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Iron and sulfur isotope constraints on redox conditions associated with the 3.2
Ga barite deposits of the Mapepe Formation (Barberton Greenstone Belt,
South Africa)

Article  in  Geochimica et Cosmochimica Acta · May 2017

DOI: 10.1016/j.gca.2017.05.002

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Geochimica et Cosmochimica Acta 210 (2017) 247–266
www.elsevier.com/locate/gca

Iron and sulfur isotope constraints on redox conditions

associated with the 3.2 Ga barite deposits of the
Mapepe Formation (Barberton Greenstone Belt, South Africa)
Vincent Busigny a,⇑, Johanna Marin-Carbonne b, Elodie Muller a, Pierre Cartigny a,
Claire Rollion-Bard a, Nelly Assayag a, Pascal Philippot a
a
Institut de Physique du Globe de Paris, Sorbonne Paris Cité, Université Paris Diderot, UMR 7154 CNRS, 75238 Paris, France
b
Univ Lyon, UJM Saint Etienne, Laboratoire Magmas et Volcans, CNRS UMR 6524, UCA, IRD, 23 rue du Dr Paul Michelon,
42100 Saint Etienne, France

Received 4 July 2016; accepted in revised form 1 May 2017; Available online 9 May 2017

Abstract

The occurrence of Early Archean barite deposits is intriguing since this type of sediment requires high availability of dis-
solved sulfate (SO2

4 ), the oxidized form of sulfur, although most authors argued that the Archean eon was dominated by
reducing conditions, with low oceanic sulfate concentration (<10 lM) relative to present day levels of 28,000 lM. In order
to better assess the redox state of the paleo-atmosphere and -oceans, we examined Fe and S isotope compositions in a sed-
imentary sequence from the 3.2 Ga-old Mendon and Mapepe formations (Kaapvaal craton, South Africa), recovered from
the drill-core BBDP2 of the Barberton Barite Drilling Project. Major elements were also analyzed to constrain the respective
imprints of detrital vs metasomatic processes, in particular using Al, Ti and K interrelations. Bulk rock Fe isotope compo-
sitions are linked to mineralogy, with d56Fe values varying between
2.04‰ in Fe sulfide-dominated barite beds, to
+2.14‰ in Fe oxide-bearing cherts. d34S values of sulfides vary between
10.84 and +3.56‰, with D33S in a range comprised
between
0.35 and +2.55‰, thus supporting an O2-depleted atmosphere (<10
5 PAL). Iron isotope variations together with
major element correlations show that, although the sediments experienced a pervasive stage of hydrothermal alteration, the
rocks preserved a primary/authigenic signature predating subsequent hydrothermal stage. Highly positive d56Fe values
recorded in primary Fe-oxides from ferruginous cherts support partial Fe oxidation in a reducing oceanic environment
(O2 < 10
4 lM), but are incompatible with a model of complete oxidation at the redox boundary of a stratified water column.
Iron oxide precipitation under low O2 levels was likely mediated by anoxygenic photosynthesis, and/or abiotic photo-
oxidation processes. Our results are consistent with global anoxic conditions in the 3.2 Ga-old sediments, implying that
the barite deposits were most likely sourced by atmospheric photolysis of S gases produced by large subaerial volcanic events,
and possibly SO2
4 produced by magmatic SO2 disproportionation in hydrothermal systems.
Ó 2017 Elsevier Ltd. All rights reserved.

Keywords: Iron isotopes; Archean; Paleo-environment; Barite deposits; Anoxic ocean

1. INTRODUCTION

Understanding the evolution of Earth’s surface oxygena-

tion through geological time is crucial for constraining the
⇑ Corresponding author. development of life on Earth. The release and accumulation
E-mail address: busigny@ipgp.fr (V. Busigny).

http://dx.doi.org/10.1016/j.gca.2017.05.002
0016-7037/Ó 2017 Elsevier Ltd. All rights reserved.
248 V. Busigny et al. / Geochimica et Cosmochimica Acta 210 (2017) 247–266
of O2 in the ocean and atmosphere imparted strong
modifications of the geochemical cycles of redox-sensitive
elements (e.g. Fe, S, Mo, U, Cr) and their co-evolution with
living organisms (Anbar and Knoll, 2002; Konhauser et al.,
2011; Lyons et al., 2014, 2015). The production of O2 on the
Earth’s surface is attributed essentially to oxygenic photo-
synthesis, implying that constraints on the timing of early
O2 production could help to establish the development of
this metabolic activity (Farquhar et al., 2011; see also
Catling, 2014, for a detailed discussion about sources and
sinks of atmospheric O2). It is generally considered that
ocean-atmosphere system during the Archean period was
depleted in O2 until the Great Oxidation Event (GOE)
sometime between 2.45 and 2.20 Ga (Holland, 1984,
2002; Bekker et al., 2004). The most compelling evidence
for low concentration of O2 in the Earth’s atmosphere is
the presence of significant mass-independent fractionation
(MIF) recorded in S isotope compositions from Archean
sedimentary sulfides and sulfates (Farquhar et al., 2000;
see also review by Johnston, 2011). The presence of S-
MIF has been interpreted as resulting from photochemical
reactions of S-species (SO2 and/or OCS) released from vol-
canoes to the atmosphere (e.g. Farquhar et al., 2000; Ueno
et al., 2009; Thomassot et al., 2015). Most authors concur
that the generation and preservation of S-MIF signal in
the Archean rock record requires extremely low atmo-
spheric O2 concentration, probably less than 10
5 present
atmospheric level (PAL; Pavlov and Kasting, 2002). During
the last decade, attempts were made to track the rise of
atmospheric O2 using several new or emerging geochemical
proxies such as redox-sensitive metals (Fe, Mo, Re, Cr, U).
These proxies have highlighted that the rise of atmospheric
O2 may have been more complex than previously thought,
and that some fluctuations in the O2 production and accu-
mulation may be tracked back several hundred million
years before O2 became a permanent part of the atmo-
sphere (e.g. Anbar et al., 2007; Wille et al., 2007; Frei
et al., 2009; Scott et al., 2011; Czaja et al., 2012; Zerkle
et al., 2012; Crowe et al., 2013; Planavsky et al., 2014).
Alternatively, oxygen could have risen in ocean oases, soil
profiles or microbial mats and have no impact on atmo-
spheric O2 levels (e.g. Kasting, 1992; Olson et al., 2013;
Lalonde and Konhauser, 2015). Much of the proxy data
could therefore have been affected by local effects, unrelated
to atmospheric ‘‘whiffs” of oxygen (Anbar et al., 2007).
Additionally, the geological record of these proxies is sparse
and difficult to correlate between cratons, and fundamental
questions about their interpretation complicate the picture.
For instance, the burial and diagenetic history of rocks (e.g.
Li et al., 2013) might lead to a false recognition of Archean
oxygenic photosynthesis or oxygenated atmosphere (tracing
for instance other oxidants than O2).
In a recent study coupling Fe isotope composition and
U concentrations in the Manzimnyama Banded Iron For-
mations (BIF) from the Fig Tree Group (Barberton Green-
stone Belt, South Africa), Satkoski et al. (2015) proposed
that the ocean was stratified, with oxic surface waters and
anoxic and ferruginous deep waters, 3.2 Ga ago (i.e.
900 Ma before the GOE). In the Fig Tree Group, two other
observations highlighted the possibility for significant
amount of O2 in the paleoenvironment: (1) a negative Ce
anomaly in some greywackes and a ferruginous chert and
(2) the presence of primary hematite in ferruginous cherts
(jaspilites). Given the apparent lack of secondary/late oxi-
dation, the signal was considered as primary (Hofmann,
2005). It could either record a hydrothermal signal being
unrelated to surface oxygenation (Hofmann, 2005), or pro-
vide geochemical evidence for some of the earliest traces of
oxygenic photosynthesis on Earth. The fact that most sam-
ples of this previous study did not show Ce anomaly sug-
gests that the underlying process causing the Ce loss was
localized and not representative of a general state of the
water column. Interestingly, the possibility for local oxygen
production at that time is further suggested by interpreta-
tion of microbial mats in the Moodies Group from Barber-
ton as cyanobacteria fossils (Homann et al., 2015, 2016).
Another important feature of the 3.2 Ga sedimentary rocks
from the Fig Tree Group is the presence of extensive sedi-
mentary barite (BaSO4) deposits. This type of sediments
requires high availability of dissolved sulfate (SO2
4 ), the
oxidized form of sulfur, and may thus point to the presence
of oceanic oxic oases. Alternatively, sulfate could derive
from photolysis of SO2/OCS in an O2-poor atmosphere
and subsequent hydrolysis of the products with water
(Huston and Logan, 2004; Bao et al., 2007; Roerdink
et al., 2012; Muller et al., 2016). Intense subaerial volcanic
activity could for instance lead to massive accumulation of
sulfate in the shallow-ocean (Philippot et al., 2012; Muller
et al., 2016). Another possibility would be that SO2
4 was
produced by disproportionation of magmatic SO2 during
hydrothermal reactions between water and volcanic rocks
(e.g. Kusakabe et al., 2000). In the present work, we inves-
tigated the redox state of the paleo-atmosphere and -ocean
by coupling S and Fe isotope compositions recorded in a
sedimentary sequence from the 3.2 Ga-old Mendon and
Mapepe Formations (Barberton Greenstone Belt, South
Africa). The Mapepe Formation represents the lowermost
unit of the Fig Tree Group, South of the Inyoka Fault
(Fig. 1), and contains abundant bedded barites, thus allow-
ing us to explore potential variations in the redox condi-
tions. The Mendon Formation, underlying the Mapepe
Formation, belongs to the Onverwacht Group and has been
selected to evaluate the chemical and isotopic effect of late
hydrothermal circulation. The advantage of coupling Fe
and S isotopic systems is that Fe isotopes provide informa-
tion about the water column and diagenetic processes
(Rouxel et al., 2005; Yamaguchi et al., 2005; Severmann
et al., 2006, 2008; Staubwasser et al., 2006; Yoshiya et al.,
2012; Johnson et al., 2013; Busigny et al., 2014), whereas
sulfur can bring insight into atmospheric processes and bio-
geochemical cycling in the water column and sedimentary
interface (Farquhar et al., 2000; Pavlov and Kasting,
2002; Bao et al., 2007; Johnston, 2011; Roerdink et al.,
2012; Muller et al., 2016).
2. GEOLOGICAL BACKGROUND
The Barberton Greenstone Belt (BGB) in South Africa
consists of a succession of Archean supracrustal rocks sur-
rounded and intruded by granitoids (Viljoen and Viljoen,
 V. Busigny et al. / Geochimica et Cosmochimica Acta 210 (2017) 247–266 249

