ARTICLE IN PRESS

Planetary and Space Science 55 (2007) 441–448

www.elsevier.com/locate/pss

Isotopic signatures of extinct low-temperature hydrothermal chimneys

in the Jaroso Mars analog
Jesús Martı́nez-Frı́asa,, Antonio Delgado-Huertasb, Francisco Garcı́a-Morenob,
Emilio Reyesb, Rosario Lunarc, Fernando Rulla,d
a
Planetary Geology Laboratory, Centro de Astrobiologia (CSIC-INTA), associated to the NASA Astrobiology Institute,
Ctra de Ajalvir, km 4, 28850 Torrejon de Ardoz, Madrid, Spain
b
Department of Earth Sciences and Environmental Chemistry, Estación Experimental del Zaidı´n (CSIC), Prof. Albareda 1, 18008 Granada, Spain
c
Departamento de Cristalografia y Mineralogı´a, Facultad de C.C. Geológicas, Universidad Complutense de Madrid, 28040 Madrid, Spain
d
Cristalografı´a y Mineralogia, Unidad Asociada CSIC-Universidad de Valladolid, Valladolid, 47006, Spain
Received 20 February 2006; received in revised form 29 May 2006; accepted 14 September 2006
Available online 15 November 2006

Abstract

The present work presents a geochemical study, focused on the oxygen and carbon isotopic signatures of shallow-marine, carbonate
extinct chimneys, from Jaroso Hydrothermal System (JHS). In each chimney a meticulous sampling from the central orifice to the outer
rim of the structure was performed. The isotopic geochemistry study allowed to establish the origin and evolution of the fluids during the
formation of the vent structures. The negative d13C values indicate a source of meteoric water for the Fe-rich fluids. More positive d13C
values are present in ankerite and in some calcite, both related with marine water. d18O in ankerite indicates low-temperature
hydrothermal conditions, while in calcite is showing either primary signatures or early diagenesis at low temperature. On the contrary,
calcite displaying more negative d13C and d18O values represents a late mineral phase which was formed under meteoric diagenesis. Each
chimney resulted from the precipitation of intergranular carbonate cement around a channellized flux of metal-rich fluid crossing a
shallow-marine, unconsolidated, sandy-marl substrate. The paleoenvironmental interpretation carried out from the isotopic data
emphasizes the importance of the stable isotopes as fluid geomarkers, also advancing in the understanding of an interesting analog for
the geological and astrobiological exploration of Mars.
r 2006 Elsevier Ltd. All rights reserved.

Keywords: Oxygen; Carbon; Isotopes; Hydrothermal; Jarosite; Mars

1. Introduction (base and precious metal sulphides and sulphosalts,

The discovery of deep-sea hydrothermal vents, in the late
1970s, opened a window into mostly unknown and
unexplored geosphere and biosphere. Undersea hydrother-
mal vents are singular sites where hot, metal-bearing
hydrothermal solutions, that have been convected through
newly formed volcanic (mainly basaltic) crust, are exhaled
onto the sea floor. On exhalation, these fluids interact with
sediments and rocks and precipitate their metallic load to
form a wide variety of edifices, mounds and venting
structures displaying a wide typological variety of minerals
Corresponding author. Tel.: +34 91 5206418; fax: +34 91 5201621.
E-mail address: martinezfrias@mncn.csic.es (J. Martı́nez-Frı́as).
carbonates, sulphates, oxides, oxi-hydroxides, etc.) and
complex parageneses) (Rona and Scott, 1993; Herzig and
Hannington, 1995; Humphris et al., 1995; Barnes, 1997;
Herzig and Petersen, 2002; Rona, 2003, among others).
Today, more than 30 years after its discovery, we know
that modern hydrothermal vent environments (and hydro-
carbon seeps) are located at characteristic geotectonic,
geochemical and biological interfaces where H2S- and CH4
rich fluids are discharged at the seafloor, sustaining
abundant chemosynthetic ecosystems (ChEss program,
http://www.noc.soton.ac.uk/chess/). In addition, it is
broadly accepted that these undersea venting episodes:
(1) contributed, through the evolution of the earth, to
nearly continuous fluid–rock interaction processes, (2) were

