et al., 2012). This means a very small D enrichment (if any)
with respect to the water picked up by Mars through planetesimal
accretion.
Next comes the orthopyroxenite meteorite ALH 84001 whose age is
4.1 Gyr as mentioned above. Its D/H was measured using the same
chlorapatite grain by Boctor et al. (2003) and Greenwood et al. (2008)
with very different results. While the first investigation found D/H  2.2,
the second found D/H  4. It thus seems that, by the time Mars was 0.5
Gyr old, a fair amount of loss of surface water had already occurred. This
led to the picture of a two-stage loss process for Martian water – an early,
very efficient one preceding ALH 84001 and a slower one operating later
on until the present.
This concept is illustrated in Fig. 3, which is copied from Villanueva
et al. (2015). These authors measured the D/H of the Martian polar ice
caps by telescopic observations, finding D/H  8. The two-stage history is
clearly exhibited with most of the water loss having occurred during the
earliest phase and most of the current deuterium enrichment deriving
from the extensive period that followed. As to the absolute amount of lost
surface water, Villanueva et al. (2015) used 21 m GEL for the ice in the
polar layered deposits (PLDs) in agreement with the above-mentioned
estimate of 20–30 m, to derive an initial amount of at least 137 m GEL
about 4.5 Gyr ago. However, the early losses of water likely involved
processes that did not lead to any isotopic fractionation, and so the initial
amount could have been much higher. In addition, by correcting for
other cryospheric ice reservoirs near the Martian surface (Carr and Head,
2014), there is obviously room for further increase.
Thus, the isotopic data seems consistent with a large amount of water
lost from the surface layers of Mars during its entire history plus an
additional large amount still residing below the surface and at larger
depths. The loss would have been very intense during the first 0.5 Gyr
and then settled at a lower pace. This would be compatible with a planet
that was geologically much more active during its youth than at later
times. The model of mantle dehydration by Balta and McSween (2013)
and Balta et al. (2013) involves a wet mantle and a strong magma out-
gassing during the early history of Mars. In this model, the upper mantle
would have suffered progressive dehydration and isolated hydrous
mantle upwelling during the Hesperian, causing a dehydrated upper
mantle in the Amazonian. The progressive dehydration of the Martian
mantle has also been discussed by McCubbin et al. (2012) and Slaby et al.
(2016).
Usui et al. (2015) measured D/H in glassy inclusions of the shergot-
tites Yamato 980459, Elephant Moraine 79001 and Larkman Nunatak
06319. The resulting values ranged from near 1 to near 3. The authors
thus found evidence for a distinct water/ice reservoir with D/H ~ 2–3
(see Fig. 4) that has existed throughout the period of formation of the
shergottites, which means several hundred Myr. This could possibly
represent the exchangeable water reservoir of the Hesperian era, but its
H. Rickman et al. Planetary and Space Science 166 (2019) 70–89

Fig. 3. Plotted versus time before present are the D/H ratios measured in different samples of Martian water, representing the surface water reservoir at the respective
occasions (red curve with axis to the right) and the calculated quantity of water in this reservoir compared to the present (blue curve with axis to the left) using a
model for fractionation by thermal escape. To the left of the diagram, an estimate is made for an early Mars ocean based on a current reservoir of 21 m GEL as derived
for the polar layered deposits. Reprinted by permission from The American Association for the Advancement of Science: Science, Strong water isotopic anomalies in
the martian atmosphere: Probing current and ancient reservoirs, Villanueva et al. (2015). (For interpretation of the references to colour in this figure legend, the reader
is referred to the Web version of this article.)

their average value, based on the limited statistics of comet measure-

ments, seems higher than the initial D/H ratios of Earth's and Mars'
accreted water. The LHB contribution of water to the terrestrial planets
should have had the same range of D/H. However, as argued above, this
is likely to have been too small to significantly influence the VSMOW
ratio.

4. Evidence from geomorphology and mineralogy

Fig. 4. Deuterium enrichments of water with respect to VSMOW in solar system
small bodies and Martian reservoirs are shown in this cartoon. Arrows indicate
possible exchanges of water between the different Martian reservoirs. Reprinted
by permission from Elsevier: Earth and Planetary Science Letters, Meteoritic
evidence for a previously unrecognized hydrogen reservoir on Mars, Usui
et al. (2015).
origin remains to be established.
The LHB impacts by comet-like projectiles would have delivered
water with a comet-like D/H, but it is not clear what that means. Jupiter
family comets are preferred as a model, as discussed in the previous
Section. If the observations by Hartogh et al. (2011) of comet
103P/Hartley 2, using the Herschel satellite, would be indicative of
Jupiter family comets at large, then one would expect D/H  1. However,
Rosetta observations of comet 67P/Churyumov-Gerasimenko (Altwegg
et al., 2015) showed D/H  3 in this Jupiter Family comet. The same
broad range is also shared by Oort cloud comets, which show a signifi-
cant scatter in D/H including values near 2 (Altwegg et al., 2015).
In the picture of Oort cloud formation developed by Brasser and
Morbidelli (2013), both this cloud and the scattered disk that is the
source population for the Jupiter family derive from the same initial
comet population, which was formed beyond the giant planet region.
This explains why they are mutually similar in their D/H values, while
There is a common agreement that about 3.8 Gyr ago, when Mars had
a denser atmosphere, and higher temperatures prevailed, liquid water
flowed on the surface of the planet. Several findings suggest the previous
existence of water under and on the surface of Mars. Remote sensing
images of the Martian surface, show the presence of interesting
geomorphic features such as channels, probably carved through erosion
by water running across the surface (e.g. Malin and Edgett, 2000; Bond,
2012), old river valleys, basins of ancient lakes, dry stream beds (Howard
et al., 2005; Plaut et al., 2009) and eroded craters. It is also possible that a
large ocean existed on Mars at that time (Baker et al., 1991; Carr and
Head, 2003; Fairen et al., 2003; Di Achille and Hynek, 2010; Bond,
2012). The regions that are most covered by valley networks are situated
between the equator and the mid-southern latitudes. Studies of the polar
caps, ground ice and numerous channel networks suggest that liquid
water may have been present in the Noachian, but favorable conditions
for the presence of water may have recurred during the Hesperian era.
