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Research Journal of Chemistry and Environment______________________________________Vol.

15 (3) Sept (2011)


Multianalytical characterization of silica-rich
megabreccias from the proposed natural area of Richat
(Sahara desert, Mauritania)
Martinez Frias Jesus,
* Rull Prez

Martn-Redondo M.Paz
, Huertas Antonio Delgado
, Sampedro
Fernndez M.Teresa
, Garca-Talavera Francisco
, Lpez-Vera Fernando
, Rodriguez-Losada J. Antonio

and Salvn Csar Menor
1. Centro de Astrobiologia, CSIC-INTA, Ctra de Ajalvir, km. 4 28850 Torrejon de Ardoz, Madrid, SPAIN
2. Unidad Asociada CSIC-UVA, Edificio INDITI, Parque Tecnolgico de Boecillo, 47152 Boecillo, Valladolid, SPAIN
3. Estacion Experimental del Zaidin (CSIC), Sede Granada: Profesor Albareda, 1. 18008, Granada, SPAIN
4. Organismo Autnomo de Museos y Centros, c/ Ramn y Cajal, 3, Edificio Salesianos, Semistano 20,38003 Santa Cruz de Tenerife, Tenerife, Islas
Canarias, SPAIN
5. Departamento de Geologa y Geoqumica, Facultad de Ciencias, C-VI, Universidad Autnoma de Madrid, Ciudad Universitaria deCantoblanco, Ctra.
de Colmenar km. 15, 28049 Madrid, SPAIN
6. Departamento de Edafologa y Geologa, Universidad de La Laguna, 38206 La Laguna (Tenerife), Islas Canarias, SPAIN

Some terrestrial areas have favourable
environmental features that allow the preservation
and scientific study of processes which can be used as
geomarkers. The crater-like Richat structure (Sahara
desert, Mauritania) is a recently proposed protected
natural area, which can be considered as one of these
sites. Volcanic, hydrothermal and arid environments
merge together, making easy their investigation in the
field and their later characterization by the use of a
set of geochemical and mineralogical techniques
(XRD, transmitted and reflected light microscopy,
SEM-EDX, laser-Raman spectroscopy, XRF, ICP-MS
and stable isotope spectroscopy).

The study presented here focuses on the
spectacular silica-rich megrabreccias which crop out,
as a large and thick lenticular body, at the centre of
the Richat structure. Based on paragenetic
relationships, six types of silica-rich megabreccias
were identified. The link between the geochemical and
mineralogical characteristics was established, from
macro to micro scale, showing the existence of: a)
variable distributions of the major, minor and trace
elements; b) polymorphic phases; c) micrometric
cataclastic features and d) different textural
intergrowths and degrees of crystallinity of some
minerals.The oxygen and carbon isotopic signatures
of the carbonates, within the silica-rich megabreccias,
point out a meteoric (low-temperature hydrothermal)
origin for the source waters.

Keywords: Mineralogical, geochemical, Protected Natural
Area, megabreccia, Richat, Sahara desert.

A protected area (PA), when using the official
IUCN definition (International Union for Conservation
Union), is "a clearly defined geographical space,
recognised, dedicated and managed, through legal or other
effective means, to achieve the long-term conservation of
nature with associated ecosystem services and cultural
. More specifically, the IUCN Category Ia is
applied for those areas possessing some outstanding or
representative ecosystems, geological or physiological
features and/or species, available primarily for scientific
research and/or environmental monitoring
. This is the
case of the spectacular Richat structure (Sahara desert,
Mauritania), a unique geological museum and first
proposed PA in the Saharan realm which has been recently
identified by the IUCN
and which in our view, could
have an additional scientific interest as a potential
terrestrial analog for the characterization of environ-
mental geomarkers

The prominent and spectacular circular feature of
Richat (also known as The Eye of Africa or The Eye of
the Sahara) has a diameter of almost 50 km
(Fig.1) and it
is located in the Sahara Desert of Mauritania, at Gres de
Chinguetti Plateau (NW Africa), within the Proterozoic
Taoudenni Basin that is bounded by the Man and Reguibat
basements of Archean age. Specifically, Richat occurs in
the intersection of two regional systems (N-S and E-W),
showing spectacular radial faults located at the outer part of
the circular structure
, some of them evidencing wedge-
shaped fault blocks displaying a downthrown of several

