Arabian Journal of Earth SciencesVol.

1 (2014) - Issue 4: 16-25 2 ‫( العدد‬4102) ‫ لسنة‬3 ‫الدورية العربية لعلوم األرض المجلد‬

‫الدوريــــــــة العــــــــربيـــة لعلوم األرض‬

Arabian Journal of Earth Sciences (AJES)
www.arabianjournalofscience.com/index.php/AJES

SILICIFICATION IN THE PHOSPHATE DEPOSITS OF MAASTRICHTIAN-LUTETIAN

OF THE OULED ABDOUN BASIN, MOROCCO: SEDIMENTOLOGY, MINERALOGY
AND GEOCHEMISTRY.
Hamid EL Haddi1*, Abdelmajid Benbouziane1, Mustapha Mouflih1 and Mohammed Laadila2

1
Laboratory of Dynamics Sedimentary Basins and Geological Correlation, Hassan II Mohammedia-Casablanca University.
Faculty of Sciences Ben M'sik, B.P 7955 Avenue cdt. Driss Elharti. Morocco.
2
Earth Sciences Department, Mohammed V University, Faculty of Sciences Agdal, Rabat. Morocco.

KEYWORDS ABSTRACT

Phosphate, In Morocco, several occurrences of sedimentary phosphates had

Diagenesis, been deposited from the upper Cretaceous (Maastrichtian)
Silicification, through the lower Paleogene (lower Lutetian). The silicification
Maastrichtian-Lutetian,
is mainly represented by silex, chert, opal and chalcedony. They
Ouled Abdoun,
Morocco
usually form lenticular layers, asymmetric lenses, nodular and
silicified rocks.
The major and trace element content of a representative set of
sample was studied. The geochemical associations of SiO2 and
all the elements have remarkable relationship with the degree of
diagenetic silicification. Their geochemistry was controlled by
some factors: pH, environment of deposition, sediment particle
size, topography, bathymetry and the upwelling currents. The
host rocks silicified mineralogy, and the types of phosphate series
minerals, have high amounts of strontium and silicium related to
organic matter and marine currents. They are comparable to those
detected in phosphate deposits in the Ganntour basin. In the
studied deposits, silicification had provided organic matter
(radiolarians and sponges), and secondarily, by the dissolution
detrital rocks.

I. INTRODUCTION Late Cretaceous and lower Cenozoic phosphate

rocks of commercial grade have been exploited in
several countries located in the Middle East and in
16
* Corresponding author: Tel.: 00212-669-014-786; fax 00212-522-704-675. E-mail address: hamid.elhaddi@univh2m.ac.ma.
North Africa regions. Morocco is the major producer,
since it has more than three quarters of global reserves
in sedimentary phosphate (Lenoble, Salvan et al.,
1952). Most of the deposits worldwide are solely
composed of minerals of the apatite group. Phosphates
are one of the few industrial minerals that have no
competition from other compounds (Savornin, 1921;
Joleaud, 1923; Depéret and Russo, 1925).
The most important deposits have been reported
from the late Cretaceous (Maastrichtian) trough the
lower Paleogene carbonated series in center and
Saharan desert of Morocco. The pure phosphates are
studied and treated by the Office Cherifien of
Phosphates Group (OCP), and produce fertilizers
phosphates. These huge deposits are located in four
major basins. The largest is the Ouled Abdoun basin
with a size of about 100 km long, out of 80 km wide.
Others are relatively smaller, but cover vast areas,
explored by the OCP Group. These basins are marked
by diagenetic silicification phenomena.
The aim of the present paper is to study the
sedimentology, mineralogy and geochemistry
(depositional and diagenetic environment of silicified
Fig.1: Location map of phosphate occurrences in Ouled Abdoun Basin: EL Halassa, Ghar Tager and Sidi Chennane.
facies) of the silicification of the phosphates series
deposited in the Maastrichtian - Lutetian Oulad
Abdoun basin (Arambourg, 1952; Salvan, 1952-3;
Noubhani, 1993 and Noubhani and & Cappetta (1994
and 1997).
II. GEOLOGICAL SETTING
The Ouled Abdoun basin covers an area of more
than 10,000 km2 with at least thirteen phosphate
localities (Fig. 1). All deposits of those localities are
aged from late Cretaceous (Maastrichtian) to the lower
Tertiary (Paleogene). Our study focuses on the EL
Halassa, Ghar Tager and Sidi Chennane areas because
the silicification is various, abundant and had been,
relatively, studied morphologically and genetically.
The sedimentation deposit is located on the wide
continental shelf (Arambourg, 1952; Wadjinny, 1979;
Belfkira, 1980; Sancini, 1992; Noubhani and
Cappetta, 1992; Moutaouakil and Giresse, 1993;
Noubhani and Cappetta, 1995). Phosphate facies are
deposit in basin marked by eustatic and low
subsidence (Moutaouakil, 1990; Mouflih, 1991;
Mouflih et al, 1994).
17
III. SAMPLES AND ANALYTICAL
METHODS
Careful and systematic sampling was done in the
phosphate series. The siliceous facies and silicified
representative samples were collected from different
lithologic units. Twenty-four indurated samples were
studied in thin section by polarized microscope. The
nomenclature adopted for the petrographic study is
inspired of the carbonates classification of Dunham
(1962) and Folk (1975), and the phosphate
classification of Wadjinny (1979), Slansky (1980),
Belfkira (1980), Jourani (1988) and Mouflih (1991).
The samples were crushed in a steel mortar to a coarser
fraction, and then crushed in porcelain mortar until it
became fine-grained range in size from 50µm to
250µm. The product is powdered up to suitable mesh
sizes in an agate mortar, which was then transferred
into polythene bags; they are, then, numbered and
packed properly for geochemical analysis. All analysis
has been made out into the National Centre for
Scientific and Technological Research (CNRST)
Rabat Morocco. X-Ray Diffraction (XRD) examined
the mineralogical composition of the thirty samples.
The major elements (SiO2, Al2O3, CaO, MgO, P2O5,
Fe2O3, K2O and Na2O) and trace elements (Sr, Cu,
Cd, and Mn) have been analyzed by Inductively
Coupled Plasma/Optical Emission Spectrometry (ICP-
OES).