0032-0633/$ - see front matter r 2006 Elsevier Ltd. All rights reserved.
doi:10.1016/j.pss.2006.09.004
 ARTICLE IN PRESS
442 J. Martı´nez-Frı´as et al. / Planetary and Space Science 55 (2007) 441–448
particularly remarkable in relation with the behaviour and
geochemical cycle of some elements and minerals (oxides
and oxi-hydroxides, sulfides, sulfates), mainly iron and
metal sulfides (Schoonen et al., 2004), and (3) revealed a
new world related with the origin of life and biominer-
alization processes (Fortin et al., 1998) (for instance,
certain bacteria such as Leptothrix and Gallionella
precipitate ferrihydrite, an amorphous iron oxyhydroxide).
All these new findings have changed our viewpoints about
fluid geodynamics, building mechanisms of new submarine
structures, microbial metabolism and survivability under
extremophilic conditions, biological origins, etc. But also
they have deeply introduced new questions about the
physical and chemical limits to life (Prieur et al., 1995), and
how this knowledge can be used to find out terrestrial
analogues for searching Mars and other further planetary
bodies of the solar system (e.g. Europa, Titan).
Considering the importance of defining bio and geo-
markers at selected terrestrial areas, which allow to
determine the formation conditions and their evolution
for later extrapolation to the geological and astrobiological
exploration of Mars, the present work presents a detailed
geochemical study, focused on the oxygen and carbon
isotopic signatures of shallow-marine, carbonate extinct
chimneys (which still are ‘‘in situ’’) from Jaroso (SE Spain).
The Mars Exploration Rover Opportunity’s Moessbauer
spectrometer, showed in 2004 the presence of an iron-
bearing mineral called jarosite in the set of rocks dubbed
‘‘El Capitan.’’ in Mars’ Meridiani Planum (Squyres et al.,
2004; Klingelhöfer et al., 2004; Madden et al., 2004;
Christensen et al., 2004). ‘‘El Capitan’’ is located within the
rock outcrop that lines the inner edge of the small crater
where Opportunity landed. The Jaroso Ravine (Fig. 1) is
the world type locality of jarosite (Amar de la Torre, 1852;
Martı́nez-Frı́as, 1999), and the Jaroso Hydrothermal
System (JHS) has been recently proposed as a possible
Fig. 1. General view of the Jaroso ravine (Almeria province, Spain), world type locality of jarosite. Note the remains of old mining buildings.
terrestrial geodynamic model of astrobiological relevance
(Martı́nez-Frı́as et al., 2004; Rull et al., 2004, 2005; Grymes
and Briggs, 2005; Martı́nez-Frı́as et al., 2006).
2. The JHS vent chimneys
2.1. Geodynamic framework and mineralizing processes
The SE Mediterranean margin of Spain is an extremely
interesting area of synchronous interaction of tectonic,
volcanic, evaporitic and mineralizing hydrothermal pro-
cesses during the Upper Miocene. Considering this
peculiarity, some previous works had suggested the
significance of this Mediterranean area as a relevant
geodynamic and metallogenetic model to follow (Martı́-
nez-Frı́as et al., 2000, 2001). Geodynamically, a ‘‘Basin and
Range-type’’ model has been proposed for this sector of the
southeast Iberian margin (Lopez Gutierrez et al., 1993a,b)
to explain the morphology of high zones (Sierras) and
depressed zones (basin) as well as the structural relation-
ships between the volcanic and mineralizing hydrothermal
processes. According to this model, the Sierras acted as
recharge zones for meteoric waters while the discharge
took place in the basin zones, where a mixture of meteoric,
marine and magmatic waters occurred. For instance, Las
Herrerias trough inside the Vera-Garrucha Basin is
controlled by both NNE-SSW and N150E normal faults
and WNW-ESE reverse faults. The scheme of fluid
circulation proposed by Martı́nez-Frı́as et al. (1993) fits
this structural scheme well. The convective movements of
the mineralising fluids would have been conducted by the
Upper Miocene magmatic source which, as previously
defined, is spatially and temporally associated with the
mineralising hydrothermal system. In accordance with
Lopez Ruiz and Rodriguez Badiola (1980) and Bellon
et al. (1964, 1983) the first magmatic events began in the
 ARTICLE IN PRESS
J. Martı´nez-Frı´as et al. / Planetary and Space Science 55 (2007) 441–448 443