Fig. 1. (A) Geological map of the Barberton Greenstone Belt, South Africa, showing the location of the drill-core BBDP2 (red star). (B)
Stratigraphic log of BBDP2 drill core after Philippot et al. (2012). Stratigraphic legend: 1, shales with local ferrigenous chert beds (red layer);
2, Felsic volcanoclastic and terrigenous sediments with local barite beds (green layer) and ferrigenous cherts; 3, bedded barite with pyrite
laminates; 4, Laminated black chert with local breccia and vein network; 5, Strongly silicified basaltic komatiites preserving local spinifex
texture (v) and cut across by numerous black and white hydrothermal chert veins. (For interpretation of the references to color in this figure
legend, the reader is referred to the web version of this article.)

1969). Supracrustal rocks from the BGB are termed the
Swaziland Supergroup and are subdivided into three strati-
graphic units: the Onverwacht, Fig Tree and Moodies
Groups (Fig. 1). Samples analyzed in the present work rep-
resent the transition between the Onverwacht and Fig Tree
Groups. They belong to the Mendon and Mapepe Forma-
tions, which correspond respectively to the upper section of
the Onverwacht Group and lower section of the Fig Tree
Group. The Mendon Formation is a dominantly ultramafic
volcanic succession, interpreted to reflect large mantle
plume magmatic activity (Lowe, 1994). Basaltic komatiites
from Mendon Formation are alternated with bedded
cherts, probably recording deep-water sedimentation dur-
ing times of magmatic quiescence (Hofmann and Harris,
2008). A tuffaceous band from the upper Kromberg Forma-
tion, underlying the Mendon Formation, contains zircons
with a mean age of 3334 ± 3 Ma (Byerly et al., 1996), thus
providing a lower age limit for Mendon Formation.
Komatiites and cherts from Mendon were affected by wide-
spread hydrothermal alteration as illustrated by a petrolog-
ical study of samples from various localities (e.g. Barite
Valley Syncline, Power Line Road section, Msauli Gorge;
Farber et al., 2015). The Mapepe Formation at the base
of the Fig Tree Group records shallow-water terrigenous
and volcanoclastic sediments, interbedded with felsic vol-
canic deposits. The Fig Tree Group sediments were depos-
ited between 3259 ± 3 and 3226 ± 3 Ma, as determined
from zircon of volcanoclastic rocks at the base and the
top of the group, respectively (Kröner et al., 1991; Byerly
et al., 1996). Rocks from the Onverwacht and Fig Tree
Groups experienced low greenschist facies regional meta-
morphism with temperatures not exceeding 350 °C (Xie
et al., 1997; Toulkeridis et al., 1998; Knauth and Lowe,
2003; Tice et al., 2004; Farber et al., 2015).
3. SAMPLES DESCRIPTION
In the present study, samples were collected from a
weathering-free drill-core recovered by the Barberton Bar-
ite Drilling Project (BBDP2; Fig. 1, Philippot et al., 2009,
2012). Samples were selected as representative of the diver-
sity of lithologies forming the Mendon and Mapepe For-
mations. These include basaltic komatiites and
carbonaceous black cherts from Mendon, together with
bedded barites, ferruginous cherts, and silicified terrigenous
and volcanoclastic sediments from Mapepe.
Basaltic komatiites from Mendon display locally spini-
fex textures with olivine and pyroxene pseudomorphed by
quartz, carbonate and chlorite (Lowe, 1994). These rocks
were extensively hydrothermally-altered and silicified, and
occur transected by numerous generations of quartz-
carbonate and black-chert veins. Three meta-komatiite
samples were studied here: 180-32, 160-12 and 143-7. Sam-
ples 180-32 and 143-7 are silicified meta-komatiites, while
sample 160-12 represents a vein composed of quartz, car-
bonate, pyrite and organic material. Basaltic meta-
komatiites from Mendon are intercalated and overlain by
finely-laminated black cherts (Fig. 2D, H) containing a sig-
250 V. Busigny et al. / Geochimica et Cosmochimica Acta 210 (2017) 247–266

Fig. 2. Selected cm-scale photographs (A-D) and photomicrographs (E-H) illustrating the variety of samples from Mapepe and Mendon
Formations analyzed in the present study. (A) and (E): ferruginous chert layer interleaved with fine-grained volcanoclastic sediments. (B) and
(F): terrigenous and volcanoclastic sediments. (C) and (G): bedded barite with laminated pyrite layers located at the base of the Mapepe
Formation. (D) and (H): laminated black chert of the Mendon Formation. Fe-ox: iron oxides, l-qtz: microquartz, Carb: carbonate, Py:
pyrite, Bar: barite.