Different hypotheses have been proposed to try to
explain the Richat structure: a) due to a meteorite impact
b) as the results of basement adjustments, which originated
vertical telescopic movements
; c) granitic plutonic
processes related to lithospheric doming
and d) a
genetic model, basically involving doming and
hydrothermal fluids which originated a favorable setting for
. This last one attempts to unravel the origin of
the Richat structure. In accordance to the work, both the
structure and its breccia core would represent the surface
expression of an alkaline complex, with a remarkably well
preserved hydrothermal karst infilling at its summit
Anyway, in our opinion none of the previously defined
Research Journal of Chemistry and Environment______________________________________Vol.15 (3) Sept (2011)

hypotheses can explain, as a whole, its geological,
mineralogical and geochemical complexity and above all,
its enigmatic perfect aligning with the confirmed impact
crater of Tenoumer
and the proposed (but still
unconfirmed) Temimichat impact structure

It is also important to stress a very recent and
interesting study centered on the Tawaz breccia
, within
the Mesoproterozoic (~1.1 Ga) Atar Group on the West
African Craton. In order to explain its origin, a comparative
research of fourteen common breccia formational
mechanisms (glacial, tsunami, storm, turbidite, debris
flow/alluvial fan, rock fall/talus slope, fault, pyroclastic
flow, auto-brecciation, karst collapse, evaporite collapse,
lithic ejecta, suevite ejecta and impact tsunami) was
undertaken. The results obtained indicated that although the
Tawaz breccia was likely formed by a tsunami, preliminary
analyses can not completely eliminate the possibility that
the tsunami was triggered by an impact event (of possible
iron composition)

The multianalytical study presented here was
carried out in the framework of a scientific campaign to
, organized by the Natural Science Museum of
Tenerife (Canary Islands, Spain). It specifically focuses on
the spectacular megrabreccias which crop out, as a large
and thick lenticular body, at the centre of the singular
crater-like Richat structure (Fig.1). Large brecciated
boulders, some reaching meter-size, are also observed in
the field displaying rounded to faceted shapes (Fig.1).
Megabreccias were characterized in detail by the
application of a set of geochemical and mineralogical
techniques which allow a better understanding of the
paragenetic relationships and the hydrothermal environ-
ment in which the megabreccia developed.

Material and Methods
The diverse lithology of Richat includes a set of
rocks and alteration types (mainly limestone, dolomite,
sandstone, mudstone and chert). Specifically, the location
of the megabreccia body is well defined within the
Proterozoic rocks, between partially dolomitized limestone
and an overlying sandstone sequence
. Four types of
magmatic rocks intersect the Richat structure: a): basalts;
b) carbonatites; c) extrusive and intrusive alkaline rocks; d)
kimberlitic rocks
. The megabreccia lenticular body and
boulders display various shapes and sizes; they are
polymictic and the whole setting is intensely silicified
Sampling of the megabreccia was made trying to represent
the different compositional features and fabric properties of
the body. A more detailed typological classification mostly
based on their mineralogical and textural assemblages, was
lately made in the laboratory.

The set of analytical studies that were carried out
comprises the combination of transmitted and reflected
light microscopy, X-Ray Diffraction (XRD), laser-Raman
spectroscopy, SEM-EDX, X-Ray Fluorescence (XRF),
Inductively Coupled Plasma Mass Spectroscopy (ICP-MS)
and stable isotope spectroscopy. The mineral composition
of all samples (selected from more than 200 kg of material
collected during the field campaign) was determined by
XRD (Seifert XRD 3003 TT). This mineralogical
characterization was linked to their petrographic study by
transmitted and reflected light microscopy (Nikon Eclipse
6600 POL polarized light microscope).

SEM-EDX (Jeol JSM-5600 LV SEM coupled to a
Cambridge INCAx SIGHT EDS 110) and Raman
spectroscopy were also applied to reveal the compositional,
textural and structural features of some specific minerals.
Raman spectroscopy was performed on the megabreccia
samples without any preparation using a Raman
spectrometer from Kaiser Optical Hololab System with a
microscope attachment. This spectrometer is coupled to a
Raman probe head through optical fibers. Excitation was
performed by a He-Ne laser at 632.8 nm and a NeYAG
doubled laser at 532nm. Spot diameters ranged between 20
and 50 m and irradiance on the sample was kept below the
threshold of thermal damage. This mineralogical study was
the first step of the research which allowed to establish the
existence of well-defined compositional types of
megabreccias for further geochemical characterization.

