Isotopic signatures of extinct low-temperature hydrothermal
chimneys in the Jaroso Mars analog
Jesús Martinez-Friasa*, Antonio Delgado-Huertasb , Francisco García-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 Zaidín (CSIC), Prof.
Albareda 1, 18008 Granada, Spain
c Departamento de Cristalografia y Mineralogía, Facultad de C.C. Geológicas, Universidad Complutense de Madrid,
28040 Madrid, Spain
d Cristalografía y Mineralogia, Unidad Asociada CSIC-Universidad de Valladolid,
Valladolid, 47006, Spain
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 δ13C values indicate a source of meteoric water for the Ferich fluids. More positive δ13C values are present in ankerite and in some calcite, both
related with marine water. δ18O 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 δ13C and δ18O 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, sandymarl 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.
Keywords: oxygen, carbon, isotopes, hydrothermal, jarosite, Mars
* corresponding author: Tel.: +34-91-5206418; fax: +34-915201621
E-mail address: martinezfrias@mncn.csic.es (J. Martinez-Frias)
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 (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 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 sulphides
(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 iron-bearing mineral called jarosite in
the set of rocks dubbed "El Capitan." in Mars' Meridiani Planum (Squyres et. al., 2004;
Klingelhofer 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; Martinez-Frias, 1999), and the Jaroso Hydrothermal System
(JHS) has been recently proposed as a possible terrestrial geodynamic model of
astrobiological relevance (Martinez-Frias et al., 2004; Rull et al., 2004, 2005, Grymes
and Briggs, 2005).
2. The JHS vent chimneys
2.1. Geodynamic framework and mineralization process
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 (Martinez-Frias 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., 1993) to explain the morphology of high zones
(Sierras) and depressed zones (basin) as well as the structural relationships between the
volcanic and mineralizating 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 Martinez-Frias 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., (1983) the first magmatic
events began in the Late-Burdigalian/Early-Langhian with the generation of the calcalkaline 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
(Martinez-Frias et al., 1993); b) “Almagrera-Herrerias” system, Navarro & Virto, 1994);
Aguilas-Sierra Almagrera hydrothermal deposits (Morales, 1994, Morales et al., 1995).
Recently it has been more unambiguously named as “Jaroso Hydrothermal System”
(JHS) (Martinez-Frias et al., 2004), given that the Jaroso vein (Pb,Ag) of Sierra
Almagrera, discovered in 1838 with around 58,000 t 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 (Martinez-Frias, 1999).
All mineral deposits originated by the JHS make up a metallogenetic belt of
hydrothermal mineralizations 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 (Martinez-Frias 1991, Morales 1994, Martinez-Frias et
al., 1997, Carrillo-Rosúa et al., 2003, Carrillo-Rosúa 2005) and stratabound ores hosted
in Upper Miocene, shallow-marine sandy marls (Martinez-Frias et al., 1993).
Paleobathymetry data offered by Montenat & 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 sulphosalts (mainly rich in
Ag and Sb) (Martinez-Frias et al., 1989; Martinez-Frias, 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.
Some extinct undersea hydrothermal vent structures (see figures 2 and 3), which
are associated with the mineralizing 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 (Martínez-Frías et al., 1992).
Morphologically these vent structures are similar (but much smaller) to the the typical
"mud-volcanos": 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 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 crossfractures, of N-S and N20-25W 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 figures 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 recrystallisation and alternating hard and soft
concentric bands (abundant), and b) totally recrystallised bodies (scarce), in which the
sandy marls suffered an intense mineralogical and textural transformation and a strong
silica cementing (Martínez-Frías 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 (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 figures 2 and 3).
Isotope measurements were carried out at the Stable Isotope Laboratory of the
Estación Experimental del Zaidín (CSIC, Granada). For isotopic measurements, all
samples were ground to <200 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´s et al., (1990)
method. This method essentially consists in three steps: 1) obtention of CO2 from
calcite, after a 2hr reaction with phosphoric acid at 25ºC; 2) elimination of CO2 from
residual calcite and small amount from ankerite carbonates, after reaction between the
insoluble residue and phosphoric acid, during 24hr; and 3) obtention of CO2 from
ankerite, after a 4hr reaction with phosphoric acid at 50ºC; 4) elimination of CO2 from
residual ankerite and small amount from siderite, after reaction between the insoluble
residue and phosphoric acid, during 24hr at 50ºC; and 5) obtention of CO2 from ankerite
and/or siderite after 11 days reaction with phosphoric acid at 50ºC. 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 ± 0.1‰ for (δ13C
and δ18O), using Carrara and EEZ-1 internal standards, previously compared with NBS18 and NBS-19 and the experimental reproducibility error was ± 0.2‰ for the samples.