nificant content of organic matter between 0.21 and 0.87%.
Five sedimentary black cherts were analyzed: 181-19, 139-8,
114-33, 95-41 and 85-45. They are composed of micro-
quartz, iron carbonate (ankerite), sulfide (pyrite), chlorite
and ganterite (i.e. Ba-muscovite). Iron oxide and chalcopy-
rite are found in some samples as minor phases.
The overlying Mapepe Formation consists of volcan-
oclastic and terrigenous sediments (Fig. 2B) interleaved
with local barite beds (Fig. 2C) and ferruginous cherts
(Fig. 2A). Low-grade hydrothermal alteration is wide-
spread, resulting in the replacement of many primary con-
stituents by silica, ankerite and sericite. It has been
suggested that perhaps 50% of the Mapepe Formation is
 V. Busigny et al. / Geochimica et Cosmochimica Acta 210 (2017) 247–266
composed of altered dacitic erupted ash and volcanoclastic
material and that the associated terrigenous sediments were
derived from uplift and erosion of the Onverwacht Group
together with previously formed units of the lower Fig Tree
Group (Lowe and Nocita, 1999). In the BBDP2 drill-core,
the contact between Mendon and Mapepe is an erosional
discontinuity, marked by brecciated tuffaceous material
overlain by barite beds. The barite beds consist of green-
colored1 cm-scale barite blades and cauliflowers in associa-
tion with disseminated and bedded pyrites (Fig. 2C). Sec-
ondary hydrothermal alteration overprint led to intense
silicification and partial replacement of barite by
microquartz.
Eight bedded barite samples were investigated: 78-18,
78-08, 78-06, 77-5, 77-30, 76-76, 67-95 and 67-93. The sam-
ples located immediately above the Mendon-Mapepe con-
tact (78-18, 78-08 and 78-06) are generally laminated with
large barite crystal fans alternating with mm-scale pyrite
layers, while other samples display accumulation of non-
oriented barite crystals with local needle-like texture
(Fig. 2C, G).
Five samples representing terrigenous and volcanoclas-
tic sediments have been selected: 68-42, 68-05, 56-66, 56-
30 and 45-99. They are composed of silica shards of various
sizes and large pseudomorphs of barite grains, replaced by
microquartz. They are strongly silicified and contain locally
rounded to angular pyrites, and rounded quartz grains. On
the basis of trace element abundances and modeling,
Hofmann (2005) suggested that hydraulic sorting did not
affect the sedimentary abundances of Rare Earth Elements
(REE) and High-Field Strength Elements (HFSE), imply-
ing short distances of sedimentary transport of the detrital
phases. This conclusion is consistent with the dominant
angular shape of the sedimentary particles included in our
samples. The angular grains present in our samples corre-
spond to quartz, iron carbonate (siderite and ankerite), iron
oxide, barite needle and pyrite. These grains are embedded
in a fine matrix dominated by quartz and ankerite. Samples
68-42 and 68-05 contain local spherule textures composed
mainly of quartz and phyllosilicates (i.e. chlorite and seri-
cite). The spherules are thought to represent distal fallout
formed within an impact plume after large meteoritic
impact event at 3.24 Ga (Lowe et al., 2003). However, the
low abundance of spherules in sample 68-05, relative to typ-
ical spherule beds (e.g. Krull-Davatzes et al., 2012; van
Zuilen et al., 2014), likely indicates a re-depositional/
detrital origin.
Four ferruginous cherts were analyzed: 39-75, 50-25, 52-
72a and 52-72b (Fig. 2A, E). They are composed of micro-
quartz with various proportions of ankerite and Fe oxides
(present as tiny crystals <2 lm), together with minor Ba-
rich feldspar or mica (ganterite) and calcite. Samples 52-
72a and 52-72b (ferruginous chert, this one can directly
be compared to the study of Satkoski et al., 2015) are
two different pieces of the same rock, allowing us to evalu-
ate potential heterogeneities due to finely laminated
structures.
1
For interpretation of color in Fig. 2, the reader is referred to the
web version of this article.
251
4. ANALYTICAL METHODS
For each drill-core sample, uniform layers of 0.5–2 cm
thickness were selected, cut and powdered to a fraction
<60 lm. The same powders were used for Fe, S and major
and trace element analyses. Iron isotope compositions were
determined using a method thoroughly described in
Busigny et al. (2014) and only summarized herein. About
10–35 mg of each sample were acidified by successive mix-
tures of HF, HNO3 and/or HCl to ensure complete diges-
tion. For samples containing barite, a solid residue
(corresponding to barite insoluble fraction) could not be
dissolved and was removed by centrifugation. Iron con-
tained in the soluble fraction was separated from matrix
elements on anion exchange chromatography in HCl med-
ium (Strelow, 1980; Dauphas et al., 2004). Iron concentra-
tions and isotopic compositions were measured using a
ThermoFischer Neptune MC-ICP-MS (Multiple Collector
Inductively Coupled Plasma Mass Spectrometer). Sample
solutions were nebulized and introduced using ESI Apex-
HF desolvating apparatus. Iron isotopes were resolved
from argide interferences using the high-resolution mode
of the Neptune (Weyer and Schwieters, 2003; Schoenberg
and von Blanckenburg, 2005). Instrumental mass bias was
corrected by using the conventional sample-standard brack-
eting (SSB) approach (Rouxel et al., 2003; Albarède and
Beard, 2004). The 56Fe/54Fe and 57Fe/54Fe ratios were
expressed in the d notation in per mil (‰) as:
d56 Fe ¼ ½ð56 Fe=54 FeÞsample =ð56 Fe=54 FeÞstandard
1  1000
and
d%57 Fe ¼ ½ð57 Fe=54 FeÞsample =ð57 Fe=54 FeÞstandard
1  1000
where the standard is IRMM-014, from the Institute for
Reference Materials and Measurements (Taylor et al.,
1992). The analytical blank was always below 30 ng Fe
and represented less than 0.3% of the bulk Fe in the sam-
ples. Based on replicate analyses of international rock geo-
standards (IF-G, ACE and BCR2), the external precision
and accuracy were always better than 0.06‰ for d56Fe
and 0.12‰ for d57Fe (2SD).
Multiple sulfur isotope analyses of pyrites and sulfates
have been performed on bulk rock powders. The pyrites
were extracted from bulk sample powders with standard
chromium reduction technique, converting S into Ag2S
(Canfield et al., 1986), while sulfates were reacted using
Thode’s solution (Thode et al., 1961) and converted to
Ag2S. Ag2S was then converted to SF6 by fluorination,
purified first by cryogenic separation and then by gas chro-
matography (Labidi et al., 2012). Finally, the purified SF6
was introduced into a MAT253 isotope-ratio mass spec-
trometer (IRMS) for multiple sulfur isotope measurement
in dual-inlet mode. All isotopic compositions are reported
as per mil (‰) deviations from V-CDT standard using
the conventional notation: d34S = [(34S/32S)sample/
(34S/32S)V-CDT
1]  1000.
D33S and D36S are used as a measurement of the devia-
tion from the terrestrial mass-dependent fractionation line
252 V. Busigny et al. / Geochimica et Cosmochimica Acta 210 (2017) 247–266
and represent the Mass Independent Fractionations (MIF)
expressed as (Farquhar et al., 2001):
D33S = 1000  [(1 + d33S/1000)
(1 + d34S/1000)0.515]
D36S = 1000  [(1 + d36S/1000)
(1 + d34S/1000)1.89]
The analytical reproducibility (2SD) on d34S, D33S and
36
D S, estimated from replicate analyses of the IAEA-S1
standard, was better than ±0.2‰, ±0.02‰ and ±0.2‰
respectively.
Whole rock major element concentrations were mea-
sured using ICP-OES at the Service d’Analyse des Roches
et des Mineraux (SARM) of the Centre de Recherches
Pétrographiques et Géochimiques (CRPG) of
Vandoeuvre-Lès-Nancy, France, following the method
described in Carignan et al. (2001). Analytical precision
and detection limits for major element concentrations are
typically better than ±10%. The determination of the major
element composition of bedded barite samples was incom-
plete because of the difficulty of dissolving barite minerals.
Barite solid residue was thus separated by centrifugation
after conventional dissolution of other phases using mixing
of HNO3-HF, and HF-HCl. Only elements with reliable
concentration estimates are provided for these samples.
5. RESULTS
5.1. Major element concentrations: a mineralogical control
Major element concentrations in Mapepe and Mendon
samples are given in Table 1 and some general features
are illustrated in Fig. 3. SiO2 content shows a large range
from 17 to 96 wt% (with most samples >60 wt%). SiO2 con-
tent is inversely correlated with MgO and CaO (Fig. 3A).
This indicates that the composition of these samples is
dominated by a mixture of quartz and carbonate, in good
agreement with thin section observations. Al2O3 and TiO2
contents vary from 0.14 to 4.76 wt%, and 0.02 to 0.66 wt
%, respectively. TiO2 is linearly correlated with Al2O3 and
shows two different trends for the Mendon and Mapepe
Formations (Fig. 3B). K2O shows also a linear correlation
with Al2O3 but with no distinction between Mendon and
Mapepe data. Mineralogical analysis indicates that K and
Al are both carried by mica, suggesting that the variations
in K and Al contents reflect various proportions of mica in
the host rock (Fig. 3C).
5.2. Iron concentration and isotope distribution
Iron concentration in Mendon samples covers a wide
range from 0.55 to 9.11 wt%, while Mapepe samples display
even larger variations between 0.07 and 21.38 wt%
(Table 1). In order to avoid any dilution effect by carbonate
or quartz precipitation, Fe variations can be evaluated
using the Fe/Al molar ratio rather than pure concentration.
The Fe/Al molar ratio ranges from 0.26 to 10.53 in Mendon
and 0.10 to 37.54 in Mapepe. Compared to the average Fe/
Al ratio in shales deposited in oxic and suboxic environ-
ments (0.5; Taylor and McLennan, 1985; Lyons and
Severmann, 2006), four samples from the Mapepe Forma-
tion are extremely depleted in Fe, with Fe/Al ratios between
0.10 and 0.17 (samples 45-99, 67-93, 76-76, 77-30; Table 1).
These four Mapepe samples are not restricted to any given
lithology and occur in bedded barites, as well as terrigenous
and volcanoclastic sediments.
Iron isotope compositions are given in Table 2 and illus-
trated as a function of depth in Fig. 4. The d56Fe values in
Mendon vary in a limited range from
0.15 ± 0.03 to
+0.50 ± 0.05‰, in comparison with Mapepe samples,
which show a high variability between
2.04 ± 0.04 and
+2.14 ± 0.07‰. For the latter, there is a strong mineralog-
ical control, with the most negative values observed in bed-
ded barites containing pyrite laminates, while the most
positive values are recorded in ferruginous cherts contain-
ing Fe oxides. Mn/Fe ratios display large variations over
three orders of magnitude, with values from 0.007 to 0.08
in Mendon and 0.0001 to 0.246 in Mapepe samples
(Table 1). Interestingly these variations are also related to
mineralogy. Low Mn/Fe ratios correspond to samples in
which Fe-bearing phases are mostly pyrite or Fe-oxides,
while high Mn/Fe ratios are attributed to carbonates (i.e.
ankerite, as observed by SEM analyses on thin sections).
A plot of d56Fe values as a function of Mn/Fe ratio
(Fig. 5) shows linear trends clearly linked to mineralogical
variations. It can be emphasized that the strongly
hydrothermally-altered basaltic komatiites from Mendon
show a large variability in Mn/Fe ratios (0.023–0.080)
and d56Fe values (
0.15 ± 0.03 to +0.49 ± 0.02‰) com-
pared to fresh komatiites, which are characterized by Mn/
Fe  0.015 ± 0.004 (Arndt, 1986) and d56Fe  0.04
± 0.03‰ (Dauphas et al., 2010). Hydrothermal alteration
thus modified both the Fe content and isotope composition
of Mendon komatiites.
5.3. Multiple sulfur isotope compositions
Sulfur isotope compositions of bulk sulfides in Mapepe
and Mendon samples are shown in Table 2 and illustrated
as a function of depth in Fig. 4. d34S values in Mendon dis-
play relatively uniform and positive values between +0.28
and +3.27‰ (±0.02‰, 2SD). In contrast, Mapepe samples
show a larger variability, with mostly negative d34S values
from
10.84 to
1.25‰, except one sample with a positive
value of +1.44‰ (sample 56-66). The three samples with
the most negative d34S values show the lowest Fe content
and Fe/Al ratio (samples 67-93, 76-76, 77-30). D33S is sig-
nificantly different from 0‰ in most samples, with values
ranging from
0.15 to +2.55‰ in Mendon and
0.35 to
+0.87‰ in Mapepe (±0.02‰, 2SD). D36S varies from