The observational evidence concerning the past presence of water on the
surface of Mars will be discussed in the next sections.
Compositional measurements from orbiter observations indicate that
an important fraction of the water is stored in minerals. Multiple in-
struments orbiting Mars, operating in the near- and mid-infrared spectral
range, have been able to identify and characterize most of the surface
constituents. Hydrated silicates, particularly phyllosilicates, were iden-
tified by the spectrometers OMEGA of Mars Express (MEx; e.g., Bibring
et al., 2006, Bibring, 2011) and CRISM of Mars Reconnaissance Orbiter
(MRO; e.g., Murchie et al., 2009), as well as TES onboard Mars Global
Surveyor (MGS) and THEMIS onboard Mars Odyssey (MO; e.g., Chris-
tensen et al., 2004).
4.1. Valley networks, outflow channels, and northern hemisphere ocean
Numerous landforms observed on the Martian surface provide evi-
dence of extensive past, hydrous activity. The morphology of valley

79
H. Rickman et al.
networks and outflow channels indicate that liquid water is responsible
for formation of these features. The mode, timing and long-term cycling
of water in surficial processes are phenomena to be considered when
interpreting the various signs of activity (Baker, 2001).
The valley networks are integrated channel systems, with individual
channels up to a few kilometers wide and lengths up to a few hundreds of
kilometers (Baker, 1982, 2001). These are primarily found on Noachian
units, although some are seen on the flanks of younger volcanoes and in
Valles Marineris. Several studies have attempted to estimate, when the
most extensive period of valley network formation occurred, using
stratigraphic and crater counting analysis to date the termination of
valley network activity (Fassett and Head, 2011). These suggest that
regional to global scale valley formation persisted until approximately
the Noachian/Hesperian boundary or into the Early Hesperian at the
latest (e.g., Fassett and Head, 2008; Hoke and Hynek, 2009; Barnhart
et al., 2009).
Rosenberg and Head (2015) using a methodology in which fluid/-
sediment flux ratios are based on empirical data, found
(0.4–14)  1015 m3 of water (corresponding to a GEL of 3–100 m) to be
the most probable cumulative volume that passed through the valley
networks. Luo et al. (2017) employed a mathematical morphology
method to estimate the volume of valley network cavity and the amount
of water needed to create the cavity on a whole planet. The minimum
cumulative volume of water required is ~5–6 km of GEL, i.e.,
(700–800)  1015 m3, suggesting a relatively high rate of water recycling
involved in valley network excavation and consistent with a large open
water body (Luo et al., 2017).
Morphological variations between channels provide insights into the
local topography and surface characteristics (e.g., Hynek et al., 2010).
The dendritic appearance of many Martian valley networks indicates
gentle slopes with water moving down small channels to merge with
larger river networks. Steeper slopes produce channels where the tribu-
taries are almost parallel to the main river channel. Regions with strong
tectonic control (faults, fractures, or joints) produce channels with sharp
angles rather than gentle meanders. Regions where channels form cir-
cular patterns indicate either domes or basins, depending on the direc-
tion of flow. Many valley networks have orientations consistent with the
effects of surface deformation by extensive volcanic loading in the
Tharsis region, inferred to have occurred by late Noachian time (Phillips
et al., 2001). These networks occur in heavily cratered terrains that show
evidence of extensive erosion during the Noachian (Craddock and
Maxwell, 1993; Hynek and Phillips, 2001).
The proposed origins of the Noachian-aged valley networks include
widespread precipitation (Craddock and Howard, 2002; Howard et al.,
2005), groundwater sapping (Carr, 1995; Malin and Carr, 1999; Gold-
spiel and Squyres, 2000; Harrison and Grimm, 2005) and subglacial
water circulation (Fairen et al., 2009; Fairen, 2010). A rainfall origin is
supported by the highly integrated nature of the valley networks and
drainage areas (Grant and Parker, 2002; Irwin and Howard, 2002) and
presence of interior channels, which tend to form by precipitation but not
by sapping. Estimated discharge rates of valley network systems are
similar to terrestrial floods produced by rainfall (Irwin et al., 2005).
However, not all valley networks display the features indicative of
rainfall, and geomorphic analysis suggests that both precipitation and
sapping contributed to valley network formation. Groundwater-driven
valley erosion alone seems inconsistent with many valley characteris-
tics, particularly the dendritic, high-order tributaries that extend to
drainage divides (Hynek et al., 2010). The characteristics of valley net-
works thus seem to require, at a minimum, time periods when precipi-
tation on the surface was possible, water was cycled through the early
atmosphere of Mars, and water was stable or metastable at the Martian
surface (Craddock and Howard, 2002; Hynek et al., 2010).
The period of phyllosilicates formation that indicates pervasive
aqueous alteration on Mars, is not readily connected to the period of
valley network formation
many of the observed alteration products are
likely to be older than at least the last period of valley formation (Fassett
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Planetary and Space Science 166 (2019) 70–89
and Head, 2011). Water–rock interactions that formed clays may have
mostly ended by the time of the Isidis impact in Nili Fossae (e.g., Mustard
et al., 2007). In this case, the phyllosilicates may be older than the Late
Noachian to Early Hesperian valley systems where clay-bearing sedi-
ments were transported and deposited, such as in Eberswalde, Holden,
and Jezero craters (e.g., Ehlmann et al., 2008; Milliken and Bish, 2010).