For the geochemical analysis, major elements were
determinated by XRF (Scientific Technical Services of the
Oviedo University, Spain). A sequential X-ray fluorescence
spectrometer (PW2404, Philips) equipped with an
automatic charger (PW22540, Philips), a rhodium X-ray
tube, 4kW generator and 5 analyzing crystals (LiF 200, LiF
220, PE, Ge y PX 1) was used. XRF analysis was done on
fused glass beads. For preparating the samples into glass
beads, the megabreccia material was first milled to less
than 75 m particle size. Then, to determine the loss on
ignition (LOI), 5g of sample material was heated at 975C
for 1h. Subsequently, 0.5 g of the residue was mixed with 6
g of lithium tetraborate and the mixture was fused at 1100
1150C for 5min using a PerlX 3 automatic fusion
machine (Philips). The instrumental total error for each
sample was less than 1%. For the particular case of
performing the XRF analysis onto glass beads, the
detection was limited to approximately 0.1%.

The measurement of trace elements was performed
on a PerkinElmer ELAN9000 ICP-MS quadrupole
spectrometer. All samples were crushed into small-sized
pieces, cleaned with deionized water, dried in an oven at
60C and finally grinded in an agate mill. The dissolution
of the megabreccias was achieved using a closed vessel
digestion system, described as a programmable Microwave
(Milestone Ethos Touch Control), equipped with a high
temperature and pressure rotor for ten 100 mL Teflon
vessels (maximum work conditions of 1500 psi and 300C).
An amount of around 250 mg of powdered samples was
loaded into Teflon vessels. Different mixtures of HF,
, HCl and H
were used depending on the sample
Research Journal of Chemistry and Environment______________________________________Vol.15 (3) Sept (2011)

composition. The final solution was brought to a total
volume of 100 mL with deionized water ready for the ICP-
MS analysis.

The samples were introduced into the ICP-MS via
a Ryton cross-flow nebulizer, scott spray chamber and
Cetac ASX-510 autosampler. The sample transport from
the autosampler to the nebulizer was established by a
peristaltic pump. The operating parameters of the
spectrometer are summarized in table 1. The instrument
was calibrated and optimized daily using a standard
solution from PerkinElmer containing 10 ppb of Mg, Cu,
Rh, Cd, In, Ba, Ce, Pb, U in 1% HNO
, in order to obtain
the maximum precision, i.e. to achieve the maximum
103Rh intensity (>300 000 cps) and acquire an oxide/doble
charge ion levels lower than 3%. Internal standard and
external calibration were used. The internal standard is
103Rh and was added to the blank and standard solutions.
The multielement external standard solutions consisted of a
mixture of diluted solutions and were prepared from initial
monoelement solutions of 1000 mg L
(all from Panreac
Qumica SA, Spain), containing the analytes: V, Cr, Co, Ni,
Cu, Sr, Zr, Y, Ba, La, Ce, Nd and Pb.

The reproducibility of the measurements was
studied by doing 3 replicates of the analysis, monitoring the
relative standard deviations (RSD). It was < 5 % for most
elements.All reactives employed were suprapure reagent
grade (Merk), H
O was deionized water (18.2 M) treated
by a Milli-Q water system (Millipore).

Finally, isotope measurements (oxygen and carbon
isotopic signatures) of the carbonates which form part of
the silica-rich mega breccias were carried out at the Stable
Isotope Laboratory of the Estacin Experimental del
Zaidn (CSIC, Granada). Samples were ground to < 200
mesh to be later treated with 100% phosphoric
; the
analyses were performed using a Finnigan Mat 251 mass
spectrometer. Each sample was analyzed at least, three
times. The experimental error found was 0.1 for (
O), using Carrara and EEZ-1 internal standards,
previously compared with NBS-18 and NBS-19 and the
experimental reproducibility error was 0.2 for the