2.05 to
0.06‰ in Mendon and from
0.87 to +0.09‰
in Mapepe (±0.2‰, 2SD; Table 2). A plot of D36S vs.
D33S shows a rough inverse correlation (not shown), with
a slope of
0.81 (R2 = 0.38), similar to the trend defined
by most sedimentary rocks from the Archean eon
(slope 
0.9; e.g. Farquhar et al., 2000). Fig. 6A displays
the relation between D33S and d34S values in Mendon and
Mapepe samples, together with barite data from Mapepe
reported by previous studies (Bao et al., 2007; Roerdink
et al., 2012; Montinaro et al., 2015). Fig. 6B reports d56Fe
vs d34S for Mendon and Mapepe samples. Although no
Table 1
Major element concentrations, total organic carbon content (TOC) and selected molar ratios in Mapepe and Mendon samples from the core BBDP2.
Sample Rock type Deptha (m) SiO2 (wt%) Al2O3 (wt%) Fe2O3 (wt%) MnO (wt%) MgO (wt%) CaO Na2O K2O TiO2 PF Total TOC Mn/Fe Fe/Al
(wt%) (wt%) (wt%) (wt%) (wt%) (wt%) (wt%) (molar) (molar)

V. Busigny et al. / Geochimica et Cosmochimica Acta 210 (2017) 247–266

Mapepe Formation
39-75 Ferruginous chert 39.75 87.70 0.14 1.39 0.090 1.33 2.48 0.01 0.03 4.94 98.10 0.03 0.07 6.53
45-99 Terrig. & volc. sed. 45.99 65.69 4.76 0.74 0.006 0.12 0.17 0.06 0.88 0.66 5.95 79.03 0.02 0.01 0.10
50-25 Ferruginous chert 50.25 69.03 1.96 2.70 0.295 4.22 7.66 0.03 0.40 0.15 12.43 98.88 0.02 0.12 0.88
52-72a Ferruginous chert 52.72 94.73 0.17 0.74 0.009 0.13 0.41 0.02 0.03 1.59 97.81 0.02 0.01 2.79
52-72b Ferruginous chert 52.72
56-30 Terrig. & volc. sed. 56.30 79.61 0.65 1.19 0.260 3.23 5.62 0.02 0.15 0.04 8.76 99.53 0.25 1.17
56.66 Terrig. & volc. sed. 56.66 78.24 2.13 1.28 0.213 2.83 4.87 0.03 0.46 0.21 7.91 98.16 0.04 0.19 0.38
67-93 Bedded barite 67.93 0.40 0.08 0.002 0.06 0.07 0.10 0.03 0.12
67-95 Bedded barite 67.95 0.01
68-05 Terrig. & volc. sed. 68.05 61.51 1.63 2.52 0.400 5.20 8.85 0.03 0.25 0.13 13.72 94.24 0.02 0.18 0.98
68-42 Terrig. & volc. sed. 68.42 61.98 0.90 1.47 0.145 2.66 4.44 0.14 0.07 9.83 81.63 0.03 0.11 1.05
76-76 Bedded barite 76.76 0.34 0.07 0.010 0.20 0.29 0.16 0.13
77-30 Bedded barite 77.30 0.26 0.07 0.007 0.11 0.11 0.11 0.17
77-50 Bedded barite 77.50 0.93 18.01 0.004 0.07 0.21 0.09 0.00 12.43
78-06 Bedded barite 78.06 0.34 20.00 0.002 0.00 37.54
78-08 Bedded barite 78.08 0.17 0.31 0.003 0.09 0.13 0.03 0.01 1.16
78-18 Bedded barite 78.18 0.53 21.38 0.003 0.10 0.04 0.00 25.76
Mendon Formation
85-45 Black chert 85.45 77.89 1.94 3.40 0.196 2.82 4.79 0.04 0.44 0.06 9.06 100.64 0.06
95-41 Black chert 95.41 96.05 1.34 0.55 0.004 0.13 0.11 0.02 0.29 0.05 1.46 100.00 0.40 0.01
114-33 Black chert 114.33 84.77 3.01 4.44 0.067 1.04 0.05 0.02 0.73 0.13 4.63 98.88 0.87 0.02
139-80 Black chert 139.80 82.57 1.12 7.81 0.153 1.64 0.15 0.01 0.27 0.05 5.72 99.49 0.25 0.02
143-70 Komatiite 143.70 16.81 2.38 6.79 0.483 12.96 23.02 0.04 0.68 0.07 35.95 99.19 0.08
160-12 Komatiite 160.12 75.07 4.39 4.25 0.089 2.13 3.80 0.05 1.21 0.15 7.93 99.06 0.02 0.02
180-32 Komatiite 180.32 24.38 0.55 9.11 0.434 12.39 19.03 0.04 0.05 0.02 32.83 98.84 0.05
181-19 Black chert 181.19 45.99 3.58 5.58 0.287 7.69 13.45 0.19 0.02 0.12 21.56 98.45 0.06
a
Depth in the drill-core recovered by the Barberton Barite Drilling Project BBDP2. terrig. & volc. sed.: terrigenous and volcanoclastic sediment.

253
254 V. Busigny et al. / Geochimica et Cosmochimica Acta 210 (2017) 247–266
Fig. 3. Major element concentrations (in wt%) showing the main
geochemical features of the samples from Mapepe (square) and
Mendon (circle) Formations. (A) SiO2 vs CaO: samples are mostly
composed of quartz and carbonate. (B) Al2O3 vs TiO2: the two
different trends illustrate that the rocks from Mendon are not the
source of Mapepe detrital component. (C) K2O vs Al2O3: the single
trend for Mapepe and Mendon indicates that all the rocks were
hydrothermally altered.
clear trend can be observed, the distribution of the data
illustrates a strong petrological control, with the various
lithologies corresponding to separate fields. The most strik-
ing feature is that bedded barites define two different
groups, which are not detected in a D33S-d34S plot. The first
group, with the most negative d34S (
10.84 to
5.59‰) and
d56Fe from
0.90 to 0.00‰, corresponds to samples with
the lowest Fe concentration (0.05 wt% Fe; Table 2). The
second group has moderately negative d34S (
5.27 to

2.03‰) and extremely negative d56Fe (
2.04 to

1.60‰) and corresponds to samples with the highest Fe
concentrations (0.22–14.93 wt%). Two groups of bedded
barite can thus be distinguished based on their Fe concen-
trations, reflecting pyrite content, and its associated Fe
and S isotope compositions.
6. DISCUSSION
6.1. Evidence for detrital and hydrothermal influences
Before deciphering primary authigenic signatures and
reconstructing paleo-environmental conditions associated
with Mapepe and Mendon sediment deposition, it is impor-
tant to evaluate the role of detrital and hydrothermally-
altered components on chemical and isotope compositions
of bulk samples. Detrital influence can be evaluated using
Al and Ti contents since these elements are generally not
mobilized by fluid circulation (Rouxel et al., 2003;
Dauphas et al., 2007), except under exceptionally low pH
(<2; Rusk et al., 2008) or high pressure and temperature
conditions (>1 GPa, 800 °C; Manning, 2006). The correla-
tions observed between Al and Ti in Mapepe and Mendon
Formations are consistent with minimal hydrothermal
alteration for these elements, and support their use as indi-
cators of detrital input. The two different trends defined by
Mapepe and Mendon data indicate that Al and Ti sources
were distinct in these formations (Fig. 3B). Lowe and
Nocita (1999) and Hofmann (2005) suggested that the detri-
tal component included in the Mapepe sedimentary depos-
its derived from uplift and erosion of rocks from the
Onverwacht Group, possibly the Mendon Formation. This
hypothesis was also suggested earlier for the Loenen For-
mation of the Fig Tree Group based on major element
chemistry and petrographic work (Heinrichs, 1980). The
different Al/Ti ratios observed here for Mapepe and Men-
don indicate that Mapepe detrital fraction was not derived
from erosion of the Mendon Formation, and therefore that
another detrital source is required at least in this part of the
oceanic basin.
Contrasting with the two different trends observed
between Al and Ti, plotting Al2O3 vs K2O concentrations
results in a single correlation including samples from both
Mapepe and Mendon Formations (Fig. 3C). This likely
reflects the addition of K by fluid-rock interaction (e.g.
Toulkeridis et al., 1998; Hofmann, 2005). Mineralogical
observations coupled with SEM analyses of our samples
indicate that K is mostly hosted by mica, in the form of ser-
icite and ganterite. The capacity of a rock to incorporate K
Table 2
Iron and sulfur isotopes data in Mapepe and Mendon samples from the core BBDP2.
Sample Fea d56Fe ±2r d57Fe ±2r Sulfide Sulfate
(wt%) (‰) (‰) (‰) (‰) 34
d S ±2r 33
D S ±2r 36
D S ±2r d34S ±2r D33S ±2r D36S ±2r
(‰) (‰) (‰) (‰) (‰) (‰) (‰) (‰) (‰) (‰) (‰) (‰)

