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The Naica Project - A multidisciplinary study of the largest gypsum crystals of the world

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The caves of Naica (Chihuahua, Mexico) are perhaps the most famous mine caves of the world due to the presence of gigantic gypsum crystals. Nevertheless, very little research has been carried out on these crystals until now. An international multidisciplinary investigation started in 2006 with the aim not only to define the genesis and the age of the Naica gypsum crystals, but also to focus other important scientific aspects of these caves and to ensure a complete documentation and knowledge of these natural wonders which will not be accessible anymore in a few couple of years. The preliminary results of this, still in progress, research allow to date the giant crystals and to define the boundary conditions and the mechanisms which induced their development. For the first time pollens have been extracted from gypsum crystals and their analyses evidenced that some 35 Ky BP the Naica climate was cooler and more humid than today.
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Episodes Vol.33 , no. 1
1
by Paolo Forti1 and Laura Sanna2
The Naica Project – A multidisciplinary study of
the largest gypsum crystals of the world3
1 Earth and Geological-Applied Science Department, University of Bologna and La Venta Exploring Team
2 Italian Institute of Speleology
3 Research performed in the framework of the “Naica Project” lead by Speleoresearch and Films in cooperation with La Venta Exploring Team
fact many are their features worth to be studied, from biology to
microclimate, from physiology to palynology etc.
The study of Naica caves and crystals is a part of a general research
project which the owner of the mine, the Peñoles Company, committed
to La Venta Exploring Team and Speleoresearch & Films in 2006
(Bernabei et al. 2009).
A workshop was organized at the end of the first year of the project,
which was attended by researchers from 16 Universities of 6 Countries
(Mexico, USA, Spain, Italy, Switzerland and Norway). The presented
talks covered all the research fields of the project: from palinology to
laser scanner techniques, from physiology to mineralogy, from
climatology to speleogenesis, from geochemistry to documentation.
When all the researches will be over (probably in 2011) a symposium
will be organized in Mexico to share the results of the Naica project
with the whole scientific community.
In the present paper, after a short geological outline of the area,
the Naica project and its first achieved results within the field of earth
sciences are presented.
Geological Setting
Naica mine is located in a semi-desertic region some 100 km
southeast of Chihuahua, the capital town of the homonymous Mexican
State bordering the USA (Fig. 1). The mine opens at 1385 m a.s.l. in
the northern flank of the Sierra de Naica, a 12 km long, 7 km wide,
anticline structure of carbonate formations oriented northwest-
southeast. This antiform outcrops from a very extensive alluvial plain.
At the regional scale the Naica carbonate sequence consists of
limestone, dolomitic limestone and calcitic dolostone with lutitic
interbeds overlying an Aptian evaporitic sequence. The carbonate
sequence started its deposition during Albian age (Cretaceous) and its
sedimentation went on for several tens of millions of years. In the
mine location the whole ore body is within the carbonate sequence
and up to now no trace of the Aptian evaporites has been found within
cores drilled up to over 1 km in depth.
Tertiary intrusive magmatic activity, which characterized this part
of the North American subcontinent, caused the development of acid
dikes, some 26.2-25.9 Myr BP within the carbonate sequence (Megaw
et al., 1988). Recent magnetometric studies have unveiled an igneous
source at a depth of between 2.5 and 5 km some 4 km south of
Naica, while in 2007 a drilling close to the mine shaft met an igneous
body about 1140 m below the surface.
The polysulphide (Pb, Zn, Ag) ore bodies are related to
hydrothermal flows (Erwood et al., 1979) induced by the Tertiary dykes.
The caves of Naica (Chihuahua, Mexico) are perhaps
the most famous mine caves of the world due to the
presence of gigantic gypsum crystals. Nevertheless, very
little research has been carried out on these crystals until
now. An international multidisciplinary investigation
started in 2006 with the aim not only to define the genesis
and the age of the Naica gypsum crystals, but also to
focus other important scientific aspects of these caves
and to ensure a complete documentation and knowledge
of these natural wonders which will not be accessible
anymore in a few couple of years. The preliminary results
of this, still in progress, research allow to date the giant
crystals and to define the boundary conditions and the
mechanisms which induced their development. For the
first time pollens have been extracted from gypsum
crystals and their analyses evidenced that some 35 Ky
BP the Naica climate was cooler and more humid than
today.
Introduction
The systematic study of “mine caves” has emphasized the high
scientific interest of the minerogenetic processes active therein and
consequently of the crystals that they sometimes host (De Waele and
Naseddu, 2005).
From this point of view, the natural cavities crossed by mine
galleries in Naica (Chihuahua, Mexico) (Fig. 1) have been world
renowned for over a century, due to the dimension and purity of their
gypsum crystals (Hill and Forti, 1997). Beside Cueva de las Espadas
(Swords cave), unveiled at the beginning of the 20th century at the
-120 level, where crystals up to 2 meters in length exist (Degoutin,
1912, Foshag, 1927, Rickwood, 1981), in the last 6-7 years mine
galleries at the -290 level have intercepted several natural cavities, the
most important of which are Cueva de los Cristales (Crystal Cave),
Ojo de la Reina (Queen’s Cave) and Cueva de las Velas (Sails Cave)
(Fig. 1). All these caves host gypsum crystals much bigger that those
in the Cave of the Swords. The largest of these crystals, over 13 m in
length, has been found in Crystal Cave (Fig. 2) (London, 2003). Even
if these crystals are by far the largest gypsum crystals in the world the
scientific importance of the caves is not confined to this aspect: in
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The mineral deposit (consisting mainly of pyrite, pirrotine, sphalerite,
galena and chalcopyrite) displays chimney and manto shapes
developed within dikes and hosting carbonate formations. The latter
are consequently strongly altered and partially transformed into
calcosilicates. During a later stage, when the thermal fluids got colder,
calcite, anhydrite and quartz formed veins within the ore bodies (Stone,
1959).