The outflow channels are much larger than valley networks, with
channel widths up to several tens of kilometers and lengths of thousands
of kilometers (Baker, 1982, 2001). The sizes of Martian outflow channels
imply immense discharges of water, exceeding any known flood flows on
Earth. The outflow channels are Hesperian to Amazonian in age and
originate from large depressions, often filled with jumbled material
called chaotic terrain. Such channels form by the sudden melting of
ground ice due to volcanic or impact processes (e.g., Rodriguez et al.,
2015). The water floods across the surrounding terrain, producing the
channel and associated morphological features. The surface material
overlying the outburst area collapses into the voided region, producing
the chaotic terrain.
At their largest scale, the outflow channels are broadly anastomosing
and split by residual uplands of pre-flood-modified terrain. The channels
have low sinuosity and high width-depth ratios. Pronounced flow ex-
pansions and constrictions occur, as do prominent divide crossings,
hanging valleys and structural control of erosion. At a finer scale,
streamlining of the residual uplands is very well developed, as are lon-
gitudinal grooves, inner channels, cataract complexes, scabland and bar
complexes (Baker, 2001). The whole assemblage of these landforms is
best explained by cataclysmic flood processes.
The largest outflow channels delivered their immense discharges to
the northern plains of Mars. Parker et al. (1989) considered the grada-
tional nature of the dichotomy boundary in western Deuteronilus Mensae
as evidence of sedimentary deposition that occurred in a sea produced
during outflow channel flooding of the northern plains. Identification of
the surface features that ring the plains for thousands of kilometers,
interpreted as a series of paleo-shorelines of different age, led to the
proposal of one or more oceans forming in this area during Hesperian to
Amazonian (Parker et al., 1993).
Clifford and Parker (2001) concluded that the nature of the Late
Hesperian outflow channels requires that in the Noachian at least one
third of the surface have been covered by standing bodies of water and
ice, including specifically, an ice-covered ocean in the northern lowlands.
The great predominance of valley networks in Noachian terrains
certainly indicates a more active hydrological cycle during this period.
The same high level of surface activity has also resulted in very high
surface degradation rates during the Noachian (e.g., Golombek and
Bridges, 2000). Analysis by Carr and Head (2003) shows that erosion and
post-emplacement geologic events and processes conspire to modify and
obscure any evidence for such subtle features as contacts and shorelines.
They found that the most compelling evidence for former standing bodies
of water lies in the deposits themselves, not in the marginal relations of
these deposits. On the basis of their assessment of the Hesperian-aged
deposits, Carr and Head (2003) predicted that testing of the Clifford
and Parker (2001) hypothesis (namely, that a Noachian-aged ocean
covered up to one third of the surface of Mars) will be made very difficult
by the enhanced degradation rates in the Noachian and subsequent
geological events in the northern lowlands.
Perron et al. (2007) demonstrated that the long-wavelength topog-
raphy of the shorelines is consistent with deformation caused by polar
wander – a change in the orientation of a planet with respect to its
rotation pole – and that the inferred pole path has the geometry expected
for a true polar wander event that postdated the formation of the massive
Tharsis volcanic rise.
Di Achille and Hynek (2010) used global databases of known deltaic
deposits, thousands of valley networks, and present-day Martian topog-
raphy to test for the occurrence of an ocean on early Mars. The distri-
bution of ancient Martian deltas delineates a planet-wide equipotential
surface within and along the margins of the northern lowlands. Di Achille
H. Rickman et al.
and Hynek (2010) suggest that the level reconstructed from the analysis
of the deltaic deposits may represent the contact of a vast ocean covering
the northern hemisphere of Mars around 3.5 Gyr ago. This boundary is
broadly consistent with paleo-shorelines suggested by previous geo-
morphologic, thermophysical and topographic analyses, and with the
global distribution and age of ancient valley networks.
Over the past two decades, the existence of an ancient ocean on Mars
has been repeatedly proposed and challenged (e.g., Carr and Head, 2003;
Ghatan and Zimbelman, 2006; Perron et al., 2007; Di Achille and Hynek,
2010). Numerical modeling of an impact-induced tsunami on a hypoth-
esized northern plains paleo-ocean of Mars by Iijima et al. (2014) indi-
cated the approximate tsunami wave height and velocity. Rodriguez et al.
(2016), based on geomorphic and thermal image mapping in the
circum-Chryse and northwestern Arabia Terra regions of the northern
plains, in combination with numerical analyses, disclosed evidence for
two enormous tsunami events. The results presented by Iijima et al.
(2014) and Rodriguez et al. (2016) thereby shed new light on the past
existence of an ocean on Mars. A recent paper by Citron et al. (2018) dealt
with a problem facing the interpretation of Martian surface features as
ancient shorelines, namely, that these shorelines deviate from the in-
tersections with an equipotential surface (e.g., Malin and Edgett, 1999).
According to Citron et al. (2018), these deviations can be explained by a
proposed scenario, where the Tharsis uplift caused a deformation of the
surface such that previously or concurrently formed shorelines no longer
Fig. 5. Geological cross-sections at selected points of three largest Martian craters: Hellas, Isidis and Argyre, on the basis of THEMIS, TES, OMEGA and CRISM data.
Red dot indicates the location of cross-section. Comparison of three geological cross-sections is not scaled in altitude. Based on: Bandfield et al. (2013), Bishop et al.
(2013), Buczkowski et al. (2010), Fassett and Head (2011), Moore and Wilhelms (2007), and Werner (2008). (For interpretation of the references to colour in this
figure legend, the reader is referred to the Web version of this article.)
81
Planetary and Space Science 166 (2019) 70–89
appeared as equipotential curves. This means a dating of the Martian
paleo-ocean further back in time than has usually been assumed.