2.3 Results and discussion
δ18O calcite values range between -6‰ and -1.9 ‰ (V-PDB) (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. δ13C calcite values range between -4.1 and -1.9 ‰ (VPDB) (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 occurred. The negative δ13C carbon source isotopic 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 δ18O and δ13C suggests
three possibilities: a) an increase of temperature (more negative values of δ18O) linked
to a more significant contribution of magmatic waters (more negative values of δ13C); b)
an increase of the role of the meteoric waters in the system (more negative δ18O and
δ13C), 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 δ18O water for a same certain range of temperatures. Only
a strong increasing of the temperature could justify the more negative values of δ18O.
The projection of the experimental values in the plot temperature versus δ18O fluid
(Fig.5) strongly points out equilibrium between marine water and surficial water (1525ºC). 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 & Reyes (1996) using hydrogen and oxygen in
clay minerals.
Isotopic composition of ankerite is constrained in a narrow range. δ13C values
range between -2.2 and -0.35 ‰ (V-PDB) which are closed to the typical marine water.
δ18O values range, in most samples, between -5.2‰ and -4.3‰ (V-PDB) (see figure 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 hydrothermal episode. This is also mineralogically supported as ankerite
was identified both in the chimneys and the marly substrate (Martinez-Frias, 1993).
Considering a marine water of 0 ‰ (V-SMOW) these values are typical of low
temperature hydrothermal environments (around 60ºC, see figure 5).
Ankerite and siderite are the main minerals representing the vent emission of the
fluids. δ13C 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). δ18O values range between -9.1‰ and -7‰ (V-PDB),
indicating low hydrothermal temperatures, which range from 30 to 60ºC (considering
the most negative meteoric waters). However, 18O 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 δ13C and δ18O values around -8‰ (V-PDB) and -10.3 ‰ (VPDB). These values are concordant with meteoric water and low temperature
hydrothermal conditions (Fig. 5).
Discussion and conclusions
Various authors (such as Jakosky, 1997; Farmer, 2000; Christensen et al., 2000;
Urquhart and Gulick, 2003, 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 pH <
4.5. 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 and characterized the alteration
products. On the basis of their experiments, they suggested that jarosite formation in
Meridiani outcrop is 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 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, dominated by the
precipitation of sulphates (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 δ13C values indicate a source of meteoric water for the Fe-rich
fluids. More positive δ13C values are present in ankerite and in some calcite, both
related with marine water. δ18O 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 δ13C and δ18O 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, sandymarl 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, Claril 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.
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 the importance of the stable isotopes as geomarkers; 2) contributes to
the knowledge of how was 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
Jaroso Hydrothermal System: 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. Also
thanks to Dr. David Hochberg for the revision of the English version.
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Fig. 1: General view of the Jaroso ravine (Almeria province, Spain), world type locality
of jarosite. Note the remains of old mining buildings.
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.
Fig.3. Chimney B (GA-B). Sampling and stable isotope variations from the central orifice to
the outer rim.
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.
Fig.5. Diagram showing temperature and δ18O (V-SMOW) values of waters. The curves
represent the theoretical temperature of carbonates in equilibrium with different types of waters.
Surficial temperatures (15–25ºC, horizontal dotted line) and the most negatives values of calcite
(δ18O = -6‰ V-PDB) were used to calculate the most negatives δ18O values of the meteoric
waters (-6.1 to -4‰ vs V-SMOW). These values indicate that even carbonatic phases with
meteoric influence (relatively negatives δ13C values in Fig. 4) have a low temperature
hydrothermal or diagenetic origin with minimal temperatures ranging between 29 and 43ºC; 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 sideritewater respectively were used for the temperature calculation.