Results and Discussion
Based on the field study and on the mineralogical,
paragenetic and geochemical relationships, a new
classiffication of the Richat megabreccias is proposed,
comprising six compositional types of silica-rich
megabreccias (Table 2): 1) quartz-dolomite-calcite-albite;
2) quartz-goethite-carbonates (calcite-aragonite); 3) quartz-
kaolinite-albite; 4) quartz; 5) quartz-carbonates (mostly
calcite, dolomite and aragonite) and 6) quartz- goethite,

The mineralogical make-up of the megabreccias
includes all previously mentioned phases along with other
mineral assemblages which occur in lesser abundance.
They involve K-feldspar, biotite, muscovite, amorphized
carbon and analcime (this last one coming very probably
from the analcimolite, which has been interpreted either
as the sodic alteration of sediments
or as a hydrothermally
altered diatreme pipe
). The link between the
mineralogical and geochemical characteristics was
established, from macro- to microscale showing the
existence of: a) variable distributions of the major, minor
and trace elements; b) polymorphic phases; c) micrometric
cataclastic features and d) different textural intergrowths
and degrees of crystallinity of some minerals (Fig.2).

Geochemically, the different groups of
megabreccias display remarkable variations of the major,
minor and trace elements (Table 2). Principally, it is
important to note the high content of Ba (up to 700.2 ppm)
of almost all groups (Table 2) and significant geochemical
anomalies of: a) Ni (up to 1613.4 ppm) in the Q
megabreccias; b) Cu and Cr (up to 11, 9 and 3366 ppm
respectively) in the QGtHt megabreccias and c) Zr (up to
877.5 ppm) in the QKAb megabreccias. In addition, other
geochemical anomalies were also found in accordance with
the following mineralogical associations: a) V (up to
2906.8 ppm), Co (up to 780.2 ppm), Cu (up to 514 ppm)
and Zr (up to 149.5 ppm) in samples rich in goethite and
hematite; b) V (up to 9385 ppm), Ba (up to 700.2 ppm) and
Zr (up to 156.8 ppm) in samples rich in quartz and calcite
and c) Ba (up to 606.4 ppm), Co (up to 255.9 ppm) and Cr
(up to 157 ppm) in samples rich in quartz and aragonite. In
addition, significant anomalies of Re and Os in some
breccias were detected, which are currently under a more
specific study, due to its potential implications regarding
the origin of the structure.

Finally, the
C (V-PDB) composition of
dolomite ranges from -5.20 to -10.06 and values of -1.08
for calcite and -0.80 for calcite-dolomite mixtures.
O (V-PDB) composition of dolomite
ranges from 12.44 to -11.06 and values of -5.44 for calcite
and -8.46 for calcite-dolomite mixtures. This suggests a
meteoric (low-temperature hydrothermal) origin for the
source waters.

In short, the multianalytical approach focused on
the study of the silica-rich megabreccias from Richat has
allowed their detailed characterization on the basis of their
mineralogical, geochemical and (some) oxygen and carbon
isotopic signatures. Of particular interest was the
comparative mineralogical analysis of the material by
Raman, XRD and optic and scanning microscopy. The
results obtained yield essential information to know better
one of the most extraordinary geological features (the
megabreccia body) of this new proposed natural area in the
Sahara realm.

In addition, they emphasize the scientific
significance and uniqueness of the core part of the crater-
Research Journal of Chemistry and Environment______________________________________Vol.15 (3) Sept (2011)

like structure, which, besides deserving special
preservation (following the indications of the International
Union for Conservation of Nature), requires further
investigation about its origin.

Table 1
ICP-MS operating parameters used for the
determination of the minor and trace elements
Instrument PerkinElmer
RF power 1000 W
Nebulizer gas flow 0.85 l min-1
Plasma gas flow
Auxiliary gas flow
15 l min-1
0.5 l min-1
Spray chamber
Cross flow
Scott Type
Lens voltage 8 volts
Analog stage voltage - 1,900 volts
Pulse stage voltage 1,100 volts
Sweep / reading 17
Reading / replicate 1
Replicate 3
Scanning mode Peak Hoppping

Thanks to the Mauritania Embassy for the
permission to carry out the scientific campaign at the area
and also to the Spain Embassy in Mauritania for its
institutional backing. JMF acknowledges the financial
support of the Centro de Astrobiologa, in the context of his
research studies on terrestrial analogs. Special thanks go to
Binter Canarias for its logistic support.