Two different fault sets were the main structural controls for
hydrothermal circulation and therefore for the location of the mineral
deposits. The most important of them are the Gibraltar, Naica and
Montaña faults (Fig. 1). These structures still control the thermal
water flow within the Naica anticline: almost all the water springing
in the deep mine galleries comes from fractures related to these faults.
Their important role in water circulation is also confirmed by the fact
that all the main karst caves are strictly related to them (Fig. 1). Mine
activities have reached -760 below the mine entrance (level 0 at 1385
m a.s.l.), and they are some 630 m below the original groundwater
level which was at -130 (1255 m a.s.l.): presently to maintain the
mine galleries water free a dewatering of about 1 m3/s is required.
All the Naica area is still under a thermal anomaly. Water springing
in the mine galleries has a temperature close to 53°C. A recent study
(García Ruiz et al., 2007) has demonstrated the meteoric origin of
these waters, even if the average residence time within the thermal
aquifer is rather long (over 50 years).
The end of the mining activities (some 5-7 years from now) will
have as a consequence the flooding of
the mine thus the gigantic crystals will
be definitively drowned in 170 m of hot
water.
The Naica Project
The aim of the four year project is to
carry out a multidisciplinary research not
only on various fields of interest in the
Naica caves but also to search for a
possibility to maintain this geological
wonder at least partially available for
future generations after the end of the
mining activity.
The first research to start was
obviously related to the presence of the
150 huge gypsum crystals (Badino et al.,
2009) inside the Cueva de los Cristales:
it was necessary to understand the
mechanism by which such gigantic
crystals grew and how long the
environmental conditions allowing their
development were maintained. In this
respect the analyses of the huge, wide-
spread fluid inclusions and small solid
inclusions (in particular spores and
pollens) proved to be fundamental
together with U/Th gypsum analyses.
Another related field of interest is the
study of the minerogenetic mechanisms
which were active before, during and
after the deposition of gypsum in order
Figure 1. Sketch of the mine in which the main natural cavities, closely connected to the main
faults, are related to the original groundwater
to clarify the relationships between the mine ore bodies, the cave
speleogenesis, and the development of the gypsum crystals: a
unexpected richness of diagenetic minerals, some of which new for
the cavern environment, has been detected, thus allowing the detailed
reconstruction of the evolution of these caves in the last half million
years.
Other ongoing researches are focused on fields apart of geology:
they deal with the physiologic behaviour of the human body when
exposed to the Naica cave climates (Giovine et al., 2009), the possible
presence of extremophile micro-organisms trapped within the huge
fluid inclusion of the giant gypsum crystals (Boston, 2007), the study
of new miniaturized devices to analyze the rock composition in non-
destructive manner for space research, and to define the present day
human impact on the caves and the better method to preserve them
and to allow their public fruition in the future (Calaforra et al. 2007).
To answer all these questions a multidisciplinary task force has
been organized (Fig. 3): presently some 40 scientists from 17
Universities and 2 Research Centres co-operate and more are expected
to join in the near future.
Exploring and mapping Naica caves
Before starting scientific research inside these caves it was
necessary to solve the problem of survival in such an hostile
Episodes Vol.33 , no. 1
3
environment (Badino and Forti, 2007). In fact, though small and not
so complex, the caves of the Naica mine are a problematic habitat
and it is impossible to venture inside without special equipment and
suitable training, in order to avoid death in a few minutes.
The temperature in itself (45-48°C), isn’t too high if compared
to what can be found outside. But, without exception, external
high temperatures are associated with a low humidity level and
this fact allows cutaneous perspiration that induces the consequent
cooling. This mechanism balances the heat transferred by the
environment.
The Humidex Index, combining air temperature and humidity,
makes it possible to represent in Humidex degrees, (Masterton and
Richardson, 1979) the “temperature actually perceived” by the human
body against the subjective evaluation of the sultry heat. In Cueva de
los Cristales the Humidex Index ranges between 90 and 100 degrees,
roughly, twice the value of the risk of death.
Apart from this unbearable heat for the human body, above 42°C,
our cells degenerate, i.e. they cook. The temperature inside the cave
is higher than that, so, there is a risk of burning. Survival techniques
for longer periods had to take in serious consideration the risk of
burns to the eyes and, even more devious and fatal, to the lungs.
For this reason, the first four expeditions were devoted to study
the environment in which we had to operate.
The most important result achieved has been the understanding
of the operating context: due to the environmental conditions, without
specific technical precautions and suitable equipment any research is
practically impossible. Thus specific materials and technologies have
been developed: in particular, the refrigerated suits (Fig. 2), and the
“crystal friendly boots” a footwear with a smooth and soft sole, made
of a special mix that assures a perfect adherence above 40°C.
The usual stay was about one-two minutes in case of untrained
personnel and up to ten minutes for the expert ones, but thanks to the
developed techniques it is now possible to stay for more than one and
a half hour.