late-Burdigalian/early-Langhian with the generation of the

calc-alkaline rocks, continued with the simultaneous
extrusion of the calc-alkaline, K-rich calc-alkaline and
shoshonitic rocks, and ended in the Messinian with the
emplacement of the ultrapotassic rocks. The second
episode began 2 Ma later, with the generation of the
alkaline basalts.
The mineralizing hydrothermal system of this area has
received, as a whole, several local names: (a) Herrerias–
Almagrera–Almenara convective hydrothermal system
(Martı́nez-Frı́as et al., 1993); (b) ‘‘Almagrera–Herrerias’’
system, Navarro and Virto, 1994); Aguilas-Sierra Alma-
grera hydrothermal deposits (Morales, 1994; Morales et al.,
1995). Recently it has been more unambiguously named as
JHS (Martı́nez-Frı́as et al., 2004), given that the Jaroso
vein (Pb, Ag) of Sierra Almagrera, discovered in 1838 with
0
around 58,000 ton of minable ore, was the main cause
which motivated the spectacular apogee of the mining of -1 Calcite

the area (Madoz, 1847) and, without doubt, constitutes the -2

most significant historical and metallogenetic feature that
-3
characterizes the whole mining district. In addition, as
previously defined, the Jaroso Ravine (Fig. 1) is the locality -4
where jarosite was firstly discovered and characterized on -5
Earth in 1852 (Amar de la Torre, 1852). Also it is a peculiar 0
geological site of the region, which typifies, given such -1 δ13C ‰ (V-PDB)
δ ‰ (V-PDB)

mineralogical singularity, the designation of the region as -2

Natural Area (Martı́nez-Frı́as, 1999). Ankerite
-3
All mineral deposits originated by the JHS make up a
-4 18
δ O ‰ (V-PDB)
metallogenetic belt of hydrothermal mineralizations, of
-5
upper Tortonian–upper Messinian age, which extends
roughly 50 km SW–NE, from Cabo de Gata region -6
0
(Almeria province) (Delgado & Reyes, 1996) to the Aguilas -1
area (Murcia province) (De Baranda et al., 2003). -2
-3 Siderite
Morphologically, the deposits are polymetallic veins and -4
hydrothermal breccias hosted in the Permian-Triassic -5
-6
basement and locally in the Neogene volcanic edifices -7
(Martı́nez-Frı́as, 1991; Morales, 1994; Martı́nez-Frı́as -8
-9
et al., 1997; Carrillo-Rosúa et al., 2003; Carrillo-Rosúa, -10
GA-A-10
GA-A-11
GA-A-12
GA-A-13
GA-A-14
GA-A-15
GA-A-16
GA-A-17
GA-A-18
GA-A-19
GA-A-20
GA-A-21
GA-A-22
GA-A-1
GA-A-2
G-AA-3
GA-A-4
GA-A-5
GA-A-6
GA-A-7
GA-A-8
GA-A-9