4.2. Large impact basins
We shall treat four of these because of the indications they provide
about the history of water on the young planet Mars. The first is Borealis,
which is believed to be extremely old, and the others (Hellas, Isidis and
Argyre) were certainly formed later. The impact origin is most clearly
established for the latter three, while Borealis does not immediately
stand out as an impact structure, and other explanations have also been
put forward. The large impact basins pre-date by several hundred million
years the end of valley network formation. Independent crater counts on
the best preserved rim regions of Hellas, Isidis, Argyre, e.g., by Schultz
and Rogers (1984), Werner (2008), suggest that the sequence of the
impact basins was: Hellas, Isidis, then Argyre (Fassett and Head, 2011).
Hellas is at the base of Noachian, and Isidis and Argyre are Early to
Mid-Noachian (Fig. 5). All basins have been incised by valley networks
on their interior or immediate exterior, implying that substantial fluvial
activity took place after their formation. This is consistent with crater
counting evidence that valley networks continued to be active until at
least the end of the Late Noachian or possibly into the Early Hesperian
(Fassett and Head, 2008). The inferred sequence of basins is also sup-
ported by the preservation state of the basins (Fassett and Head, 2011).
H. Rickman et al.
Generally speaking, Mars has two impact crater populations: one
represents the period up to and including the LHB, while the other has
accumulated on younger surfaces since the end of the heavy bombard-
ment. The craters are not uniformly distributed on the Martian surface.
There are a few areas with significant numbers of very large craters or
basins (exceeding 300 km in diameter), while all of the northern low-
lands have very few and rather smaller craters (e.g., Soderblom et al.,
1974; Snyder, 1979). Concerning the large craters, the heat produced by
the collision caused melting of the soil – a mixture of rock, dust and water
ice hidden beneath the surface. As a result, the surrounding environment
was flooded. Before drying up, this muddy fluid carved a complex pattern
of blankets surrounding the crater (Carr et al., 1977; Komatsu et al.,
2007).
4.2.1. Borealis
The bulk of the Northern hemisphere of Mars is on average 4–5 km
below the southern highlands (Watters et al., 2007). This hemispheric
dichotomy can have arisen from convective motions in the mantle
(Zhong and Zuber, 2001), but it can also be understood as a huge impact
basin, named Borealis and covering 40% of Mars' surface area. It is
usually believed to have formed very early in Martian history, perhaps
contemporary with the Moon-forming impact on Earth.
Large craters and small basins almost always become circular, inde-
pendent of the impact angles, because the impact energy is deposited as a
sub-surface explosion in a flat landscape. If the impactor is sufficiently
large relative to the target object, effects of the target curvature will
however cause the crater to become elliptic even for modest impact
obliquity. If one disregards the Tharsis region, then the Borealis basin can
be described as an ellipse of 10 650 km x 8520 km (Andrews-Hanna et al.,
2008), which is almost identical in shape to the Hellas basin (both of
ellipticity 1.25).
The fact that there is no annular thickening (“crater wall”) around
Borealis, no global melt cover and no pronounced antipodal crustal
disruption, was used by Marinova et al. (2008, 2011) in spherical hy-
drodynamic calculations to constrain the impact energy, velocity, and
obliquity to around 5  1029 J, 8 km/s, and 45 , respectively, consistent
with an impactor with a diameter 2000 km impacting with a velocity
only slightly above the Mars escape velocity of 5 km/s. This puts the
impactor in the same class as the Moon-forming impact on Earth (1031 J
according to Canup and Asphaug 2001), and may even have been the
cause for the Martian moon formation (Citron et al., 2015).
In the numerical simulations, the impactor removes all of the crust
within the basin area, and penetrates into the mantle. The result is the
formation of a thin new crust in the melt area (the basin) and a thickening
of the crust with a factor around two in the southern hemisphere (Mar-
inova et al., 2008). The southern hemisphere thus represents the
composition of the solidified, original magma ocean, while the northern
lowland is dominated by a shock melted deep and previously depleted
mantle composition (Nimmo et al., 2008).
The isostatic balance with the mantle causes the observed dichotomy
between inside and outside of the Borealis basin (i.e., between the
northern and southern hemispheres). The thick southern crust may have
made it difficult for the magma to form volcanoes, resulting in slow
plume migration from the southern hemisphere (presumably from a re-
gion near the south pole) toward the dichotomy boundary, resulting in
the build-up of the 300 million km3 Tharsis volcanic region around 3.8
Gyr ago (Hynek et al., 2011).
In their discussion of Mars, Morbidelli et al. (2018) proposed the
formation of Borealis as a solution to an apparent problem with the
interpretation of the LHB as the tail end of a long-lasting stray plane-
tesimal bombardment. The problem is that, in that case, the Martian
surface should feature more large craters than we see due to the
bombardment that started 4.55 Gyr ago, when the planet was formed.
The suggestion was that a major resurfacing event took place about 4.4
Gyr ago, and it was speculated that this could have been the formation of
Borealis.
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Planetary and Space Science 166 (2019) 70–89
Some issues remain to be clarified concerning this relatively late
dating of Borealis. However, one interesting consequence would be a
specific scenario for the important loss of water that occurred early in
Martian history (Villanueva et al., 2015). The dating of NWA 7533, from
which we estimated several km GEL of water in the crustal rocks, is about
4.4 Ga, so Borealis may have formed shortly after this regolith breccia
was formed. As a consequence, a vast magma ocean would arise, through
which much of the early water would make its way into the atmosphere.
The ensuing impact erosion (Schlichting and Mukhopadhyay, 2018)
would remove most of this atmosphere, and in the meantime the loss of
large amounts of H2O by photodissociation and hydrogen escape is likely.