But the environment appeared more hostile than expected and
these prolonged stays caused unexpected and really dangerous
situations of physiological stress. A correlated study of the matter
became therefore part of the present project (Giovine et al., 2009).
Once solved the survival problems an extremely detailed survey
of the Cueva de los Cristales was realised by using laser scanner
techniques (Canevese et al., 2009), this because all the teams needed
a reliable map to locate samples and/or field observations.
The genesis and evolution of the giant crystals
These studies were the first to be developed. Before the discovery
of these caves four different reactions were known to cause the
Figure 2. A general view of the giant gypsum crystals inside the
Cueva de los Cristales: explorers are equipped with refrigerated
suits and breathing (photo by Paolo Petrignani, La Venta & S/F
Archives)
Figure 3. The Naica multidisciplinary team
evolution of big gypsum crystals in
cavern environment (Hill and Forti,
1997), evaporation, acid aggression,
sulphide oxidation and incongruent
dissolution. The study of the geo-
chemical and physicochemical
characteristics of the thermal aquifer
evidenced the existence of a
completely new mechanism for the
genesis and evolution of these giant
crystals (García Ruiz et al., 2007),
which is based upon the gypsum-
anhydrite solubility disequilibrium.
At 59°C the gypsum and anhydrite
solubilities are the same. At lower
temperatures the solubility of
gypsum becomes smaller than that
of anhydrite (Fig.4).
Therefore, below this
temperature a solution saturated with
respect to anhydrite is automatically
super-saturated with respect to
gypsum, thus inducing the
deposition of gypsum and a under-
saturation with respect to anhydrite.
Anyway to avoid the immediate stop
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4
of this process the super-saturation with respect to gypsum must be
maintained by introducing into the system new Ca2+ and SO42- ions,
which may be simply supplied by dissolution of new anhydrite (Forti,
2009).
Hydrothermal anhydrite lenses are dispersed in the whole
carbonate sequence of Naica as a consequence of the late stage of the
formation of the ore deposit and it allows for continuous supply of
Ca2+ and SO42- ions to maintain the uplifting solution supersaturated
with respect to gypsum and slightly undersaturated with respect to
anhydrite (Garcia Ruiz et al., 2007)
Such a small difference between the solubility of gypsum and
anhydrite slightly below 59 °C provides a very stable mechanism to
constantly maintain the crystallizing system close to equilibrium.
The role played by the anhydrite-gypsum solubility disequilibrium
in the development of the Naica giant gypsum crystals is indirectly
corroborated by the widespread presence of euhedral celestite (SrSO4)
crystals in the thin layer of clay and iron oxides just below the gypsum
crystals of all the Naica caves and also trapped within the them (Panieri
et al., 2008). It is well known that the anhydrite structure hosts more
strontium than does gypsum (Butler, 1973). Therefore, instead of being
incorporated into the structure of newly forming gypsum, this excess
strontium released through dissolution of anhydrite precipitated as a
separate mineral phase. Another indirect proof of the active
transformation of anhydrite to gypsum is given by the presence of
microscopic gypsum crystals actively growing inside anhydrite lenses
close to the Cueva de los Cristales (Garcia Ruiz et al., 2007).
The development of few huge crystals instead of many small ones
is justified by the fact that the temperature drop was extremely slow
(data from fluid inclusions demonstrate that the giant crystals
developed in a temperature range between 55-58°C) over a relatively
long time interval (Garofalo et al., 2009).
In order to evaluate the time interval in which the giant crystals
developed several samples of already broken crystals have been taken
from Cueva de los Cristales, Ojo de La Reina and Cueva de las Espadas
to try to obtain dates by the 230Th/ 234U method.
A few samples were analysed by using thermal ionization mass
spectrometry (TIMS) on a Finnigan 262RPQ instrument (Lauritzen
et al., 2008), but this dating methodology proved to be inefficient
due to the very scarce amount of uranium trapped within the gypsum.
Only one sample taken some 50 mm below the outer surface of a
prismatic crystal from Cueva de los Cristales gave a good result
(34.544 ± 0.819 kyr).
In order to improve the U/Th dating it was then decided to use a
multi-collector inductively coupled plasma mass spectrometry (MC-
ICP-MS) technology and a new extraction chromatographic method
(Sanna et al. 2009). The first two achieved results are satisfactory: in
fact even though the analysed samples display low uranium
concentration and high background thorium level, the obtained ages
are within reliable ranges. The first sample was taken from the inner
core (some 13 cm from the outer surface) of a broken prismatic crystal
in Cueva de los Cristales and gave an age of 164±48 kyr. The second
one was taken at the entrance of the Ojo de la Reina cave, which is
only a few tens of meters apart of Cueva de los Cristales: the sample
was extracted from the base of a pinacoidal crystal a few centimetres
apart from the contact with the limestone rock of the cave floor: its
resulting age was 213 ± 12 kyr (Sanna et al., 2009).
Based on its location with respect to the hosting rock, the data of
this sample should represent the very beginning of the gypsum
deposition within the caves at the -290 level of the Naica Mine.
In order to test the validity of this assumption an experimental
unit has been built, and placed in one of the “water springs” at -590
level, where the original thermal water, not yet contaminated, spills
out from the ceiling of a mine gallery.