2005) and stratabound ores hosted in Upper Miocene,

shallow-marine sandy marls (Martı́nez-Frı́as et al., 1993).
Paleobathymetry data offered by Montenat and Seilacher
(1978) for the time (Upper Miocene) of emplacement of the
hydrothermal fluids indicate an approximated depth of
200–300 m beneath the sea. The JHS includes oxy-
hydroxides (e.g. hematite), gold, silver, Hg–Sb, and base-
metal sulfides and different types of sulfosalts (mainly rich
in Ag and Sb) (Martı́nez-Frı́as et al., 1989; Martı́nez-Frı́as,
1991). Hydrothermal sulfuric acid weathering of the ores
has generated huge amounts of oxide and sulfate minerals
of which jarosite is the most abundant. It has been
proposed and generally accepted that the JHS is genetically
linked with the late episodes of the Upper Miocene calc-
alkaline and shoshonitic volcanism of the area. Additional
information about these volcanic rocks of SE Spain can be
found in Benito (1993) and Benito et al. (1999).
Some extinct undersea hydrothermal vent structures (see
Figs. 2 and 3), which are associated with the mineralizing
Samples
Fig. 2. Chimney A (GA-A). Sampling and stable isotope variations from
the central orifice to the outer rim. Note that siderite is not present where
ankerite (more stable phase) occurs.
process of the JHS, are still preserved ‘‘in situ’’ in the sandy
mars substrate (Figs. 2 and 3), constituting perfect targets
for carrying out the detailed isotopic analysis comparing
chimneys and marls (Martı́nez-Frı́as et al., 1992). Mor-
phologically these vent structures are similar (but much
smaller) to the typical ‘‘mud-volcanoes’’: a term which is
generally applied to the more or less violent eruption or
surfaces extrusion of watery mud or clay which almost
invariably is accompanied by methane gas, and which
commonly tends to build up a solid mud or clay deposit
around its orifice which may have a conical or volcano-like
 ARTICLE IN PRESS
444 J. Martı´nez-Frı´as et al. / Planetary and Space Science 55 (2007) 441–448

recrystallized bodies (scarce), in which the sandy marls

suffered an intense mineralogical and textural transforma-
tion and a strong silica cementing (Martı́nez-Frı́as et al.,
1992). The extraction of these vent structures from the
sandy marls substrate is extremely difficult given the labile
nature of the rocks, but we succeeded with two well
developed chimneys (chimneys GA-A and GA-B, Figs. 2
and 3).

2.2. Methodology

In each chimney a meticulous sampling from the central

orifice to the outer rim of the structure was performed.
Small cores were carefully extracted from each chimney by
a drilling process using a clean diamond-steel micro-drill
(see Figs. 2 and 3).
0
-1
Isotope measurements were carried out at the Stable
Calcite
-2 Isotope Laboratory of the Estación Experimental del
-3 Zaidı́n (CSIC, Granada). For isotopic measurements, all
-4 samples were ground to o200 mesh to be later treated with
-5 100% phosphoric (McCrea, 1950). Those samples contain-
δ ‰ (V-PDB)

-6 ing calcite–ankerite–siderite carbonates, either as major,

-7 minor or trace component were also treated according to
0
-1
the Al-Aasm et al.’s (1990) method. This method essen-
-2 δ13C ‰ (V-PDB)
tially consists in five steps: (1) obtention of CO2 from
-3 calcite, after a 2 h reaction with phosphoric acid at 25 1C;
Ankerite
-4 (2) elimination of CO2 from residual calcite and small
-5 amount from ankerite carbonates, after reaction between
δ18O ‰ (V-PDB)
-6 the insoluble residue and phosphoric acid, during 24 h; (3)
-7 obtention of CO2 from ankerite, after a 4 h reaction with
GA-B-1