V. Busigny et al. / Geochimica et Cosmochimica Acta 210 (2017) 247–266

Mapepe Formation
39-75 0.98 1.20 0.02 1.81 0.06
2.27 0.02 0.31 0.02
0.36 0.20
45-99 0.50 0.17 0.03 0.24 0.08
1.25 0.02 0.06 0.02
0.29 0.20
50-25 1.67 0.22 0.08 0.54 0.01
4.59 0.02 0.40 0.02
0.08 0.20
52-72a 0.51 2.14 0.07 3.33 0.10
4.44 0.02 0.87 0.02
0.87 0.20
52-72b 2.65 0.01 0.04 0.04 0.03
56-30 0.85
0.39 0.04
0.56 0.06
2.47 0.02 0.01 0.02
0.50 0.20
56.66 0.77
0.25 0.05
0.33 0.07 1.44 0.02 0.17 0.02 0.08 0.20
67-93 0.05 0.01 0.05 0.02 0.08
6.82 0.01
0.10 0.02
0.20 0.20 3.92 0.02
0.60 0.02 0.28 0.20
67-95 0.06
0.38 0.03
0.63 0.03
5.59 0.02
0.05 0.02
0.10 0.20
68-05 1.96
0.33 0.03
0.44 0.06
3.47 0.01
0.25 0.02 0.09 0.20
68-42 1.37
0.37 0.05
0.54 0.10
6.16 0.01
0.23 0.02
0.07 0.20
76-76 0.05
0.90 0.02
1.34 0.03
10.84 0.02
0.35 0.02
0.36 0.20 3.62 0.02
0.66 0.02 0.43 0.20
77-30 0.05
0.53 0.04
0.78 0.03
9.08 0.02
0.15 0.02
0.13 0.20 3.95 0.02
0.55 0.02 0.55 0.20
77-50 13.40
1.60 0.03
2.37 0.05
2.03 0.03 0.38 0.02
0.69 0.20
78-06 14.00
2.04 0.04
2.99 0.05
4.22 0.02
0.10 0.02
0.56 0.20
78-08 0.22
1.92 0.05
2.81 0.06
5.27 0.01
0.14 0.02
0.27 0.20 3.01 0.02
0.57 0.02 0.62 0.20
78-18 14.93
1.94 0.02
2.92 0.08
4.61 0.01
0.11 0.02
0.11 0.20 4.69 0.02
0.42 0.02 0.43 0.20
Mendon Formation
85-45 2.25
0.01 0.04
0.05 0.04 0.08 0.01 0.08 0.02
0.64 0.20
95-41 0.40 0.11 0.03 0.26 0.03 1.18 0.01 1.00 0.02
1.31 0.20
114-33 2.66 0.50 0.05 0.78 0.09 2.75 0.02 2.55 0.02
2.05 0.20
139-80 5.04 0.15 0.03 0.23 0.10 0.52 0.03 1.69 0.02
0.93 0.20
143-70 4.80
0.15 0.03
0.23 0.04 2.55 0.03
0.15 0.02
0.34 0.20
160-12 2.69 0.49 0.02 0.80 0.07 0.34 0.01
0.12 0.02
0.06 0.20
180-32 6.47
0.03 0.04 0.00 0.03 3.27 0.02 0.23 0.02
1.03 0.20
181-19 3.93 0.00 0.06
0.02 0.08 0.28 0.02 0.92 0.02
1.25 0.20
a
Iron concentration measured by MC-ICP-MS, after column chemistry.

255
256 V. Busigny et al. / Geochimica et Cosmochimica Acta 210 (2017) 247–266

Fig. 4. Variations in Fe/Al molar ratio, Fe (d56Fe in ‰ relative to IRMM-014) and S isotope compositions (d34S relative to V-CDT, and D33S
in ‰) as a function of depth in the drill-core for Mapepe (squares) and Mendon (circles) Formations. The red dotted line corresponds to the
erosional contact between Mendon and Mapepe Formations. The grey line on Fe/Al plot represents the average ratio in shales deposited in
oxic and suboxic environments (0.5; Taylor and McLennan, 1985; Lyons and Severmann, 2006). Other gray vertical lines represent
references at 0‰ for d56Fe, d34S and D33S, respectively. Error bars are smaller than symbols. (For interpretation of the references to color in
this figure legend, the reader is referred to the web version of this article.)

Fig. 5. Bulk rock Mn/Fe molar ratio versus Fe isotope composition (d56Fe), showing that Fe isotope compositions are controlled by
mineralogy. (A) The correlation labeled Fe-carb/Fe-ox refers to Fe-carbonate/Fe-oxyhydroxide in Mapepe samples with well-preserved, non-
hydrothermally altered signatures. The grey area represents samples (basaltic komatiites, black cherts, some bedded barite and terrigenous
and volcanoclastic sediments) with low Fe contents and hydrothermally modified d56Fe values. (B) Zoom on the hydrothermal-alteration
trend shown in A. Data from Mendon and Mapepe are represented as circles and squares, respectively. Error bars are smaller than symbols.

is dependent on the Al content of the initial rock, before mica. Other evidence in support of a strong fluid influence
hydrothermal alteration. In other words, the more a rock in these rocks was noted in previous studies. For instance,
was Al-rich, the more it is capable of incorporating K into multi-isotope dating (Pb-Pb, Sm-Nd and Rb-Sr) of the
 V. Busigny et al. / Geochimica et Cosmochimica Acta 210 (2017) 247–266 257

Fig. 6. (A) Multiple S isotope composition of bulk-rock sulfides in samples from Mapepe (squares) and Mendon (circles) Formations. Sulfate
S-isotope data (open diamonds) are from Bao et al. (2007), Roerdink et al. (2012) and Montinaro et al. (2015). Data of sulfides disseminated in
bedded barites are from Roerdink et al. (2013). Error bars are smaller than symbols. The two arrows represent potential processes explaining
S isotope variations in sulfides from bedded barites, as well as terrigenous and volcanoclastic sediments: (1) microbial reduction from a sulfate
pool in seawater, followed by (2) a mixing with hydrothermally-derived juvenile sulfur (Roerdink et al., 2013; see Section 6.2. for more
details). (B) Iron versus sulfur isotope compositions for Mapepe and Mendon samples; symbols as in (A).

silicic carbonates from Onverwacht and Fig Tree Groups
yielded an age of 2.7 Ga, interpreted as post-
depositional isotope resetting related to fluid circulation
(Toulkeridis et al., 1998). In situ O and Si isotope measure-
ments coupled to fluid inclusion analysis of chert from the
Onverwacht Group were interpreted as a late-stage fluid-
rock exchanges at temperature between 200 and 300 °C
and depth of 1–4 km (Marin-Carbonne et al., 2011). In
other volcanic rocks and cherts from the Barberton Green-
stone Belt (Theespruit, Hooggenoeg and Kromberg Forma-
tions), positive correlations were found between bulk rock
SiO2 contents and O and Si isotopes, and were interpreted
as evidence for pervasive silicification by large volumes of
Si-rich fluids (Abraham et al., 2011). Silicification of these
volcanic rocks produced a depletion in elements commonly
mobile during fluid-rock interaction (e.g. Co, Ni, Cu, Zn,
Na), but an enrichment in K, Rb and Ba (Hofmann and
Harris, 2008). Accordingly, the well-defined K-Al correla-
tion reported here (Fig. 3C) is interpreted to reflect a perva-
sive hydrothermal alteration process affecting both Mapepe
and Mendon sedimentary successions, a conclusion in good
agreement with previous studies.
An important question to address is the potential impact
of fluid overprint on the bulk Fe and S isotope composi-
tions. Plotting Mn/Fe vs d56Fe can provide valuable insight
into this question. As shown in Fig. 5B (gray area), black
cherts and basaltic komatiites from Mendon display a
strong correlation with five samples from Mapepe
(R2 = 0.85), including bedded barites (76-76, 77-30 and
67-93), and terrigenous and volcanoclastic sediments (68-
42 and 45-99). This correlation likely reflects a fluid-
induced overprint as it includes various lithologies and
stratigraphic intervals. Importantly, the three bedded barite
samples involved in this correlation have the lowest Fe con-
tents (0.07–0.08 wt% Fe2O3). This suggests that they were
more sensitive to the effect of Fe-bearing fluids compared
to other barite samples, which have higher Fe contents
(0.3–21 wt% Fe2O3). More specifically, we interpret the
258 V. Busigny et al. / Geochimica et Cosmochimica Acta 210 (2017) 247–266
fluid-influenced trend shown in Fig. 5B as a mixing between
Fe-bearing carbonates and sulfides, this suggestion being
again supported by petrographic observations. In these
fluid-influenced samples, both sulfides and carbonates were
either precipitated or reset by isotope exchange during late
hydrothermal event. SEM analyses of sulfides in these sam-
ples show that they contain negligible amount of Mn. Thus
hydrothermally altered sulfides can be approximated from
the correlation plotted in Fig. 5B at Mn/Fe  0 and d56Fe
of +0.46 ± 0.27‰. The Fe/Mn ratios of carbonate mea-
sured by SEM analyses of hydrothermally altered samples
show relatively large variations between 0.08 and 0.16.
From the trend in Fig. 5B, this Fe/Mn ratio corresponds
to d56Fe values of Fe carbonates of
0.59 ± 0.35‰. Inter-
estingly, the Fe isotope fractionation between pyrite and
Fe-carbonate (D56Fepyrite-carb) in these hydrothermally
altered samples is around 1.05‰, a value similar to that
determined by density functional theory calculation for pyr-
ite and siderite at 300 °C (1.3‰; Blanchard et al., 2009).
The good agreement between our measurements and data
predicted from theoretical calculation supports our
conclusion that Fe isotope compositions of sulfides and
Fe-carbonates were modified by late fluid overprint at
300 °C.
Sulfide S-isotope data of strongly hydrothermally-
altered Mapepe samples (i.e., plotting in the gray area in
Mn/Fe vs d56Fe, Fig. 5B) show the largest range of d34S val-
ues between
10.84 and
1.25‰ (Table 2) and lowest Fe
and sulfide contents. This contrasts with the more restricted
range of d34S values (
3.7 ± 2.4‰, 2r, n = 9) defined by
other Mapepe samples. The Mapepe samples with low Fe
and sulfide contents could therefore have been modified
by late fluid overprint. However, this is inconsistent with
the fact that their d34S vs D33S values define distinct isotopic
arrays related to rock lithology and no evidence for
hydrothermal influence such as isotope homogenization
(Fig. 6A). In other words, hydrothermally altered Mapepe
samples identified from Mn/Fe-d56Fe relationships show,
in a d34S-D33S diagram, the same general trends than other
samples, with strong petrological control. This suggests that
S isotope compositions were not homogenized on large
scale and preserved pristine signatures inherited from
depositional environment, a suggestion consistent with
Roerdink et al. (2013). If true, then it implies that sulfides
in hydrothermally altered Mapepe samples did not
precipitate during fluid overprint but rather experienced
Fe isotope exchanges during fluid-rock interaction (while
S isotopes remained unaffected). This may have been
possible for instance if hydrothermal fluids were S-free (or
at least S-poor). Finally, mass-independent signatures,
reflected by D33S values, are significantly different from
0‰ for all Mendon and Mapepe samples (Fig. 6A).
This indicates that the source of S input to the rocks
was not strictly of mantle origin but rather experienced
surface (atmospheric and oceanic) cycling before being
reintroduced into the crust by fluid infiltration processes.
We thus emphasize that 33S-anomalies can be preserved in
sulfide minerals despite evidence of strong hydrothermal-
alteration overprint.
6.2. Assessing primary mineral composition
Although some of the rock samples from Mapepe and
Mendon were strongly overprinted by hydrothermal fluids,
the Fe isotope composition of several samples appears to
preserve a primary authigenic signature. The distinction
between both types of samples can be made from Fig. 5,
where the trend highlighted by the gray area (containing
basaltic komatiites, black cherts, some bedded barites as
well as terrigenous and volcanoclastic sediments) is inter-
preted as hydrothermally-modified d56Fe values (see discus-
sion above in Section 6.1). In contrast, several samples from
the Mapepe Formation stand apart from this hydrothermal
trend and are suggested to record primary geochemical sig-
nature from textural, petrological and geochemical evi-
dence. For instance, ferruginous cherts (39-75, 50-25, 52-
72) and several terrigenous and volcanoclastic sediments
(56-30, 56-66, 68-05) display a linear correlation
(R2 = 0.903) in a Mn/Fe vs d56Fe diagram (Fig. 5A), which
is clearly distinct from the hydrothermal alteration trend.
Petrographic observations indicate that Fe in ferruginous
cherts is carried by tiny crystals (<2 lm) of Fe oxides and
ankerite included in a cherty matrix. Interestingly, the rocks
with the highest proportion of Fe oxides correspond to the
most positive d56Fe values. In contrast, iron in terrigenous
and volcanoclastic sediments exclusively occurs in ankerite,
with no visible trace of Fe oxides. The linear correlation in
Fig. 5A between Mn/Fe and d56Fe thus represents a mixing
trend between Fe oxide and ankerite (noted Fe-carb in
Fig. 5A). Since Fe oxide contains limited amount of Mn rel-
ative to Fe, their Mn/Fe ratio can reasonably be considered
to be 0. The d56Fe values of these oxides can then be
derived from the linear correlation, providing a value of
+2.19 ± 0.69‰ (Fig. 5A). The positive d56Fe values in fer-
ruginous cherts are positively correlated with the SiO2 con-
tent, thus suggesting that silicification protected primary Fe
oxides – and their Fe isotope composition – from reductive
dissolution. Together with textural observations, this indi-
cates that silicification may have acted as an impermeable
barrier inhibiting cation and isotope exchanges relatively
early in the rock history. The Fe isotope composition of
Fe-carbonate matching Fe-oxides in Fig. 5A can also be
deduced from their Mn/Fe ratios. Considering a mean
Mn/Fe value of 0.21, it yields a d56Fecarbonate value of