The experimental unit was planned to completely avoid the contact
of the thermal water with the mine atmosphere in order to reproduce
the condition of complete saturation existing inside the cave until the
mine dewatering caused their emersion (Forti and Lo Mastro, 2008).
Thus the single unavoidable difference existing between the present
day water and that feeding the crystals in the caves until twenty years
ago is its temperature which dropped to 51°C.
Other affecting factors, like variation of ionic effect as a
consequence of the variation in salinity of the feeding solution (from
the original 4-5% to the present day 2%) and the flux effect (the
residence time of the solution inside the caves may be estimated in 1-
2 days, while that inside the experimental vessel is only of 2-3
minutes), were not taken into consideration because their effect on
the supersaturation was evaluated to be extremely scarce with respect
to that of the temperature.
The device to reproduce the “cave conditions” for gypsum
development (Fig. 5a) was installed at the end of 2006 and the
experiment was successful. Euhedral gypsum monocrystals started
growing (Fig. 5b) and the first available data covering an interval of
over 480 days evidenced a very good correlation between crystal
growth and time (Forti et al. 2009). The resulting average growth
(corrected for the temperature factor) is 0.004 ± 0.0002 mm/yr. The
experimentally measured growth rate gives an extrapolated age for
the biggest crystals of 250000 yr, a value extremely close to that
Figure 4. The development of the gypsum crystals induced by the
gypsum-anhydrite solubility disequilibrium and (upper right)
Gypsum-Anhydrite solubility diagram with evidenced (in red) the
temperature range in the caves of Naica at the time in which gypsum
crystals were growing
Episodes Vol.33 , no. 1
5
obtained with U/Th method for the crystal of the Ojo de la Reina.
Considering the experimental errors which characterize both
independent methods of dating, the agreement between the two values
can be considered extremely good.
Using recent data on the dissolution kinetics of crystalline gypsum,
(Jeschke, 2002), and assuming that dissolution and precipitation
kinetics is symmetric around the saturation point (i.e. no nucleation
threshold), the growing rate of 0.004 mm/yr converts to a
supersaturation of about 1.005. This value corresponds to a nucleation
probability (García Ruiz et al., 2007)
less than 1 over 1 million which is
reasonable for the growth of a hundred
of giant crystals over a period of two-
three hundred thousand years.
Finally it must be stressed that
Naica caves are important not only for
giant gypsum crystals, in fact they also
host two new forms of gypsum. The
first, named sails (Fig. 6a), have been
discovered (Bernabei et al., 2007),
inside the Cueva de las Velas. They
are very thin fibres of gypsum, the
evolution of which is closely related
with the very first moment of the
artificial lowering of the ground water
table at Level -290. They are
crystalline forms which have
developed in a few days or months,
about 20 years ago and their
development and shape are totally
controlled by capillary lifting and
strong evaporation over the tips of the
giant crystals pointing upward.
The second, named “gypsum
hooks”, were observed only in the
upper part of Cueva de Las Espadas
Figure 5. Left: the device placed at -590 to restore the conditions for the development of gypsum
crystals; Right: gypsum crystals developed in about one year (photo Antonio Rossi, University of
Modena, Italy)
Figure 6. Left: Cueva de las Velas: a “sail” growing epitaxially over a pre-existing large gypsum
crystal (photo by Tullio Bernabei, La Venta & S/F Archives); Right: gypsum hooks from Cueva de las
Espadas (photo by Paolo Forti, La Venta & S/F Archives)
(Fig.6b). They are partially re-dissolved and bended crystals and their
evolution was controlled by condensation and consequent strong
heating of the crystal tips, when the cave became partially aerated
during the latest phase of presence of thermal water (Forti et al., 2009).
The other chemical deposits
Even if 99% of the chemical deposits developed within Naica
caves consist of gypsum, the scientific interest of the other deposits
is very high. The mineralogical
analyses are still in progress but
already evidenced the presence of 40
different cave minerals, 10 of which
(antlerite, hectorite, orientite, penta-
hydriote-Cu, plumojarosite, starkeyite,
szmikite, szmolnokite,and woodruffite,
and an Al, Mg, Cu, Zn silicate) new
for the cavern environment. Most of
them developed in two distinct periods
of oxidation of the ore bodies. In the
first one, which occurred deep inside
the thermal aquifer before and/or
during the first stage of the deposition
of the giant gypsum crystals, a large
quantity of material was deposited but,
due to the scarce variability of such
an environment, only a few minerals
developed (Panieri et al., 2008). This
process was clearly controlled by
micro-organisms, as testified by
widespread biogenic structures
preserved within these deposits
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(Fig. 7) and gave rise to the deposition of the following 9 minerals:
calcite, coronadite, celestite, dolomite, fluorite, göthite, hectorite, opal
and quartz (Forti et al. 2009). The genesis of hectorite
[Na0.3(Mg,Li)3Si4O10(F,OH)2] was observed for the first time in a cave
and is related to the pH decrease as a consequence of the ore bodies
oxidation, which reduced the silica solubility enhancing also the opal
and quartz deposition, and the increase of magnesium concentration
in the feeding waters (Garofalo et al., 2009)
The second oxidation stage, started less than 20 years ago when
mine dewatering allowed aerate conditions within the caves. In this
case the process was totally abiotic as proved by the total absence of
stalagmites” developed at the bottom of the Cueva de las Espadas
(Fig. 8) are worth of mention.