4.2.2. Hellas
The first data from the Hellas basin originated from the NASA Viking
orbiter. Based on these data, it was possible to distinguish areas that
differ in morphology: the rim unit covered by sediments from late
Noachian, the sediments of the interior of the basin from early Hesperian,
and the rim unit covered by sediments from late Hesperian and early
Amazonian (Fig. 5; Tanaka and Leonard, 1995). Later maps, based on
MOLA/MGS and MOC/MGS data, provided more morphological details
on the shaping of the crater by water erosion during the Noachian period.
Moore and Wilhelms (2007) emphasize that Hellas must have been
formed in Noachian and filled with water. The oldest units have been
exposed and transformed by the glacier that was present there during
Hesperian, as indicated by geomorphological traits of the crater (Moore
and Wilhelms, 2001, 2007). Channels on the east side of Hellas may have
been water flows at some point in the history of Mars (Kostama et al.,
2010). Significant erosion of the interior and north side of Hellas, where
accumulation of clay minerals and hydrated silica are observed, may
have been caused by huge flows of water (Crown et al., 2009).
Mineralogical analysis of the northwest rim of the basin has been
made, based on CRISM/MRO data. Products of Noachian basaltic rock
transformation, such as prehnite, chlorite, illite, muscovite, and saponite
have been observed in the ejecta. Prehnite is a product of low-
temperature hydrothermal metamorphic processes, which probably
occurred due to impact. On the northwest wall of the crater, Fe/Mg
phyllosilicates have been observed (Noe Dobrea et al., 2014a). Based on
CRISM data in conjunction with HiRISE/MRO and CTX/MRO data, large
quantities of Fe/Mg smectites, Al phyllosillicates (including kaolin-group
minerals), polyhydrated sulphates, chlorites, a smectite/chlorite layer,
and prehnite are amassed in pitted terrain in recesses formed through
sedimentation (Noe Dobrea et al., 2014b). Hydrothermal alteration
products, such as prehnite, chlorite, and illite assemblages, are associated
with Hilly Unit and interpreted as uplifted crustal material and ejecta
from the Hellas impact and post-impact structural and erosional modi-
fications. Subsequent erosion of Noachian plains material resulted in
dissection and redeposition to form smooth embaying plains and
intra-crater units 200–400 m in thickness (Noe Dobrea et al., 2014a).
Bandfield et al. (2013) indicate the occurrence of hydrated silica in
the northwestern part of the Hellas interior. Hydrated amorphous silica
(opal) has been identified on the basis of measurements by the in-
struments TES/MGS, THEMIS/MO, and CRISM/MRO. Opal was also
identified inside the Tereby crater located on the north rim of Hellas
(Carter et al., 2011). Bandfield et al. (2013) indicate that the hydrated
silicates on the surface of Hellas have been converted by a glacier. Before
glaciation, the Hellas crater was filled with water for a long period of
time, as long as climate conditions allowed. The hypothesis of the pres-
ence of a lake in the Noachian is confirmed by a survey using spectra from
CRISM/MRO and OMEGA/MEx from the western rim of the Hellas basin,
where large clusters of clay minerals were identified (Carter et al., 2011).
Multiple channels and deltas, which were probably water flows in the
direction of the crater in the Noachian era, can be observed on the rim of
Hellas.
Clay minerals have been identified on the basis of the OMEGA spectra
in the central part of the crater and in the surrounding channels Dao
Vallis (Zalewska, 2013). These clay minerals were formed mainly in the
H. Rickman et al.
Noachian era, when Hellas could have been filled with water. The
appearance of clay minerals in areas from Hesperian and Amazonian
suggests reworking of the material by the glacier (Bandfield et al., 2013).
Runoff water appeared not only in the Noachian but also in the late
Hesperian and early Amazonian, from the melting of a subsurface ice
layer and/or lingering ice caps due to episodes of late volcanism, when
the Dao, Harmakhis and Niger Vallis channels were formed (Levy et al.
2017).
One might expect clay minerals in the Dao, Harmakhis and Niger
Vallis channels based on their geomorphological features, indicating that
huge flows of water were provided to Hellas, but the origin of these
channels and their age are understood differently. The age of the lake
accumulation and runoff channel features from Dao, Harmakhis and
Niger Vallis is estimated at Late Hesperian and Early Amazonian.
Possibly, the channels were carved by underground water, which formed
a frozen layer and was melted during late volcanic activity in the area.
These flows are defined as catastrophic. Channels show features like
sinkholes or sudden ground collapse. Embedded volcanic material ap-
pears on these surfaces. The outflow hypothesis still has several un-
certainties. Another, more likely process is ice cap melting, since these
channels exhibit characteristics of melting forms, presumably due to the
melting of residual ice on the surface under the influence of late episodes
of volcanism (Kostama et al., 2010). These examples demonstrate the
appearance of water not only during the Noachian.
4.2.3. Isidis
Isidis is another impact crater from the Late Heavy Bombardment
period, followed by an episode dominated by volcanic and fluvial/glacial
activities (~3.8–2.8 Ga). Glaciers and/or ice sheets probably resulted in a
massive glaciation of the rim and the floor of the Isidis basin (Ivanov
et al., 2012). The oldest materials inside the crater and its rim from
Noachian (Fig. 5) were formed mostly by impact reworking and
mass-wasting (Ivanov et al., 2012). There are two rings forming around
the crater hills, which arose in this way and are eroded by subsequent
erosion activity (Mustard et al., 2007). Many volcanic forms were
covered later by eolian and alluvial sediments. The thickness of the
deposited interior material is 40–60 m (Ivanov et al., 2012).