GA-B-3

GA-B-4

GA-B-5

GA-B-6

GA-B-7

GA-B-8
GA-B-2

phosphoric acid at 50 1C; (4) elimination of CO2 from

residual ankerite and small amount from siderite, after
Samples
reaction between the insoluble residue and phosphoric
Fig. 3. Chimney B (GA-B). Sampling and stable isotope variations from acid, during 24 h at 50 1C; and (5) obtention of CO2 from
the central orifice to the outer rim. ankerite and/or siderite after 11 days reaction with
phosphoric acid at 50 1C. Carbon dioxide obtained was
analyzed using a Finnigan Mat 251 mass spectrometer.
shape. However, the special geodynamic and metalloge- Each core sample was analyzed, at least, three times. The
netic features of the JHS, the mineralogical and geochem- experimental error found was 70.1% for (d13C and d18O),
ical differences of the vent structures with respect to those using Carrara and EEZ-1 internal standards, previously
found in the mud volcanoes and, as it will be later shown, compared with NBS-18 and NBS-19 and the experimental
the conspicuous lack of a methanogenic signature indicates reproducibility error was 70.2% for the samples.
the singularity and uniqueness of the JHS chimneys.
Three types of vent structures have been observed: (1) 2.3. Results and discussion
‘‘pores’’ of millimetric size dispersed throughout the marls
affected by the vent activity; (2) small cross-fractures, of N- d18O calcite values range between 6% and 1.9% (V-
S and N20-25 W strike, with maximum width and length of PDB) (Fig. 4). Considering a marine water source (above
10 cm and 2 m, respectively; and (3) small tubes and 0% V-SMOW), these values are typical of low temperature
concentric circular chimneys (up to 11 rings), whose hydrothermal environments. Formation water, usually
diameters vary from 5 to 50 cm. These structures preserve more positive, involve higher temperatures. d13C calcite
even the central orifice (see Figs. 2 and 3) which served as values range between 4.1 and 1.9% (V-PDB) (Fig. 4).
the conduit for the hydrothermal fluids. Sometimes, they This values are, however, relatively negatives for marine
stand out above the marls some 10 cm, opening upwards in water (Anderson and Arthur, 1983). As previously defined,
the form of a ‘‘mushroom’’. Among this last type of vent the geodynamic model for this specific area indicates that
structures, two textural subtypes can be distinguished: (a) Sierras acted as recharge zones for meteoric waters while
bodies with partial recrystallization and alternating hard the discharge took place in the basin zones, where a
and soft concentric bands (abundant), and (b) totally mixture of meteoric, marine and magmatic waters
 ARTICLE IN PRESS
J. Martı´nez-Frı´as et al. / Planetary and Space Science 55 (2007) 441–448 445

Marine water
4 Calcite Ch-A Meteoric
Ankerite Ch-A water Formation water
2 Siderite Ch-A 130
Calcite Ch-B 120
δ13C ‰ (V-PDB)