The analyses (FORTI, 2007) of a polished section of these
speleothems evidenced the presence of an inner nucleus consisting of
a prismatic gypsum euhedral crystal over which developed two white
layers of acicular aragonite alternating with two layers of gypsum
macrocrystals. Then the speleothem was covered with a thin layer
(1-2 mm) of hazel-brown calcite and finally by poorly cemented clay-
silty deposits, which represent the latest stage in the depositional
sequence of this cave. During the low stand of the groundwater, the
ingression of air in the upper part of the cave is responsible for the
development of aragonite due to the diffusion of CO2 into the thermal
water. The subsequent highstand levels of groundwater re-established
saturated conditions and therefore gypsum was deposited. The film
of brown calcite corresponds to the definitive lowering of the thermal
aquifer below the level of Cueva de las Espadas, which was started
by a moderate flow of fresh water which induced the deposition of
calcite instead of aragonite. This period was drastically interrupted
by mining activities, which changed dramatically the hydrogeology of
the whole area and also intercepted fresh water seepage feeding the
cave, thus causing the deposition of the silt and clay deposits, which
are the latest deposits in this cave. By using the thickness of all
these different layers, it seems that the whole sequence of observed
events (from layering of the gypsum crystals to silt deposition) took
only a few thousand years.
To confirm these hypothesis two samples were taken from one of
the pseudo stalagmites. The first one from the inner core of the gypsum
macrocrystal (S1 in Fig. 8) and the second one from the first aragonite
layer (S2 of Fig. 8) about 2 mm above the gypsum surface.
Both these samples were dated with the multi-collector inductively
coupled plasma mass spectrometry (MC-ICP-MS) technology (Sanna
et al., 2009) and the obtained ages are respectively: 60 ± 0.7 Kyr for
the core of the gypsum and 15 ± 2 kyr for the aragonite layer.
The age of the inner gypsum core should correspond to the
Figure 7. An electron microscope image of Fe/Mn oxides that
fossilized clear biogenic forms (Laboratorio Grandi Strumenti,
University of Modena, Italy).
any biogenic form and it induced
the deposition of small amounts
of material but with an extremely
high minera-logical variability
due to the high number of active
minerogenetic meghanisms
(Table 1). 36 different minerals
have been detected: anglesite,
anhydrite, antlerite, apatite,
aragonite, azurite bassanite,
blödite, calcite, celestite,
chalcantite, chrysocolla, dolo-
mite, epsomite, fluorite, frai-
pontite, göthite, guanine,
gypsum, halite, hematite, hexa-
hydrite, jarosite, kieserite,
magnetite, malachite, orientite,
Cu-rich variety of pentahydrite,
plumbojarosite, pyrolusite,
rozenite, starkeyite, szmikite,
szmolnokite woodruffite and an
Al, Mg, Cu, Zn silicate, which
is still under study and may result
a new mineral for science).
Finally some small “pseudo-
Figure 8. Vertical (1), horizontal (2) sections and graphical restitution of the pseudo-stalagmite grown
inside the lake of the Cueva de las Espadas: A gypsum, B aragonite, C gypsum, D aragonite, E gypsum, F
calcite, G clay and silt. S1 and S2 are the sampling point for the U/Th datings.
Episodes Vol.33 , no. 1
7
beginning of a new step of gypsum deposition after a long corrosional
period which caused the partial and /or total destruction of most of
the largest gypsum crystals previously developed inside this cave.
The age of the first aragonite layer corresponding to the first
fluctuation of the groundwater level gave an age which is in good
agreement with the supposed one derived by the morfometric analyses
of the 5 overgrowth layers, whose thickness suggest a rather constant
time span of each of them. In the near future the radiometric ages of
all the layers of the “pseudo-stalagmite” will allow for a detailed
reconstruction of the fluctuation of the thermal groundwater level
within the last 15 Kyr BP.
Stages in the development of the cave
Until recently, studies were focused on the mechanisms allowing
for the development of the giant crystals, while the genesis and the
evolutionary steps of the Naica caves were completely neglected. The
thermal fluids responsible, since 25 Myr BP, of the evolution of the
Naica ore bodies were always characterized by net deposition,
therefore the permeability of the hosting formation was greatly reduced
and no karst voids had the possibility to develop.
Very recently (1-2 Myr BP), tectonic stresses partially displaced
the ore bodies giving rise to open joints and fractures closely related
to three main faults (Naica, Gibraltar e Montañas), which control the
uplift of the thermal fluids.
In the mean time the temperature of the thermal water lowered
below 100-120°C and they became aggressive with respect to
carbonate formations, thus small cavities had the possibility to develop
at different levels inside the aquifer. This first stage of deep karst
development was common to all the caves of Naica but it was surely
how different from cave to cave, being, time by time, related to deep
phreatic, epi-phreatic and vadose environments (Table 1).
From this point of view the most interesting cave is the Cueva de
las Espadas, the evolution of which was characterized in time by
several changes between these three environments, while the deeper
caves (Cristales, Ojo de la Reina and Velas) suddenly changed from
Figure 9. Stratigraphic sketch of the deposits present in each of the Naica caves and their relationships
short and the corrosion
process not very effective. In
fact, the presently known
caves are small and they
always correspond to scarcely
widened fractures (Ojo de la
Reina and Cueva de las
Espadas) or bedding planes
(Cueva de las Velas). The few
corrosional features (mainly
bell domes on the ceilings) did
not allow for a detailed
reconstruction of the cave
evolution, which was in turn
achieved by a multi-
disciplinary analysis of the
thick deposits hosted inside
each cave (Fig. 9).
