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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
Jesu ´ s Martı´ nez-Frı´ asa,Ã, Antonio Delgado-Huertasb, Francisco Garcı´ a-Morenob, Emilio Reyesb, Rosario Lunarc, Fernando Rulla,d
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 ´n Experimental del Zaidı ´n (CSIC), Prof. Albareda 1, 18008 Granada, Spain Department of Earth Sciences and Environmental Chemistry, Estacio c ´a, Facultad de C.C. Geolo ´gicas, Universidad Complutense de Madrid, 28040 Madrid, Spain Departamento de Cristalografia y Mineralogı d ´a y Mineralogia, Unidad Asociada CSIC-Universidad de Valladolid, Valladolid, 47006, Spain Cristalografı Received 20 February 2006; received in revised form 29 May 2006; accepted 14 September 2006 Available online 15 November 2006
a

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 The discovery of deep-sea hydrothermal vents, in the late 1970s, opened a window into mostly unknown and unexplored geosphere and biosphere. Undersea hydrothermal 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
ÃCorresponding author. Tel.: +34 91 5206418; fax: +34 91 5201621.

E-mail address: [email protected] (J. Martı´ nez-Frı´ as). 0032-0633/$ - see front matter r 2006 Elsevier Ltd. All rights reserved. doi:10.1016/j.pss.2006.09.004

(base and precious metal sulphides and sulphosalts, 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 hydrocarbon 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

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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 biomineralization 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 geomarkers 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 ironbearing mineral called jarosite in the set of rocks dubbed ‘‘El Capitan.’’ in Mars’ Meridiani Planum (Squyres et al., 2004; Klingelho ¨ fer 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; Martı´ nez-Frı´ as, 1999), and the Jaroso Hydrothermal System (JHS) has been recently proposed as a possible

terrestrial geodynamic model of astrobiological relevance (Martı´ nez-Frı´ as et al., 2004; Rull et al., 2004, 2005; Grymes and Briggs, 2005; Martı´ nez-Frı´ as 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 processes 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 (Martı´ nez-Frı´ as 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 relationships 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 Martı´ nez-Frı´ as 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

Fig. 1. General view of the Jaroso ravine (Almeria province, Spain), world type locality of jarosite. Note the remains of old mining buildings.

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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 (Martı´ nez-Frı´ as et al., 1993); (b) ‘‘Almagrera–Herrerias’’ system, Navarro and Virto, 1994); Aguilas-Sierra Almagrera hydrothermal deposits (Morales, 1994; Morales et al., 1995). Recently it has been more unambiguously named as JHS (Martı´ nez-Frı´ as et al., 2004), given that the Jaroso vein (Pb, Ag) of Sierra Almagrera, discovered in 1838 with around 58,000 ton of minable ore, was the main cause which motivated the spectacular apogee of the mining of the area (Madoz, 1847) and, without doubt, constitutes the most significant historical and metallogenetic feature that characterizes the whole mining district. In addition, as previously defined, the Jaroso Ravine (Fig. 1) is the locality where jarosite was firstly discovered and characterized on Earth in 1852 (Amar de la Torre, 1852). Also it is a peculiar geological site of the region, which typifies, given such mineralogical singularity, the designation of the region as Natural Area (Martı´ nez-Frı´ as, 1999). All mineral deposits originated by the JHS make up a metallogenetic belt of hydrothermal mineralizations, of upper Tortonian–upper Messinian age, which extends roughly 50 km SW–NE, from Cabo de Gata region (Almeria province) (Delgado & Reyes, 1996) to the Aguilas area (Murcia province) (De Baranda et al., 2003). Morphologically, the deposits are polymetallic veins and hydrothermal breccias hosted in the Permian-Triassic basement and locally in the Neogene volcanic edifices (Martı´ nez-Frı´ as, 1991; Morales, 1994; Martı´ nez-Frı´ as et al., 1997; Carrillo-Rosu ´ a et al., 2003; Carrillo-Rosu ´ a, 2005) and stratabound ores hosted in Upper Miocene, shallow-marine sandy marls (Martı´ nez-Frı´ as 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 oxyhydroxides (e.g. hematite), gold, silver, Hg–Sb, and basemetal sulfides and different types of sulfosalts (mainly rich in Ag and Sb) (Martı´ nez-Frı´ as et al., 1989; Martı´ nez-Frı´ as, 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 calcalkaline 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

0 -1 -2 -3 -4 -5 0
Calcite

δ ‰ (V-PDB)

-1 -2 -3 -4 -5 -6 0 -1 -2 -3 -4 -5 -6 -7 -8 -9 -10

δ13C ‰ (V-PDB)

Ankerite
18 δ O ‰ (V-PDB)

Siderite

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 (Martı´ nez-Frı´ as et al., 1992). Morphologically 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

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 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