0.50 ± 0.52‰ (Fig. 5A). As detailed below, we suggest
that this value reflects the primary signature of Fe carbon-
ates, either formed in the water column or, most likely, dur-
ing early diagenetic processes in the sediment.
The primary vs hydrothermal origin of the carbonates
contained in Mapepe terrigenous and volcanoclastic sedi-
ments has been the subject of discussion. From Sm-Nd,
Rb-Sr and Pb-Pb isotopes systematic, Toulkeridis et al.
(1998) suggested that Mapepe sedimentary rocks represent
primary carbonates, which have experienced silicification
and sericitization during a late hydrothermal event 2.7 Ga
ago. Yet part of the carbonates in Mapepe likely experi-
enced chemical and isotopic exchanges and possibly recrys-
tallization through hydrothermalism, while others may
have been preserved, for instance due to early silicification
 V. Busigny et al. / Geochimica et Cosmochimica Acta 210 (2017) 247–266
(Hofmann, 2005). In the present work, the two different
trends interpreted as reflecting primary and hydrothermal
features (Fig. 5) are also supported by two other geochem-
ical arguments. First, the partitioning behavior of Mn and
Fe in carbonates is temperature dependent. An experimen-
tal study demonstrated that Mn is preferentially incorpo-
rated in carbonates relative to Fe with decreasing
temperature (Dromgoole and Walter, 1990). Considering
a fluid of similar composition (either deep Archean seawa-
ter or hydrothermal fluid), high Mn/Fe are indeed mea-
sured among inferred primary carbonates, supposed to be
precipitated at lower temperature. Second, bulk rock anal-
yses for Mapepe terrigenous and volcanoclastic sediments
show a bimodal distribution interpreted as a mixture
between Ba-poor primary (0.08, 0.35 and 3.19 wt% for sam-
ples 56-3, 56-66 and 68-05, respectively) and Ba-rich sec-
ondary (i.e. hydrothermally-altered) minerals (12.82 and
11.74 wt% for samples 45-99 and 68-42). Assuming Ba con-
tent can be used as a proxy for the degree of hydrothermal
overprint, then the high and low Ba contents are in perfect
agreement with the conclusions deduced from the two
trends observed in Fig. 5. Furthermore, if all minerals were
secondary, the bimodal distribution would not exist.
Another primary signature is likely recorded in Fe-rich
bedded barites. These rocks contain 18–21 wt% Fe2O3,
except one sample (78-08) with 0.3 wt% (Table 1). The
main Fe-bearing mineral is pyrite, which generally occurs
as thin layers (mm-scale) alternating with beds of barite
(Fig. 2C). These specific samples were selected for their
abundant pyrite layers with parallel and undeformed
structures, believed to be pristine sedimentary feature. In
a Mn/Fe-d56Fe diagram, these sulfides cluster around a
mean d56Fe value of
1.88 ± 0.38‰. This d56Fe value is
significantly different from the Fe sulfide signature of
+0.46 ± 0.27‰ associated with the hydrothermal-
alteration trend, and could therefore reflect a pristine
d56Fesulfide composition. The particularly high Fe content
of these rocks makes Fe isotope resetting by late fluid
circulation unlikely.
The S isotope signatures determined in the present study
for sulfides and barite from Mapepe sediments are similar
to those measured in previous studies (see Fig. 6; Bao
et al., 2007; Roerdink et al., 2012, 2013; Philippot et al.,
2012; Montinaro et al., 2015; Muller et al., 2016). Like
for Fe isotopes, a pristine sulfide S-isotope composition is
expected for sulfide-rich bedded barites because these sul-
fide layers are finely laminated and their high abundance
implies that their isotope compositions were hardly modi-
fied by hydrothermal fluids. At first glance, a primary com-
position of these sulfides may appear incompatible with the
observation that pyrite and barite in these samples do not
carry similar D33S values (Fig. 6). If pyrite and barite were
secondary, either formed or re-equilibrated, they would
have the same D33S and D36S values, which is not the case.
Also barite samples have the typical negative D33S values
inferred for Archean seawater sulfate (e.g. Bao et al.,
2007; Shen et al., 2009), and hydrothermalism would shift
their D33S towards higher values. It must be noted that bar-
ite and sulfide D33S signatures could be pristine but not
identical because of different mechanisms of formation
259
(Roerdink et al., 2012, 2013; Philippot et al., 2012;
Montinaro et al., 2015; Muller et al., 2016). At least two
scenarios could explain the different D33S values observed
in sulfides and barite. First, we could consider that barite
formed in the water column and recorded dissolved sulfate
D33S values, while pyrite formed in a more complex path-
way including several S sources with distinct D33S values
(e.g. Roerdink et al., 2013). For instance, pyrite formation
could require sulfur addition to a pyrite precursor, such as
iron monosulfide (FeS, mackinawite) or iron polysulfide
(Fe3S4, greigite) (Rickard and Luther, 2007; Farquhar
et al., 2013; Marin-Carbonne et al., 2014). In the present
study, Mapepe samples show a large range of d34Spyrite val-
ues, from
10.84 to +1.44‰, and both negative and posi-
tive 33S-anomalies, thus indicating that different sources
of sulfur are involved in sulfide formation. From quadruple
S isotope analyses by secondary ion mass spectrometry on
disseminated pyrite in barite beds from Mapepe, it was sug-
gested that these pyrites resulted from a mixing between S
derived from microbial sulfate reduction and juvenile man-
tle sulfide (Roerdink et al., 2013). Our data on sulfides from
bedded barites and volcanoclastic and terrigenous sedi-
ments fall on the same trend in a D33S-d34S diagram
(Fig. 6A) and could thus be explained similarly by mixing
various sources. Alternatively, a decoupling between barite
and pyrite D33S values in Mapepe sediments could also be
produced if pyrite formed through water column and sedi-
mentary processes, while barite would result from atmo-
spheric precursor. In a subaerial volcanic plume, barium
could react with sulfate aerosols to form microscopic barite,
which then will remain insoluble and be transferred to sed-
iments (Muller et al., 2016). This could explain the system-
atic MIF signature of Archean sulfate (Muller et al., 2016).
Finally, the highest D33S values of Mapepe are recorded in
ferruginous cherts, with positive values up to +0.87‰
(Fig. 6A). If, as suggested above, early silicification pro-
tected Fe sulfides from late fluid-induced re-equilibration,
then these strong MIF-S signatures should also be consid-
ered as primary. Roerdink et al. (2013) obtained similar sig-
natures in sulfides from cherts and proposed that positive
D33S values reflect sulfides derived from elemental sulfur
metabolism (e.g. Philippot et al., 2007) when dissolved sul-
fate concentration were too low for microbial sulfate reduc-
tion to occur. This conclusion is also compatible with our
data, implying that microbial processes, either sulfates
and/or elemental sulfur reduction, possibly played an
important role in determining S isotope composition of
the 3.2 Ga Mapepe sedimentary rocks.
6.3. Implications for paleo-environmental conditions
The Fe isotope signature recorded in the most pristine
minerals (Fe oxides, carbonates and sulfides), deciphered
above, can be used to reconstruct paleo-redox conditions
in the Mapepe depositional environment. A schematic
model is presented in Fig. 7. A well-accepted feature for
the Archean ocean is that deep waters were anoxic and fer-
ruginous (e.g. Holland, 1984; Poulton and Canfield, 2011).
The main source of Fe to the ocean was hydrothermal sys-
tems associated with submarine volcanic activity (Kump
260 V. Busigny et al. / Geochimica et Cosmochimica Acta 210 (2017) 247–266