The evolutionary steps
were several and complex
ones, related to different
speleogenetic mechanisms
(corrosion, double exchange,
acid aggression, CO2 diffu-
sion, condensation corrosion,
etc). Even if they always were
controlled by the presence of
the thermal aquifer, the
resulting evolution was some-
Table 1. Environmental control over the active speleogenetic processes
and related temperature variations.
Environment Processes Chemical Deposits T° decrease
Organic matter Organic mineral
mineralization and phospates
deposition
CO2 diffusion Calcite speleothem
evolution
Vadose Acid aggression Gypsum, metallic Very fast
sulphate & silicate
deposition
Inorganic Oxide-hydroxide
oxidation deposition
Evaporation “sails” development,
sulphate and halide
deposition
Epi-Phreatic CO2 diffusion Aragonite deposition Slow
Organic Oxide-hydroxide Extremely
oxidation deposition and slow
Deep Phreatic limestone corrosion
Gypsum/ Giant gypsum crystals
anhydrite and celestite
disequilibrium development
March 2010
8
deep phreatic to vadose conditions when the mine dewatering lowered
the groundwater below the -290 level 20 years ago. The +50 cave is
the only one in which the deposition of phreatic gypsum never
occurred because the thermal water left it before its cooling down
reached the gypsum-anhydrite equilibrium temperature.
The gypsum deposition went on until 20 years ago, when the
mine exploitation caused the complete dewatering of the caves:
anyway this fact did not represent the end of the cave development,
which was characterized by a last stage active in all the cavities. The
depression cone had relevant consequences on the cave development
giving rise to the evolution of several new diagenetic minerals but
also greatly enhancing the condensation corrosion and dissolution
processes which, in a few years, will be responsible not only for the
damage of the giant gypsum crystals but also for their complete
destruction.
Fluid Inclusion Analyses
The study of fluid inclusions is aimed at determining the
fundamental physical-chemical properties of the fluid that generated
the giant gypsum crystals and its evolution in time and space (Garofalo
et al., 2009). Fluid inclusions are abundant in all the studied samples
and are commonly big (>200 ìm, Fig. 10). They were typically found
along crystallographic planes (primary fluid inclusions).
About four hundred microthermometric measurements were
carried out at the Department of Earth and Environmental Sciences
of the University of Bologna with a Linkam THMSG 600 heating/
freezing stage attached to an Olympus BX51 petrographic microscope.
This stage is calibrated periodically using synthetic fluid inclusions
(H2O and H2O-CO2 fluids) and laboratory standards.
In all the occurrences the trapped fluid is mostly one-phase (liquid)
at Tlab, and only occasionally two-phase (liquid-vapour). Freezing
experiments show the presence of two aqueous fluids with distinct
bulk salinity within the cave crystals: one in the range 3-6 wNaCl
equiv.(characterizing most of the fluid inclusion of the -290 caves) and
the other between 7 and 8 wNaCl equiv (the highest values being observed
mainly in the dark portion of the crystals of Cueva de las Espadas).
Finally samples of the gypsum crystals actually developing close to
the thermal springs in the mine galleries at -590 exhibited fluid
inclusions with a even lower bulk salinity 1,8-2.0 wNaCl equiv.
Laser Ablation-ICP-MS analyses were carried out at the
Department of Chemistry and Applied Biosciences of the ETH-Zurich
on 71 individual inclusions adjacent to those studied by
microthermometry by using two UV 193 nm excimer lasers (GeoLasQ
and GeoLasC, Lambda Physik, Göttingen, Germany) coupled with a
quadrupole ICP mass spectrometer (ELAN 6100DRCplus, Perkin-
Elmer, Waltham, Massachusetts).
Preliminary chemical analyses of single fluid inclusions by LA-
ICP-MS show that, in addition to Ca and S, the major components of
the cave fluid were Mg, Na, and K (in order of abundance), while Mn
and Pb are minor and below the limit of detection in many inclusions.
Only the fluid inclusions within the dark rims (rich in solid inclusion
of oxides-hydroxides) of the crystals of Cueva de las Espadas, where
Na and Mg reach high concentration ranges (10000-70000 µg/g),
exhibit a relatively high Pb content (up to about 10000 µg/g).
The distribution of total homogenisation temperatures in Cueva
de los Cristales display a mode in the 49-57 °C interval, which is
rather undistinguishable from that of Las Espadas, while in Ojo de la
Reina this interval is narrowed to 56-57°C. Hence, in contrast with
the distribution of bulk salinity and Mg-Na concentration values, the
total homogenisation occurs in a narrow range within the entire Naica
karst-system.
A still open question is the definition of the mechanism responsible
for this relatively high increase of Mg-Na content in the upper part of
the thermal aquifer. These events may be explained by periods in
which the Cueva de las Espadas was partially dissected from the
main thermal aquifer, thus allowing for strong evaporation processes
and consequent high concentration of Mg-Na ions in the residual
water. On the basis of theoretical evaluation of ionic activities of the
main ionic species present within the Naica aquifer (Garofalo et al.,
2009), it was possible to demonstrate that the partial mixing of the
hypersaline upper solution with the deeper less concentrated ones
will constantly induce a slight supersaturation with respect to gypsum
thus enhancing the growth of the giant gypsum crystals within the
Cueva de los Cristales and Ojo de la Reina caves. Exceptional crystal
growth was not possible in Cueva de las Espadas because of periods
of high supersaturation induced by evaporation, which obviously
induced a fast new nucleation.