Samples

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recrystallized bodies (scarce), in which the sandy marls suffered an intense mineralogical and textural transformation and a strong silica cementing (Martı´ nez-Frı´ as 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). Isotope measurements were carried out at the Stable ´ n Experimental del Isotope Laboratory of the Estacio Zaidı´ n (CSIC, Granada). For isotopic measurements, all samples were ground to o200 mesh to be later treated with 100% phosphoric (McCrea, 1950). Those samples containing calcite–ankerite–siderite carbonates, either as major, minor or trace component were also treated according to the Al-Aasm et al.’s (1990) method. This method essentially consists in five steps: (1) obtention of CO2 from calcite, after a 2 h reaction with phosphoric acid at 25 1C; (2) elimination of CO2 from residual calcite and small amount from ankerite carbonates, after reaction between the insoluble residue and phosphoric acid, during 24 h; (3) obtention of CO2 from ankerite, after a 4 h reaction with phosphoric acid at 50 1C; (4) elimination of CO2 from residual ankerite and small amount from siderite, after reaction between the insoluble residue and phosphoric acid, during 24 h at 50 1C; and (5) obtention of CO2 from 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. Each core sample was analyzed, at least, three times. The experimental error found was 70.1% for (d13C and d18O), using Carrara and EEZ-1 internal standards, previously compared with NBS-18 and NBS-19 and the experimental reproducibility error was 70.2% for the samples. 2.3. Results and discussion d18O calcite values range between À6% and À1.9% (VPDB) (Fig. 4). Considering a marine water source (above 0% V-SMOW), these values are typical of low temperature hydrothermal environments. Formation water, usually more positive, involve higher temperatures. d13C calcite values range between À4.1 and À1.9% (V-PDB) (Fig. 4). This values are, however, relatively negatives for marine water (Anderson and Arthur, 1983). As previously defined, the geodynamic model for this specific area indicates that 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

GA-B-1

GA-B-3

GA-B-4

GA-B-5

GA-B-6

GA-B-7

GA-B-2

Samples
Fig. 3. Chimney B (GA-B). Sampling and stable isotope variations from the central orifice to the outer rim.

shape. However, the special geodynamic and metallogenetic features of the JHS, the mineralogical and geochemical differences of the vent structures with respect to those found in the mud volcanoes and, as it will be later shown, the conspicuous lack of a methanogenic signature indicates the singularity and uniqueness of the JHS chimneys. Three types of vent structures have been observed: (1) ‘‘pores’’ of millimetric size dispersed throughout the marls affected by the vent activity; (2) small cross-fractures, of NS and N20-25 W strike, with maximum width and length of 10 cm and 2 m, respectively; and (3) small tubes and concentric circular chimneys (up to 11 rings), whose diameters vary from 5 to 50 cm. These structures preserve even the central orifice (see Figs. 2 and 3) which served as the conduit for the hydrothermal fluids. Sometimes, they stand out above the marls some 10 cm, opening upwards in the form of a ‘‘mushroom’’. Among this last type of vent structures, two textural subtypes can be distinguished: (a) bodies with partial recrystallization and alternating hard and soft concentric bands (abundant), and (b) totally

GA-B-8

0 -1 -2 -3 -4 -5 -6 -7 0 -1 -2 -3 -4 -5 -6 -7

Calcite

δ ‰ (V-PDB)

δ13C ‰ (V-PDB) Ankerite

δ18O ‰ (V-PDB)

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4 2 δ13C ‰ (V-PDB) 0 -2 -4 -6 -8 -10 -16

Calcite Ch-A Ankerite Ch-A Siderite Ch-A Calcite Ch-B Ankerite Ch-B Siderite (Ore Dep.)

Meteoric water 130 120 110 100 90 80 70 60 50 40 30 20 10 0 -12

Marine water Formation water

Temperature (°C)

e erit Sid dep.) e (Or

e Sid

rite

Ch

-A

An

ke

rite

calc

ite

-14

-12

-10

-8

-6

-4

-2

0

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.

-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 À6% V-PDB) were used to calculate the most negatives d18O values of the meteoric waters (À6.1 to À4% 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.

occurred. The negative d13C carbon isotopic source can be congruent with magmatic contribution (typically about À6% V-PDB) or meteoric water (ranging from À6 to À12% 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 (À6% to À4% 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 À2.2 and À0.35% (V-PDB) which are closed to the typical marine water. d18O values range, in most samples, between À5.2% and À4.3% (V-PDB) (see Fig. 4) indicating a diagenetichydrothermal low-temperature marine environment. This could be reflecting the existence of a marine diagenetic dolomitization background previous to the Fe-rich hydrothermal episode. This is also mineralogically supported as

ankerite was identified both in the chimneys and the marly substrate (Martı´ nez-Frı´ as, 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 À8.9 and À6.2% (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 À9.1% and À7% (V-PDB), indicating 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 À8% (V-PDB) and À10.3% (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,

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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 precipitated 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 precipitates, 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 substrate. 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 hydrothermal chimneys themselves; (2) the geodynamic peculiarities 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 hopefully 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

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Hochberg for the revision of the English version. Also thanks to three anonymous referees for their extremely useful remarks which greatly improved the original manuscript.

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