Fig. 7. Schematic model illustrating Fe geochemical cycle in 3.2 Ga-old ferruginous ocean, recorded by the Mapepe sedimentary rocks. Fe
(II)aq is released from hydrothermal system to the ocean and diffuses from deep to shallow waters. In the photic zone, Fe(II)aq is oxidized to Fe
(III)aq and precipitates as Fe-(oxy)hydroxide. Iron precipitates sink in the water column down to the sediment, and are trapped as ferruginous
cherts. Iron carbonates are formed either in the water column, or more likely during sediment diagenesis from porewater buffered by high
concentration of Fe(II) (initially derived from hydrothermal system).

and Seyfried, 2005). Iron present as Fe(II) in minerals
forming the ocean crust was released to hydrothermal fluids
during alteration processes under anoxic conditions and
injected to the ocean (Fig. 7). It is generally assumed that
the isotopic composition of hydrothermal Fe(II) has not
varied significantly over Earth’s history (Johnson et al.,
2008) and has probably been similar to modern hydrother-
mal vent systems with d56Fe values mostly between
0.5
and 0‰ (Sharma et al., 2001; Beard et al., 2003;
Severmann et al., 2004; Rouxel et al., 2008). Dissolved Fe
(II) accumulated in the deep ocean would then have dif-
fused to shallow water to be oxidized to Fe(III) in the pho-
tic zone. Fe(III) is insoluble at circumneutral pH and would
thus have precipitated as iron oxyhydroxides (Fe(OH)3).
Iron oxyhydroxide particles would have sunk in the water
column before being incorporated into the sediment
(Fig. 7). The highly positive d56Fe value recorded in Fe oxi-
des from Mapepe Formation (+2.2‰) is compatible with
partial oxidation of aqueous Fe(II) with d56Fe  0‰, con-
sidering the 2.5–4‰ isotope fractionation between oxides
and aqueous Fe(II) (Johnson et al., 2002; Welch et al.,
2003; Anbar et al., 2005; Balci et al., 2006; Wu et al.,
2011). Using dispersion-reaction modeling of the Fe(II) oxi-
dation developed in previous studies (Czaja et al., 2012,
2013; Li et al., 2013), we can estimate the concentration
of O2 dissolved in the photic zone (Fig. 8). This model pre-
dicts that under high O2 content in the photic zone (>1 lM)
– i.e. redox stratified ocean – iron is completely oxidized at
the redox boundary, thus producing Fe oxide precipitates
with d56FeFe(OH)3  0‰. In contrast, under low O2 content
in the photic zone (<1 lM), Fe is only partially oxidized
and the isotope fractionation is expressed in Fe oxide par-
ticles, with the highest d56FeFe(OH)3 values corresponding
to the lowest dissolved O2 content (Fig. 8). The extremely
positive d56Fe value of +2.2‰ estimated for Mapepe Fe
oxides suggest that O2 content in the photic zone was lower
than 10
4 lmol/L. This O2 content is particularly low and
provides evidence for anoxic conditions at the time of fer-
ruginous chert deposition, even in shallow water of the pho-
tic zone. The mechanism of Fe oxidation in Archean ocean
has been highly debated in the literature (see review in
Bekker et al., 2010). This may have resulted from either
(1) interaction with O2 produced by oxygenic photosynthe-
sis (Klein and Beukes, 1989), (2) anoxygenic photosynthesis
using Fe(II) rather than water as electron donor and pro-
ducing Fe(III) rather than O2 (Konhauser et al., 2002;
Kappler et al., 2005) or (3) photo-oxidation processes
(Braterman et al., 1983). The low O2 content determined
from the present data may be in favor of hypothesis 2 or
3 (for similar conclusions on other geological formations,
see Li et al., 2013; Czaja et al., 2013). However, oxidation
of Fe(II) by O2 (hypothesis 1) cannot be precluded since
O2 could have been produced, used as an oxidizing agent
but not be accumulated in the environment due to higher
consumption relative to production. Another interesting
result is that Fe isotope composition of carbonates from
Mapepe samples, interpreted to record primary signature
(i.e. d56Fecarb 
0.50‰), is compatible both with a precip-
itation from aqueous Fe(II) with d56Fe  0‰ (Fig. 7) and
with isotope fractionation between Fe-carbonate and aque-
ous Fe(II) of 
0.26 to
0.70‰, as determined experimen-
tally (Wiesli et al., 2004). If Fe-carbonates precipitated from
early diagenetic reactions, as suggested by earlier work in
Archean rocks (Craddock and Dauphas, 2011; Dauphas
and Kasting, 2011; Johnson et al., 2013), this would imply
that deep ocean waters were Fe-rich and buffered sedimen-
tary pore waters in Mapepe depositional environment at
d56Fe  0‰.
Although the Fe isotope composition of ferruginous
cherts indicates that anoxic conditions prevailed in the
 V. Busigny et al. / Geochimica et Cosmochimica Acta 210 (2017) 247–266 261

Fig. 8. Comparison between the Fe isotope composition of primary Fe oxides recorded in Mapepe ferruginous cherts (+2.2‰) and the
results of a dispersion-reaction modeling of the Fe(II) oxidation developed in previous studies (Czaja et al., 2012, 2013). The model was
calculated for two different depths of the water column (200 and 500 m) and a range of Fe isotope fractionation between Fe(II) and Fe(III),
from 2.5 to 4‰ (Wu et al., 2011). It shows that dissolved O2 content in the photic zone was lower than 10
4 lmol/L, thus demonstrating
anoxic conditions.

photic zone, this does not constrain directly the depositional
environment of bedded barites since they are not exactly
located on the same stratigraphic interval than cherts.
Accordingly, one could consider the possibility of rapid
fluctuation of dissolved O2 concentration in the water col-
umn, with significant increase at the time of bedded barite
formation and subsequent decrease during cherts deposi-
tion. The only reliable Fe isotope signature of bedded barite
that can be interpreted in terms of paleo-environmental
conditions is carried by Fe sulfides, which show a mean
d56Fe value of
1.88‰. Three potential scenarios are gen-
erally proposed to explain negative d56Fe values of sedi-
mentary pyrites: (1) Dissimilatory Iron Reduction (DIR)
during sediment diagenesis (Johnson et al., 2008;
Heimann et al., 2010), (2) water column Fe oxidative
cycling (Rouxel et al., 2005; Busigny et al., 2014), and (3)
kinetic isotope fractionation associated with pyrite forma-
tion in a Fe-rich aqueous system (Guilbaud et al., 2011).
These three scenarios are examined below and compared
to data obtained on bedded barites from Mapepe Forma-
tion. In the case of DIR (scenario 1), partial reduction of
Fe(III) oxide releases Fe(II) enriched in light isotopes (by

3‰; Crosby et al., 2007) to sedimentary porewater
(Severmann et al., 2006). Subsequent pyrite precipitation
from porewater may then record this light Fe isotope signa-
ture (Johnson et al., 2008). An important assumption of
this model is that Fe(III) reduction must be incomplete
since high -or complete- reduction would produce aqueous
Fe(II) with a d56Fe value similar to initial Fe(III) oxide. In
Mapepe bedded barites, we found no evidence for residual
Fe oxides. Additionally, if primary Fe oxides with d56Fe of
2.2‰ (similar to those of cherts) would have been par-
tially reduced, aqueous Fe(II) should have been >0‰,
which is strongly different from the values observed for pyr-
ites in bedded barites. Thus we conclude that the negative
d56Fe values of Mapepe pyrite were not inherited from
DIR microbial activity. In scenario 2, the pyrite isotope sig-
nature would witness a modification of the Fe redox cycling
in the water column, due to extensive Fe oxidation by O2
production in shallow water (Rouxel et al., 2005). In mod-
ern analogues of Archean ocean, Fe oxidation at the
chemocline leaves a residual dissolved Fe(II) enriched in
light isotopes, due to precipitation of Fe(III) particles
enriched in heavy isotopes (Malinovsky et al., 2005;
Teutsch et al., 2009; Busigny et al., 2014). Dissolved sulfate
is reduced into sulfide, inducing Fe sulfide precipitation
(due to significant dissolved Fe concentration and low Fe
sulfide solubility). As a consequence, the light Fe isotope
signature of the residual dissolved Fe(II) is trapped into sul-
fide precipitates, which is ultimately transferred to the sed-
iments. Iron isotope composition of pyrite thus mirrors the
light isotope signature inherited from the Fe oxidation cycle
(Busigny et al., 2014). In the Mapepe Formation, the heavy
Fe isotope composition recorded in Fe oxides from ferrug-
inous cherts indicate a very limited Fe oxidation, with resid-
ual dissolved Fe(II) remaining unchanged relative to mean
ocean Fe derived from hydrothermal system (i.e. d56-
Fe  0‰). This suggests that the negative d56Fe of Mapepe
pyrite does not record Fe redox variation related to an
increase in dissolved O2 content of shallow water, thus rul-
ing out scenario 2. The third and last scenario to be consid-
ered is the possibility for a kinetic Fe isotope fractionation
associated with pyrite precipitation in iron-rich aqueous
system. Experimental studies showed that a depletion of