Solid inclusions analyses
A detailed study of the solid inclusions trapped inside the crystals
is being carried out. Some of the solid inclusions have shown a rich
presence of “biogenic” organisms, fossilized by neo-formed minerals
during the fist oxidation stage (Fig. 7). This discovery suggests that
it might be possible to find, inside the large fluid inclusions often
present inside the crystals, some micro-organism still viable for DNA
genetic studies. Therefore a threefold research started: (1) to seek
any viable living organisms that may be trapped in fluid inclusions
and attempt to cultivate them, (2) to extract any DNA present in the
fluid inclusions and identification of organisms or closest relatives
(where possible), and (3) identification and analysis of any non-
living organic material other than DNA that may shed light on any
biological contents of the inclusions.
Figure 10. A huge biphasic fluid inclusion from Cueva de las Espadas (photo by Paolo
Forti, La Venta & S/F Archives)
Water extracted from fluid inclusions of the
gypsum crystals of Cueva de los Cristales have
been fed in oxygen rich and oxygen depleted
environments since more than one year. Biomats
started to grow but the process is so slow that
presently their amount still does not allow to
perform experiments (P. Boston personal
communication). In any case it has been
demonstrated that living organisms were
trapped inside the gypsum crystals at the time
of their development and maintained at least
some of their living activities up to present.
Episodes Vol.33 , no. 1
9
NASA is directly involved in these researches, and recently it has
successfully tested a new miniaturized Raman spectrometer inside
the Cueva de los Cristales. This apparatus will be sent in the near
future to Mars for searching living micro-organisms (extremophiles)
on the surface of that planet.
Amongst the Naica solid inclusions by far one of the most
intriguing findings was the presence of well preserved pollen grains
(Holden, 2008) trapped inside the giant gypsum crystals. Their
presence inside the gypsum crystals may be explained only assuming
that the meteoric water seepage brought them deep in the thermal
aquifer from where the pollens were uplifted into the caves by the
hot water feeding the crystals which consequently trapped them
inside their structure.
Pollens and/or sporomorphs (Garofalo et al., 2009) have been
found in all the analysed samples from all the Naica caves, but, up to
present, detailed investigation have taken place only in Cueva de los
Cristales. In this cave the pollens were extracted from the same crystal
and the same area from which the absolute age of 34.544 ± 0.819 kyr
was obtained. Extractions have been carefully repeated several times
to be sure that the presence of pollens was not due to accidental
pollution. Presently a total of over 40 pollen grains have been detected
and some of them were perfectly preserved. Among these, pollens of
Quercus cf. garryana, Lithocarpus densiflora cf., Cupressus, Taxus,
Plantago, and Lycopodium sphores have been detected.
The pollen spectrum is representative of the vegetation existing
in the feeding basin at the time of development of their deposition.
Therefore they may allow for a paleo-climatic reconstruction for the
area of Naica. Even still in progress the presently identified pollens
are coherent with a humid broadleaf forest, presently existing in the
S-Western areas of United States, suggesting that about 35 ky BP the
Naica area was characterized by a much more humid climate than
that present today.
Presently further fluid inclusion analyses and absolute dating of
the hosting crystals are in progress to validate this paleo-environmental
reconstruction.
Final remarks
Even if the research started only recently, some of the already
achieved results are of extraordinary interest. A completely new
mechanism for the development of the giant gypsum crystals based
on the anhydrite-gypsum solubility disequilibrium below 59°C has
been defined. Well preserved pollens have been found, for the first
time in the world, trapped in euhedral crystals and they seem to be,
together with the fluid inclusion and absolute dates, suitable proxy
for paleoclimatic reconstructions. Microbiological search for
extremophiles is very promising and the detection of new species is
expected in the near future.
But all these researches must be completed in a short span of
time.
In fact all the karst phenomena at the –290 level of Naica mine
will remain accessible only for a few years, and as soon as the mining
activities will stop (an event that is expected within 5-7 years), the
uplifting of groundwater will submerge them under 170 m of hot
water.
In reality, the giant crystals of Naica run the risk of destruction
even earlier due to condensation processes. The walls of all the cavities
of the –290 level, undergo a rather fast cooling due to the forced
ventilation of the mine galleries. This process may bring in a short
time the cave walls to have a temperature low enough, with respect to
that of the uplifting vapours, so that the dew point will be reached
and surpassed. When that happens, strong condensation will occur
with the consequence of a fast dissolution of the giant gypsum crystals
(Fernández-Cortés et al., 2006). This process has already started within
the smallest cave at the –290 level (Ojo de la Reina), where the large
gypsum crystals are presently intensively dissolved and transformed
into calcite speleothems. In a couple of years condensation is expected
to start also inside the Cueva de los Cristales.
Therefore a monitoring unit equipped with 20 sensors, with an
accuracy of 4 mK, probably the most precise system of this kind ever
brought inside a cave, was installed (Badino, 2009). Preliminary data
seem to confirm a rather fast cooling trend (~0.5°C/yr).
Thus, one of the project main tasks is to decide the best way to
preserve for future generations at least the memory and the records,
or, even better, a significant part of this incredible underground world.