The clay minerals inside Isidis date from the period when a network
of river channels was already developed (from 3.45 to 3.98 Ga). The
formation of river systems in these areas occurred only during the
Noachian and early Hesperian periods. Parts of the river valleys are now
heavily eroded or filled with volcanic material. The formation of clay
minerals was caused by weathering of older layers of basalt, when hy-
drous activity appeared. Bishop et al. (2013) emphasized that the for-
mation of mountains and hence clay minerals could have begun as early
as around 4 Ga shortly after the formation of the Isidis crater. The earlier
formation of clay minerals before the creation of Isidis also needs to be
taken into consideration, especially when it comes to minerals such as Al
smectite and beidellites, which also formed through hydrothermal pro-
cesses or burial diagenesis (Bishop et al., 2013).
Mustard et al. (2009) presented a geological hypothesis on the
“pre-crateredˮ appearance of phyllosilicates. On basalt breccia in the
northwest part of the crater rim near Nili Fossae, Fe/Mg phyllosilicates
estimated at Noachian have been identified. Underneath there are layers
of smectites from earlier Noachian, and lava that flowed through the Nili
Fossae troughs from Syrtis Major during the Hesperian forms basaltic
covers (Mustard et al., 2009).
In the Noachian terrain west of the Isidis basin, on the border of Isidis
and Nili Fossae, alteration minerals were identified by CRISM/MRO,
including nontronite, magnesium smectites, chlorite, prehnite, serpen-
tine, kaolinite, K-mica, analcime, hydrated silica, and magnesium car-
bonate (Ehlmann et al., 2009). The Fe/Mg smectites occur on bedrock
through 100 000 km2. Such a wide spread suggests leaching of rocks
through transformation caused by hydrothermal activity due to cooling
of the crust. This suggests the existence of long-term exposure of rocks to
interaction with water in the early Noachian and then exhumation by
83
Planetary and Space Science 166 (2019) 70–89
local impacts. On the eastern part of Nili Fossae, the presence of minerals
such as kaolinite and magnesium carbonate, which is associated with
weathering caused by surface water flows, dates back to the
mid-Noachian. Kaolinite is formed by the transformation of rocks such as
feldspar or in the process of recrystallization of smectites, as confirmed
by subsequent genesis of kaolinite at Nili Fossae (Ehlmann et al., 2009).
Magnesite is a product of serpentinization of olivine with the contribu-
tion of water and CO2. The occurrence of prehnite is explained by hy-
drothermal processes within Nili Fossae, another explanation being an
excitation of hydrothermal processes by impacts (Ehlmann et al., 2009).
Mustard et al. (2007) explain the occurrence of olivines in the outskirts of
Isidis by extraction of large amounts of olivine during the impact that
formed the Isidis basin and then the emergence of volcanism, which
transported this olivine. Only some of this was transformed into clay
minerals, whose age is not fully clarified (Mustard et al., 2007).
Studies of the rim of Isidis, Libya Montes, on the basis of the spectra
from THEMIS/MO, TES/MGS, OMEGA/MEx, and CRISM/MRO have
distinguished three layers of different origin (Bishop et al., 2013). The
oldest basalt that originated before the formation of the basin contains
layers of Fe/Mg smectite mixed with carbonate and/or other Fe/Mg-rich
phyllosilicates, and Al smectite. Above this layer there is a unit with ol-
ivines that developed by the ejection of volcanic material from the Syrtis
Major area or the influence of basaltic lava rich in olivines. The cover
layer is the youngest volcanic ash, which is probably derived from the
adjacent land of Syrtis Major. A layer of clay minerals is present in many
places on Libya Montes, especially in its central part (Bishop et al., 2013).
4.2.4. Argyre
The Argyre basin is another large, well-preserved impact basin in the
southern highlands of Mars, with seven associated ring structures (Hie-
singer and Head, 2002). The geologic units associated with the basin and
the surrounding plateau plain span the Noachian and Hesperian eras
(Fig. 5; Scott and Tanaka, 1986). The geologic history of the Argyre basin
proposed by Hiesinger and Head (2002) is consistent with the model
proposed for the Hellas basin (Moore and Wilhelms, 2001). Glacial and
fluvial or lacustrine processes in conjunction with eolian modification
were most important in the evolution of the interior of the Argyre basin
(e.g., Hiesinger and Head, 2002; Dohm et al., 2015).
There is a certain amount of geomorphic evidence for the past pres-
ence of water and ice in Argyre (Buczkowski et al., 2010). Geomorphic
features consistent with glacial flow have been identified in the basin
(e.g., Hodges, 1980; Kargel and Strom, 1992; Hiesinger and Head, 2002;
Banks et al., 2008; Dohm et al., 2015). Local alpine glacial sculpture in
the Charítum Montes, south of Argyre, includes cirques, horns, aretes,
grooves and V-shaped valley troughs. Many of the cirques and troughs
seem to be occupied by extant or relict rock glaciers or debris-covered
glaciers. The adjacent floor of Argyre Planitia has landforms that can
be interpreted as moraines, drumlins, esker-like ridges, kettles, outwash
plains and glacio-lacustrine plains (Kargel and Strom, 1992). Three val-
ley systems, generally interpreted as fluvial in nature, feed into Argyre
from the south: Surius, Dzigai, and Palacopas Valles. A fourth valley
system, Uzboi Valles, is frequently interpreted as an outflow channel
from Argyre (e.g., Parker, 1989). The primary Argyre basin contained a
large water body, sufficient in size to have sourced Uzboi Valles (Dohm
et al., 2015).
Parker et al. (2000) and Clifford and Parker (2001) present a case for
overland flow of water from the south polar region to the northern
lowlands, with water draining into and filling the Argyre basin, over-
topping it to the north, and flowing down the Chryse Planitia trough into
the northern lowlands. However, the continuity of features in this system,
their contemporaneity, and their ancient age have been questioned by
Hiesinger and Head (2002), who find that several of the elements of the
proposed system are independent features of differing ages (Carr and
Head, 2003).