2.2‰ in pyrite can be produced during formation from
aqueous Fe(II) (Guilbaud et al., 2011). This has never been
evidenced in any natural system but clearly requires more
specific study, where both pyrite and associated fluid can
be collected. However, we note that this hypothesis is con-
sistent with a Fe(II) source of d56Fe  0‰ in the water col-
umn or sediment, as deduced from the primary Fe oxides
and carbonates in Mapepe samples. If correct, it implies
that the pool of Fe was dominating over S, allowing the
expression of Fe isotope fractionation.
262 V. Busigny et al. / Geochimica et Cosmochimica Acta 210 (2017) 247–266
To summarize, the Fe isotope composition in Fe oxides
from ferruginous cherts provides indirect evidence for
anoxic conditions, with dissolved O2 concentration <10
4 -
lmol/L in the photic zone of Mapepe depositional environ-
ment. Anoxic conditions are also supported by pyrite d56Fe
values and associated mineralogical observations. The sig-
nificant mass-independent signature recorded in S isotopes
is also indicative of highly reducing conditions in the atmo-
sphere. Our conclusions contrast with those of a recent
study coupling Fe isotope data and U concentrations in
the Manzimnyama Banded Iron Formations from the Fig
Tree Group (Satkoski et al., 2015). In this previous study,
the authors proposed that the ocean was stratified, with
oxic surface waters and anoxic and ferruginous deep-
waters. The origin of the discrepancy between this previous
study and the results presented here is still unclear since the
samples are from the same geological formation (i.e. Fig
Tree Group) and are of similar ages (3.25–3.3 Ga). We
explored in detail the differences between the two sample
sets. Based on GPS coordinates, we calculated that the
drill-core site of the present work (core BBDP2, Latitude:
25°540 24.800 S, Longitude: 31°030 23.900 E) and the one of the
previous study (core BARB4, Latitude: 25°540 24.5500 S, Lon-
gitude: 31°060 18.8200 E) are apart from more than 3 km.
Local lateral variability of the sedimentary depositional
environment could thus potentially explain the discrepancy
between the two studies. For instance, ‘‘oxygen oases” with
accumulation of O2 in proximal environments associated
with shallow water have been proposed for Archean times,
while most of the ocean could have been anoxic and reduc-
ing (Kasting, 1992; Olson et al., 2013). This hypothesis can-
not be tested from available data since there is no precise
dating for any of the two sedimentary sections. Moreover,
no stratigraphic correlation can be made between the two
cores due to strongly faulted blocks in the area and the fact
that the contact between Mapepe and underlying Mendon
Formation is not conformable (e.g. Heinrichs and
Reimer, 1977). We thus conclude that lateral variability in
the depositional environment is a possibility for explaining
the differences in lithologies and geochemical models
derived in our study and the one of Satkoski et al. (2015).
A last possibility would lie in the assumptions made in
the case of the previous study by Satkoski et al. (2015), in
which Fe isotope composition of bulk rock was supposed
to represent primary Fe oxides. Although the presence of
siderite (FeCO3) was noted by the authors, no detailed min-
eralogical description of the samples was provided and the
proportion of siderite in Manzimnyama samples is
unknown. Assuming the presence of siderite in their sam-
ples, the isotopic composition of Fe oxides could have been
underestimated and the O2 concentration of the photic zone
overestimated. This possibility could be easily tested by
determining siderite content in Manzimnyama samples
and compare the values to bulk Fe isotope compositions.
The present findings also imply that high sulfate concen-
tration in the ocean, necessary for bedded-barite deposi-
tion, was not produced by sustained oxic conditions in
the Mapepe paleo-environment. Part of the sulfate required
for BaSO4 precipitation could have been generated by mag-
matic SO2 disproportionation during hydrothermalism of
volcanic rocks (Gamo et al., 1997; Kusakabe et al., 2000)
but the extent of this process in the Archean remains
unknown (Holland, 1999; Bao et al., 2007). Instead, sulfate
may derive from SO2-OCS photolysis in an O2-poor atmo-
sphere, followed by hydrolysis of the chemical products
(Pavlov and Kasting, 2002; Huston and Logan, 2004). This
may have been promoted by enhanced subaerial volcanism
specifically during this early Archean period (Philippot
et al., 2012; Muller et al., 2016). Barium in seawater was
probably derived from hydrothermal alteration of mafic
and ultramafic rocks on the seafloor. The very low solubil-
ity of barite (Hannor, 2000) requires that Ba2+ and SO2
4
cannot be transported together in solution. We propose
that the oceanic basin was stratified, with sulfate-rich shal-
low water and barium-rich deep water. The size of these
two layers could have been controlled by the fluxes of sub-
aerial volcanic activity (SO2
4 flux to shallow water) and
hydrothermal circulation (Ba2+ flux to deep water). Barium
sulfate would have been precipitated at the boundary
between these shallow and deep waters until one of the
reservoirs was exhausted. An alternative to this model
would be that barium could be expelled by subaerial vol-
canic plume of dacitic to felsic magma and react rapidly
with sulfate aerosols in the atmosphere, producing
microparticles of barite (see Muller et al., 2016). These
insoluble microparticles would be transferred and accumu-
lated in sedimentary rocks. Following a model of enhanced
subaerial volcanism for explaining the increase in sulfate
concentrations in the basin, one would expect that the
influx of elemental S should also have been increased. This
could have resulted in abundant pyrite with the opposite
sign in D33S, but not necessarily in the same stratigraphic
level as the sulfate enrichments, in particular because trans-
port and preservation of these S isotope anomalies may be
decoupled, a feature very well-established for Archean sed-
imentary record (e.g. Farquhar and Wing, 2003). In the pre-
sent dataset, positive D33S values in pyrites were found in
one bedded barite sample from Mapepe, as well as in fer-
ruginous cherts (Fig. 6A). In situ S isotope studies of
Mapepe pyrites also identified positive D33S values and neg-
ative d34S in terrigenous and volcanoclastic sediments
(Philippot et al., 2012) and in some layered and massive
pyrite bands of barite-rich samples (Roerdink et al.,
2013). Finally, it is interesting to note that barite with pos-
itive D33S matching the sulfides with negative values were
detected in several bedded barite beds, although in small
quantities (Muller et al., 2016).
7. CONCLUSION
The occurrence of Early Archean barite deposits
requires high sulfate accumulation, thus raising the ques-
tion if free O2 was an important component of the atmo-
sphere/ocean system about 1 billion years before the
Great Oxidation Event. The crux of this issue lies in the
degree and complexity of the modifications experienced
by the rocks during diagenesis, metamorphism and
hydrothermal alteration processes.
Here, we combined Fe and S isotope analyses and major
element chemistry with detailed petrological work in order
 V. Busigny et al. / Geochimica et Cosmochimica Acta 210 (2017) 247–266
to distinguish primary signatures from post-depositional,
fluid-induced, overprint. This allowed us to determine reli-
able primary signature for Fe oxides, Fe carbonates and Fe
sulfides. A global model for Fe isotope geochemical cycle
suggests that O2 concentrations in the photic zone must
have been lower than 10
4 lmol/L during the chert deposi-
tion. The presence of mass-independent signature recorded
by S isotopes in barite and sulfide supports that the atmo-
sphere was also anoxic, with O2 < 0.001% of the present
atmospheric level (Pavlov and Kasting, 2002), thus indicat-
ing global anoxic conditions of the Archean ocean at
3.2 Ga. We conclude that barite deposit must have been
formed under anoxic conditions, probably related to a sul-
fate flux formed by photodissociation of abundant sub-
aerial volcanic gases.
ACKNOWLEDGMENTS
Colleagues from the Isotope Geochemistry Laboratories in
IPGP are thanked for fruitful discussions, particularly Wafa Abou-
chami, Magali Bonifacie and Emilie Thomassot. Pascale Louvat
and Julien Moureau are acknowledged for their technical assistance
for MC-ICP-MS analyses. Marc Quintin is thanked for making
thin sections of all samples. We highly appreciated the constructive
comments of four anonymous reviewers and the editor that helped
to improve the quality of the manuscript. This work was funded by
the National Program of Planetology (PNP) 2015 of the Institut
National des Sciences de l’Univers and the UnivEarths Labex pro-
gram at Sorbonne Paris Cité (ANR-10-LABX-0023 and ANR-11-
IDEX-0005-02).
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