0
Ankerite Ch-B 110
-2 Siderite (Ore Dep.) 100 -A
Ch
90 erit
e rite

-4
-6
-8
-10
-16 -14 -12 -10 -8 -6 -4 -2
δ18O ‰ (V-PDB)
Fig. 4. Stable isotopes in carbonates indicate that siderite mineralization,
related with the genesis of the ore deposit, is a general residual processes in
the area. Ankerite represents a well defined hydrothermal event related
with the formation of the chimneys. However, calcite indicates a physical
mixing of marine and meteoric (re-crystallization) calcites.
occurred. The negative d13C carbon isotopic source can be
congruent with magmatic contribution (typically about
6% V-PDB) or meteoric water (ranging from 6 to
12% V-PDB). However, the correlation between d18O
and d13C suggests three possibilities: (a) an increase of
temperature (more negative values of d18O) linked to a
more significant contribution of magmatic waters (more
negative values of d13C); (b) an increase of the role of the
meteoric waters in the system (more negative d18O and
d13C), and (c) a mixing of marine and meteoric calcites
formed under typical low temperature surficial conditions.
Nevertheless, a higher contribution of magmatic water
would involve more positive d18O water for a same certain
range of temperatures. Only a strong increasing of the
temperature could justify the more negative values of d18O.
The projection of the experimental values in the plot
temperature versus d18O fluid (Fig. 5) strongly points out
equilibrium between marine water and surficial water
(15–25 1C). Likewise, the most negative values would be
indicating equilibrium between meteoric water (6% to
4% V-SMOW) in consonance with the later, regressive
(subaerial) conditions. This is in agreement with the
isotopic calculations determined, for the Upper Miocene,
by Delgado and Reyes (1996) using hydrogen and oxygen
in clay minerals from the close bentonite deposit at C. de
Archidona (160 m asl.; 200 90 0000 W, 3600 520 3000 N).
Isotopic composition of ankerite is constrained in a
narrow range. d13C values range between 2.2 and
0.35% (V-PDB) which are closed to the typical marine
water. d18O values range, in most samples, between 5.2%
and 4.3% (V-PDB) (see Fig. 4) indicating a diagenetic-
hydrothermal low-temperature marine environment. This
could be reflecting the existence of a marine diagenetic
dolomitization background previous to the Fe-rich hydro-
thermal episode. This is also mineralogically supported as
Temperature (°C)
Sid dep.) e rite
e Sid An
ke
80 (Or
70
60
50 ite
calc
40
30
0 20
10
0
-12 -10 -8 -6 -4 -2 0 2 4
δ18O ‰ (V-SMOW) fluid
Fig. 5. Diagram showing temperature and d18O (V-SMOW) values of
waters. The curves represent the theoretical temperature of carbonates in
equilibrium with different types of waters. Surficial temperatures
(15–25 1C, horizontal dotted line) and the most negatives values of calcite
(d18O ¼ 6% V-PDB) were used to calculate the most negatives d18O
values of the meteoric waters (6.1 to 4% vs V-SMOW). These values
indicate that even carbonatic phases with meteoric influence (relatively
negatives d13C values in Fig. 4) have a low temperature hydrothermal or
diagenetic origin with minimal temperatures ranging between 29 and
43 1C; the enrichment in 18O due to water–rock interaction or contribution
of marine or magmatic waters implicates higher temperatures. The O’Neil
et al. (1969), Sheppar and Schwarcz (1970) and Carothers et al. (1988)
equations for the systems calcite-water, ankerite-water and siderite-water,
respectively, were used for the temperature calculation.
ankerite was identified both in the chimneys and the marly
substrate (Martı́nez-Frı́as, 1993). Considering a marine
water of 0% (V-SMOW) these values are typical of low
temperature hydrothermal environments (around 60 1C,
see Fig. 5).
Ankerite and siderite are the main minerals representing
the vent emission of the fluids. d13C values range between
8.9 and 6.2% (V-PDB) which are typical of meteoric
water. These values are slightly more negative that the
typical depth carbon (Hoefs, 1973; Rollinson, 1993). d18O
values range between 9.1% and 7% (V-PDB), indicat-
ing low hydrothermal temperatures, which range from 30
to 60 1C (considering the most negative meteoric waters).
However, d18O enrichment due to water–rock interaction
points out higher temperatures.
Finally, the siderite from the massive mineralization
(adjacent 300 m to this chimney outcrop) displays d13C and
d18O values around 8% (V-PDB) and 10.3% (V-PDB).
These values are concordant with meteoric water and low
temperature hydrothermal conditions (Fig. 5).
3. Discussion and conclusions
Various authors (such as Jakosky, 1997; Farmer, 2000;
Christensen et al., 2000; Urquhart and Gulick, 2003,
 ARTICLE IN PRESS
446 J. Martı´nez-Frı´as et al. / Planetary and Space Science 55 (2007) 441–448
among others) have proposed that hydrothermal systems
may have operated beneath the Martian surface at
some time during the planet’s history. More specifically,
it had already been suggested that jarosite, hematite
and/or ferrihydrite, maghemite and/or magnetite could be
produced on Mars via hydrothermal processes (Bishop,
1999). At Meridiani Planum the presence of jarosite
indicates, in accordance with King and McSween (2005)
that the solutions were oxidized with pHo4.5. The
solutions were likely Fe–Mg–(Ca)–SO4–(Cl)-rich and pre-
cipitated Fe (hydro) oxides, Fe phosphates, Fe sulfates
with low OH/(OH+SO4), Ca–Mg sulfates, and possible
halides, along with Si-rich phases. Recently, it has been
proposed that the formation of sulfate minerals and
hydrated phases on Mars does not require long-term