According to Hiesinger and Head (2002) the evidence for water in the
Argyre basin is the formation of channels which can be traced to the basin
H. Rickman et al.
floor, the morphologies at their mouths which suggest a fluvial origin,
and the availability of large amounts of water. The source of this water is
melt-back of a formerly more extensive south polar ice cap (Head and
Pratt, 2001). Water that ponded in the Argyre basin would have sub-
limed, evaporated or migrated into the substrate rather than flowing
through the outflow channel of Uzboi Vallis. The body of water in the
Argyre basin very likely froze over. Subsequent retreat of the ice is
indicated by the formation of esker-like ridges, and eolian modification
of the basin floor is seen in numerous images from the MOC/MGS camera
(Hiesinger and Head, 2002).
MOC/MGS images of the Argyre Planitia sinuous ridges revealed
sedimentary layers, boulders and discontinuous ridges, with heights of
10–100 m, and widths of 200–2000 m. Together with the associated
glacial landforms, the esker interpretation seems to provide a consistent
hypothesis explaining all relevant observations (Baker, 2001). Studies by
Banks et al. (2008) confirmed that Argyre's ridges are most likely eskers
formed by glacio-fluvial processes. Their occurrence among layered de-
posits allows for the possibility that lacustrine processes were involved.
The nature of some eroding beds suggests induration of ridge sediments.
Alternating patterns of layers may also reflect the influence of cyclic
fluctuations in melt-water and sediment availability (Banks et al., 2008).
The northwest Argyre ring grabens are similar in orientation, loca-
tion, and presumed formation to the Nili Fossae, where one of the most
complex deposits of hydrated silicates on Mars was found (Ehlmann
et al., 2009). Argyre is thus potentially an ideal probe of the composi-
tional layering of ancient highland rocks. Examination of CRISM/MRO
spectroscopic data by Buczkowski et al. (2010) indicates the presence of
Fe/Mg-rich phyllosilicates in several outcrops in northwest Argyre. In the
Argyre ring structure itself, the phyllosilicate-bearing units are most
consistent with Fe/Mg smectite and Mg-chlorite. However, the two knob
outcrops imply variability in the formation environments of the phyllo-
silicates. The more southern knob shows only Mg-chlorite, while at the
more northern knob also prehnite was found, which is consistent with
elevated formation temperatures (Buczkowski et al., 2010).
The stratigraphic units in northwest Argyre display an inverted flap of
pre-Argyre materials; thus the phyllosilicates observed in the northwest
ring graben were not formed because of impact-driven hydrothermal
activity, but rather represent preexisting materials (Buczkowski et al.,
2010). Although iron/magnesium bearing phyllosilicates are exposed
within and by the Argyre basin structure, less mineralogical diversity is
present than in a comparable setting at Isidis. Buczkowski et al. (2010)
interpret the alteration minerals of Argyre as primarily pre-dating the
basin-forming event, which exposed pre-existing alteration products in
the Noachian crust. In the Nili Fossae area associated with Isidis the
greater diversity of alteration products is observed which requires mul-
tiple alteration events in distinct weathering environments (Ehlmann
et al., 2009). This distinction is consistent with Argyre being younger
than Isidis and with a hypothesized global decline in neutral-pH, high
water/rock ratio aqueous alteration as a function of time (Fassett and
Head, 2011).
5. Conclusions
We have reviewed both theoretical and observational evidence
regarding the role of water in the evolution of Mars from its formation
until the Amazonian era. Concerning theory, we discussed recent models
of terrestrial planet formation with emphasis on the generally accepted
framework of the Nice Model with the Grand Tack scenario. However, we
caution that this is still just a dynamical model, upon which numerical
simulations have been built. It includes crucial input assumptions,
influencing amongst others the timing of the instability. The outcome
depends strongly on these, and can only be trusted to the extent that it
accounts for all the observational evidence.
Meanwhile, we are led to tentatively assume that the baseline
dynamical model is adequate for understanding the origin of water on
both the Earth and Mars. Following many recent papers, this means in
84
Planetary and Space Science 166 (2019) 70–89
particular that a large majority of the water was acquired more than 4.5
Gyr ago, preceding the Moon-forming impact. The harbingers of this
water were ice-rich planetesimals (and also embryos in the case of the
Earth) originating near and beyond the snow line of the solar nebula. We
caution against identifying these with present-day comets and asteroids,
because comets were likely formed at larger distances, and the asteroid
main belt is mostly inhabited by objects that arose closer to the Sun. In
terms of D/H ratio, an average value close to that of carbonaceous
chondrites (i.e., close to VSMOW) is reasonable to expect.
Since our review explicitly deals with water, we prefer not to high-
light the issues concerning other volatiles. However, we need to stress
that the water picked up by Mars probably was not accompanied by an
excessive amount of CO2 (which might be hard to dispose of), since the
swept-up planetesimals would have formed inside the CO2 snow line.
Recent studies of volatile loss due to impacts up to and including the
formation of the Moon (Schlichting and Mukhopadhyay, 2018) indicate
that the loss of water from the Earth may not have been dramatic.
Meanwhile, other studies of the same problem have come to the opposite
conclusion (Connelly and Bizzarro, 2016).
Explaining the global amount of water contained in our planet may or
may not present a problem, though most recent studies (Schlichting and
Mukhopadhyay, 2018; Morbidelli et al., 2018) point at a very early ac-
cretion. Coming to Mars, recent results have shown that it differs from
the Earth by being essentially just one embryo plus lots of accreted
planetesimals. This clearly means some difference in the way that water
was accreted. In our terminology, the formation of Mars was completed
within just about 10% of the time it took for the Earth to grow and the
Earth-Moon system to arise (Dauphas and Pourmand, 2011). As a
consequence, the following late veneer should be relatively more
important in the case of Mars – in fact, for Mars this should be dominant,
while for the Earth it has recently been estimated to be of minor
importance (Fischer-G€ odde and Kleine, 2017).