Speleoresearch and Films of Mexico City, in cooperation with
La Venta, started the realization of full-length films documenting all
the explorative and scientific aspects of the Naica caves: but it’s not
enough. Crystals Cave has been laser-scanner processed to obtain
exact high definition 3D maps and eventual virtual reality trips.
But what is more worrying is the material conservation of the
crystals. It would be nice to preserve at least a portion of these caves
avoiding what happened in Cueva de las Espadas at the beginning of
last century: crystals taken away and scattered in various, more or
less important, mineralogical collections around the world.
Acknowledgments
The Authors thank Peñoles Company for allowing the access to
the Naica Mine and for helping all the scientists involved in this
program to perform their job inside the caves and Jo De Waele for the
critical review of the manuscript.
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Paolo Forti is Professor in Geo-
morphology and Speleology in the
University of Bologna (Italy). He
served as president of the Inter-
national Union of Speleology from
1994 to 1997 year in which he was
nominated Honorary President of
the UIS. Much of his work is
dedicated to gypsum caves, cave
mineralogy and speleogenesis. In
the recent years he focused his
research on hypogene and mine
caves. Since 2006 he leads the
geologic team investigating the
Naica Cave.
Laura Sanna is caver since 1998
and participated in different studies
on karst environments in Sardinia
(Italy) and a few other countries:
France (Jura Massif), Mexico (the
Naica caves), Madagascar (Belomo-
tra plateau) and Norway. Currently
she is working as a post-doc on U-
series dating at the University of
Bergen under the supervision of
Prof. Stein-Erik Lauritzen. The
study focuses on dating cave
minerals, especially referred to the
age of the giant gypsum crystals of
Naica and on speleothems of coastal
caves in Sardinia that record sea
level changes.
... In the last decade, some efforts have contributed to deciphering the growth of Naica crystals. In 2010, the first multidisciplinary endeavor was carried out by "La Venta Exploration Team" [36] based on the mechanism proposed by García-Ruiz and later, by Otálora and García-Ruiz, to explain the slow growth of the giant crystals. According to this process, which the authors have called "self-feeding", the water in the system is at a temperature slightly lower than that of equilibrium between anhydrite and gypsum, (53-58 • C), slowly dissolving the abundant hydrothermal and sedimentary anhydrite in the "Cueva de los cristales" [31,37]. ...
... For the mechanism to be viable, the system must meet two requirements; there must be enough anhydrite in the area, and the solution temperature must be close, but lower, than the transition temperature of the gypsum-anhydrite system ( Figure 10). Both conditions were met in Naica according to the information obtained from the liquid inclusions found in the crystals [36]. Dating using uranium, and other radioactive isotopes suggests, although the development of the crystals was uninterrupted, the crystal growth rate might have changed through time [30,73]. ...
... Several groups around the world have contributed to the study of their crystals through constant quality investigation. Research has been relatively robust with in situ and ex situ, experimental approaches [18,27,31,34,36,38]. In Figure 11, the unique proportions of the giant crystals can be observed. ...
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Chapter
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Contains 4 figures. Exploration in the Naica mine (Chihuahua, Mexico) recently unveiled several caves containing giant, faceted, and transparent single crystals of gypsum (CaSO4•2H2O) as long as 11 m. These large crystals form at very low supersaturation. The problem is to explain how proper geochemical conditions can be sustained for a long time without large fluctuations that would trigger substantial nucleation. Fluid inclusion analyses show that the crystals grew from low-salinity solutions at a temperature of ~54 °C, slightly below the one at which the solubility of anhydrite equals that of gypsum. Sulfur and oxygen isotopic compositions of gypsum crystals are compatible with growth from solutions resulting from dissolution of anhydrite previously precipitated during late hydrothermal mineralization, suggesting that these megacrystals formed by a self-feeding mechanism driven by a solution-mediated, anhydrite-gypsum phase transition. Nucleation kinetics calculations based on laboratory data show that this mechanism can account for the formation of these giant crystals, yet only when operating within the very narrow range of temperature identified by our fluid inclusion study. These singular conditions create a mineral wonderland, a site of scientific interest, and an extraordinary phenomenon worthy of preservation. We gratefully acknowledge Compañía Peñoles for the facilities provided during the field studies performed in the Naica mine, and the Ministerio de Educación y Ciencia of Spain for financial support. Peer reviewed
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The giant Geode of Pulpí (Almería, Spain) can be considered as one of the most significant recent mineralogical discoveries in terms of geological heritage. Any tourist exploitation of this mining environment should be sustainable, and the first step is to determine the feasibility of opening the interior of the geode to visitors. To achieve this objective it was necessary to characterize the variation of physical parameters of the air and rock (gypsum crystals) during monitored visits, similar to the hypothetical visits that would occur if the geode were opened to the public. The main environmental impact of a continuous presence of people inside the geode is condensation on the surface of the gypsum crystals as a result of increased temperature and water vapor caused by respiration. The phenomenon of condensation on the gypsum crystals begins to occur with visits of two or three people for longer than 10 min. Condensation on the crystal surface brought about by this human presence could lead to the corrosion of the crystals. The total recovery time required after a visit of this type to resume the initial natural thermal and humidity conditions was 27 h. The results obtained from the environmental monitoring of the geode suggest that it is not feasible to allow visits inside it because of the mechanical impact of the visitors on the crystals and of the risk of condensation of water vapor. Copyright © 2005 Royal Meteorological Society.