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Fig. 1 A: Richat structure (Mauritania). : around 50 km. False-colour composite image, made using shortwave
infrared, infrared and green wavelengths, which was acquired by Landsat 7's Enhanced Thematic Mapper plus
(ETM+) sensor. Courtesy of USGS EROS Data Center Satellite Systems Branch, B:
General overview of the megabreccia outcrop, displaying the classical block-splitting structure. C: Close-up of one of
the meter-size boulders of megabreccia; note its faceted shape. D: Interior of one of the megabreccia boulder,
showing the heterometric mixture of fragments (in this case, mainly quartz).
Research Journal of Chemistry and Environment______________________________________Vol.15 (3) Sept (2011)

Table 2
Geochemical composition of the six main groups of silica-rich megabreccias, Major elements (wt %), Minor and trace
elements (ppm), BDL: Below Detection Limit. QDCAb: quartz, dolomite, calcite and albite, QGCar: quartz, goethite,
carbonates (calcite and aragonite), QKAb: quartz, kaolinite and albite, Q: quartz, QCar: quartz, carbonates (calcite,
dolomite and aragonite), QGtHt: quartz, goethite, hematite.

88.66-42.29 94.34-92.04 96.66
3.80-2.31 1.01-0.75 1.36
6.91-0.66 3.17-1.82 0.40
MnO 0.32-0.17 0.04-0.02 0.01
MgO 7.56-0.13 0.14-0.08 0.04
CaO 14.89-3.23 0.75-0.65 0.05
O 1.82-0.70 0.03 0.03
O 0.41-0.24 0.02 0.02
0.15-0.08 0.10-0.06 0.10
0.23-0.04 0.24-0.21 0.04
V 92.38-8.00 27.99-22.94 5.91
Cr 31.17-12.62 43.99-10.98 3.55
Co 36.3-BDL 149.3-73.25 180
Ni 29.51-BDL 27.40-26.23 3.88
Cu 7.21-BDL 17.02-12.24 1.48
Sr 113.3-29.88 41.38-40.13 25.6
Y 6.32-0.97 2.84-2.73 BDL
Zr 23.43-9.22 168.5-13.09 877.5
Ba 296.7-5.54 372.5-314.3 112.2
La 5.49-1.10 1.99-1.91 BDL
Ce 19.30-1.49 12.05-7.42 22.23
Nd 9.22-0.96 2.42-2.05 BDL
Q QCar QGtHt
95.66-93.72 98,50-95.26 71.69-5.43
1.72-0.71 1.36-0.48 3.82-1.47
1.48-0.49 0.69-0.05 71.92-21.91
MnO 0.04-0.01 0.06-0.00 0.70-0.04
MgO 0.19-0.10 0.10-0.04 1.53-0.09
CaO 0.85-0.14 0.59-0.10 0.43-0.35
O 0.03 0.04-0.01 0.11-0.08
O 0.48-0.01 0.02-0.00 0.21-0.12
0.14-0.04 0.13-0.02 0.29-0.06
0.19-0.04 0.11-0.02 0.64-0.41
V 13.46-3.35 385-BDL 337-34.33
Cr 10.89-1.85 157.4-11.33 3366-9.93
Co 135.5-0.99 255.9-121.3 62.48-40.91
Ni 22.87-1613.4 116.2-BDL 79.97-51.18
Cu 14.41-3.51 BDL 111.9-42.88
Sr 51.97-8.57 43.10-9.01 34.73-32.51
Y 5.92-0.38 57.69-BLD 40.30-2.89
Zr 63.94-3.69 156.8-19.56 45.71-31.26
Ba 372.7-68.95 700.2-42.10 216.5-147.1
La 3.33-0.35 BDL 16.23-1.40
Ce 12.64-0.82 BDL 21.59-12.16
Nd 2.39-0.36 BDL 19.57-2.09
Pb 24.21-1.84 13.82 13.87-2.65

Research Journal of Chemistry and Environment______________________________________Vol.15 (3) Sept (2011)

Fig. 2 A: Photomicrography (parallel light) displaying
the association of mostly euhedral quartz crystals and
iron oxi-hydroxides. B: Raman spectra of goethite and
hematite (1), goethite (2) and amorphized carbon (3). 4:
reference Raman spectrum of goethite.

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(Received 18
February 2011, accepted 25
July 2011)

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