Concerning the total amount of water accreted and retained by Mars,
we still have only preliminary estimates pointing to roughly a few km
GEL. In terms of mass relative to the planet, this is comparable to the
estimate for the Earth, i.e., about 0.1 wt%. Some support for this comes
from the recently found Northwest Africa Martian meteorites. However,
there is room for more work on refining the theoretical estimate. One
may speculate that the Martian proto-planetary embryo may have carried
more water than most of the Earth's embryos on the basis of chondritic
analogues due to the higher abundance of ordinary chondrites (Tang and
Dauphas, 2014), depending on the unknown fraction of L-type,
water-bearing material. On the other hand, Mars would have been missed
by the type of water-bearing embryos that brought an important
contribution to the Earth during some of its giant impacts.
Another issue worth pursuing is the role of episodic magma oceans
during the time, when Mars acquired its water, due to large impacts.
While full-scale embryos apparently were not involved, the planetesimal
population may well have included some fraction of objects large enough
to melt the Martian surface. Such impacts would have driven some of the
water and much of the other volatiles into temporary atmospheres, from
which gases could be eroded away.
Concerning the arrival of trans-planetary water as expected from the
Nice Model, both planets should have acquired water from cometary
projectiles, whose average D/H ratio was likely twice as large as
VSMOW. This could have occurred either in the very beginning (our
baseline case) or very late, connected with the LHB. However, the
contribution has been shown to be very small (Rickman et al., 2017). For
Mars, the estimate is only about 10 m GEL.
Coming now to observational constraints, the D/H ratios of the
Martian atmosphere, surface rocks from the Hesperian, and Mars mete-
orites with a wide range of ages indicate a certain history of water loss
from the surface layer. In the beginning, the loss rate was very high,
while at about 4 Ga it settled at a lower pace. The total amount of water
thus lost is estimated to be at least of order 100 m GEL, and it may be
substantially larger. In particular, impact erosion by water-deficient
H. Rickman et al.
projectiles is not included into this estimate. Interestingly, the oldest
Martian meteorites hitherto known, which were recently found in
Northwest Africa, bear signs of a hydrated crust and wet mantle very
soon after the planet was formed. This is consistent with the above-
described picture of very early accretion of water.
The geomorphological evidence for water on the Martian surface
involves a range of different features and phenomena, as reviewed in
Section 4. In this case the dating is stratigraphic, leading to the Noachian-
Hesperian-Amazonian sequence with increasingly younger ages. How-
ever, translating this into absolute ages is a complex issue, which involves
comparison with the estimated time profile of the lunar cratering rate
and other pieces of evidence (e.g., Werner, 2014; Werner et al., 2014).
Significant uncertainties are therefore unavoidable. In particular, Mor-
bidelli et al. (2018) state that the interpretation of the LHB as an accre-
tion tail has important consequences for the dating of Martian
topography. This scenario requires a global resurfacing event on Mars
about 4.4 Gyr ago (possibly related to Vastitas Borealis), which would
make the Noachian and pre-Noachian terrains ~200 Myr older than
usually considered. Furthermore, the dating of the putative Martian
paleo-ocean with respect to the Tharsis uplift was recently challenged by
Citron et al. (2018), who favoured an earlier dating in order to resolve
the apparent conflict between the associated shorelines and the expected
equipotential surface.
Nevertheless, the evidence was found that the formation of valley
networks, primarily observed in the Noachian units, persisted until
Noachian/Hesperian boundary or into Early Hesperian. Younger outflow
channels are Hesperian to Amazonian in age. Finally, there are series of
putative shorelines of different age, which led to the idea of existence of
ocean during Hesperian to Amazonian. The large impact basins, i.e.
Hellas (base of Noachian), Isidis and Argyre (Early to Mid-Noachian),
predate the end of valley network formation. Both valley networks and
hydrated silicates prevail in Noachian terrains, but the evidence that they
are characteristic of the same environment and formed at the same time
is limited.
There are strong indications that water on Mars existed mainly in the
Noachian era, but there is also evidence that it may have been present in
more recent times. Detailed examination of the impact craters and
analysis of the evolution and transformations of the minerals formed in
the presence of water in combination with determination of their ages
may shed new light on the problem of when exactly water existed on the
Martian surface. It should be stressed that hydrated silicates have been
identified also in the Hesperian northern plains of Mars (Bibring et al.,
2006; Bibring, 2011) in and around impact craters. Of those, Mg/Fe
smectites are the most abundant type. It is tempting to conclude that
these are produced by excavation of preexisting deposits, exposed by
impacts and erosion (Bibring et al., 2006; Murchie et al., 2009; Fairen
et al., 2011, 2012; Sun and Milliken, 2014; Turner et al., 2016).
Searching for post-Noachian water activity on Mars by analysis of
phyllosilicates within impact craters is another area of Martian research.
Various craters located in the Syrtis Major region
one of large
Hesperian-aged volcanic provinces on Mars
were investigated recently.
Some theoretical and experimental studies suggest a possible later
appearance of phyllosilicates on Mars (Fairen et al., 2010; Marzo et al.,
2010). However, the problem is difficult because of many factors
changing the properties of minerals (e.g. phyllosilicates), which leads to
complex interpretations.
Acknowledgments
This work was supported by the Polish National Science Centre under
Grants No. 2011/01/B/ST9/05442 and 2011/01/B/ST10/04541 as well
as Grant No. 74/10:2 of the Swedish National Space Board. We thank
Ramon Brasser and Alessandro Morbidelli for enlightening discussions.
We gratefully acknowledge the important advice provided by both ref-
erees, Alberto Fair
en and Chris McKay, which led to great improvements
of the paper.
85
Planetary and Space Science 166 (2019) 70–89
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