aqueous processes (Bishop et al., 2005). After studying the
Kilauea caldera, these authors suggest that solfataric
alteration may have played a role in sulfate mineralization
on Mars. Fumaroles in this caldera have created a
solfataric bank on the south wall of the crater where
Keanakakoi ash was deposited. A combination of jarosite
and gypsum in a silica/clay matrix is observed here. Similar
processes may have occurred on Mars if hydrothermal
processes existed.
More recently, Golden et al. (2005) weathered basaltic
materials (olivine-rich glassy basaltic sand and plagioclase
feldspar-rich basaltic tephra) in the laboratory under
different oxidative, acid–sulfate conditions (Burns and
Fisher, 1990) and characterized the alteration products. On
the basis of their experiments, they suggested that jarosite
formation in Meridiani outcrop is a potential evidence for
an open system acid–sulfate weathering regime. Thus,
aqueous alteration of outcrops and rocks on the Martian
West Spur of the Columbia Hills may have occurred when
vapors rich in SO2 from volcanic sources reacted with
volcanic rocks. In a similar ‘‘hydrothermal’’ line of
discussion, Zolotov and Shock (2005) propose that
regional heating in the Meridiani Planum caused a release
of sulfide-rich hydrothermal waters, leading to formation
of pyrite-rich regional deposits in a depression. Aqueous
oxidation of these deposits by atmospheric O2 created an
acidic environment that allowed formation of sulfates and
goethite. A model is developed to explain the widespread
deposition of sulfates on Mars as hydrothermal precipi-
tates, generated through the interaction of magmatic H2S
in hydrothermal solutions with water in the cryosphere.
Pirajno and Von Kranendonk (2005) go even further
developing a model to explain the widespread deposition of
sulfates on Mars as hydrothermal precipitates, generated
through the interaction of magmatic H2S in hydrothermal
solutions with water in the cryosphere.
As stated before, jarosite was first characterized on Earth
in Spain in the hydrothermal area of Jaroso. The JHS has
resulted to be a volcanism-related hydrothermal system, in
which saline Cl-rich hydrothermal fluids (Lopez-Gutierrez
et al., 1993a,b), dominated by the precipitation of sulfates
(mainly jarosite and also halotrichite, Frost et al., 2005),
were responsible for the formation and emplacement of the
mineralization.
The detailed isotopic geochemistry study of the JHS
chimneys has allowed determining the origin and evolution
of the fluids during the formation of the vent structures.
The negative d13C values indicate a source of meteoric
water for the Fe-rich fluids. More positive d13C values are
present in ankerite and in some calcite, both related with
marine water. d18O in ankerite indicates hydrothermal
conditions, while in calcite is showing either primary
signatures or early diagenesis at low temperature. On the
contrary, calcite displaying more negative d13C and d18O
values represents a late mineral phase which was formed
under meteoric diagenesis. It can be said that each chimney
resulted from the precipitation of intergranular carbonate
cement around a channellized flux of metal-rich fluid
crossing shallow-marine, unconsolidated, sandy-marl sub-
strate. Chemical interactions between JHS vent fluids and
the sediments accelerated recrystallization process. The
metal content of the vent fluids was also incorporated, in a
certain way, to the very chimneys as evidenced by the
geochemical anomalies in some elements which are related
with the mineralizing process.
Considering (1) the rareness of the carbonate hydro-
thermal chimneys themselves; (2) the geodynamic peculia-
rities of the JHS and the clear mineralogical and
geochemical differences of the structures with respect to
other ancient and modern carbonate chimneys (Lost City,
Monterey, Monferrato, Mariana seamount, Guaymas
basin, Gulf of California, Gulf of Cadiz, among others
(Kelley et al., 2001; Von Damm, 2001; Stakes et al., 1999;
Teske et al., 2002; Campbell et al., 2002; Clari et al., 2004;
Kelley et al., 2005; Diaz-del-Rio et al., 2003; Merinero,
2005) and (3) the reasonably good degree of preservation of
the vent structures, the JHS chimneys can be considered
unique reflecting the last, low-temperature hydrothermal
episode (Upper Messinian) associated with the JHS.
The paleoenvironmental interpretation carried out from
the isotopic data presented here: (a) is geochemically
reflecting the geodynamic model proposed for the area. It is
important to note that, gypsum, which is also present in the
JHS, has also been unambiguously detected by OMEGA/
Mars Express on Mars (Langevin et al., 2005). This
emphasizes: (1) the importance of the stable isotopes as
geomarkers; (2) contributes to the knowledge of how were
the fluid–rock interaction processes; (3) helps to determine
the behavior of some elements associated with the
mineralization in which jarosite is a chief mineral, and (4)
permits us to advance one more step for the understanding
of the JHS: an extremely interesting analog which hope-
fully can be useful for the geological and astrobiological
exploration of Mars.
Acknowledgements
We wish to acknowledge the institutional support of the
Centro de Astrobiologia. Special thanks to Dr. David
 ARTICLE IN PRESS
J. Martı´nez-Frı´as et al. / Planetary and Space Science 55 (2007) 441–448
Hochberg for the revision of the English version. Also
thanks to three anonymous referees for their extremely
useful remarks which greatly improved the original manu-
script.
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