Fig.2: Texture of siliceous microfacies and forms of silicification of Ouled Abdoun Basin. (A) Silicification
in phosphates with ellipsoidal rognon of silicified phosphate (nougat facies). (B) Silicification of shaped cauliflower
silex in the phosphate marl. (C) Packstone to grainstone marked by ooïdes. (D) Peloids with round forms and presence
of algal fragments. (E) Micriticmicofacies with skeletal grains, peloids, algal fragment and coprolite. (F)
Pelphospharenite with microcracks filling silica in phosphate grains. (G) Texture of coprophospharenite with bioclast
test in a siliceous matrix. Silica a surrounded grains phosphatic. (H) Fringe siliceous cement (palisadic cement) and
centripetal siliceous cement (drusic cement) (EL Haddi et al, 2013).

18
IV. RESULTS
4.1 Sedimentology and petrography
The phosphate series Moroccan are reported at
intervals of marine transgression cycles of 3rd and 4th
order (Boujo 1976; Yans, 2014) while linking these
sterile deposits are interpreted as terms of marine high
level. In this study the basic sequence adopted is of
Champetier et al. (1978) of Moroccan phosphate
series. The Maastrichtian-Lutetian section of Ouled
Abdoun basin shows a thick succession of phosphate
(60 m); it is interbedded by layers of siliceous
limestones, marl and clay. The Thersites bank
(Hemithersitea, Thersitea) marks the top of this
section. In the middle of this sequence, a silicification
and many siliceous forms characterize the Ypresian
(Fig. 2 and 3).
Fig.3: Lithostratigraphic section and deposit
sequences of Maastrichtian-Lutetian of El Halassa
(Oulad Abdoun basin) by EL Haddi H et al., (2013),
modified.
4.1.1 Deposit sequences of the Maastrichtian
The identification of sequences was made
following the concept and terminology of Vail (1987).
The Stratigraphy of the phosphate series was
established from the lithological description of
outcrops and wells, basing, mainly, on fossil faunas of
Vertebrates (Arambourg, 1952) and invertebrates
(Salvan, 1952 and 1953), reviewed and refined by
Noubhani (1993) and Noubhani & Cappetta (1994 and
1997).
The Maastrichtian floor is six meters thick, it is
formed by the phosphorites with sandy texture rich on
bone debris (bone bed), and often graded on marly and
clay interbedded with phosphatic limestone. The
Maastrichtian is subdivided in two depositional
sequences SD1and SD2.
The first deposit sequence: SD1 is subdivided in
two parasequences: PS1 and PS2. The first one is
formed by two levels. At the base there is a calcareous
phosphate layer, rich on fossils, characterized by
packstone grainstone texture; the grains are poorly
sorted with various form. Above this level comes
brown to gray fossil phosphates, whose texture is
biophospharudites and intraphospharenites with a
calcitic and siliceous exogangue. The second
parasequence, PS2, is represented, at the base, by fine
marly phosphate, with intercalation of marls levels as
flasers bedding; the second terms is coarse sandy
phosphates and slightly marly, with a packstone
intraphospharenite texture. The sequence is topped by
green-yellow marl including millimetric phosphate
clay.
The second deposit of the Maastrichtian sequence,
SD2, has three parasequences: PS3, PS4 and PS5. The
first one, PS3, is formed by three terms: gray coarse
fossil calcareous phosphate (bone bed), represented by
grainstone with a biophospharudites texture at de base;
the second term appears gray marl phosphates with a
wackstone to packstone intraphospharenites texture.
This parasequence is ended, at the top, by phosphates
with a grainstone texture.
The second parasequence, PS4, begins with yellow
marl phosphates marked by wackstone to packstone
texture. It ended by yellow compact marl containing
poached phosphates.
The last parasequence, PS5, contains three facies:
the first one is gray phosphates with a grainstone
texture, the second is yellow compact marl containing
centimeter and decimeter lenticular flint, and the third
is yellow to red compact marls, which are laminated
and bioturbated.
19
4.1.2 Deposit sequences of the Danian - Thanetian
The Danian - Thanetian is seven meters thick, the
deposit sequence of the Danian, SD3, is marked by the
absence of marl and clay beds. The uppermost part is
characterized by a reshuffle the phosphate levels. This
unconformity surface is marked by calcified
phosphate which is rich by internal molds of the
Molluscan species Cardita Coquandi. This sequence is
subdivided in two parasequences: PS6 and PS7. The
first one, PS6, is beginning with phosphatic limestone
characterized by a packstone grainstone texture; the
grains size of phosphate are range between 0.2-2 mm
where it became coarse at the end of this sequences, so
it characterized by grainstone texture.
The fourth deposit sequence of the Thanetian, SD4,
is composed by two parasequences: PS8 and PS9. This
deposit sequence begins with phosphatic limestone
has a packstone texture. At the upper part, there is
coarse to average sandy phosphates with a coprolites
and grainstone texture, interbedded with calcareous
phosphate, rich in fossils; it is characterized by grains
size ranged from 200 µm to 5 mm, and cemented by
the sparite. This deposit sequence ended by green to
red clay marls, which are marked by the thin layers of
yellow compact marl with a clear red lamination,
containing the geodes of silica and lenses of
phosphates with a bioturbation intense (Fig. 2 and 3).
4.1.3 Deposit sequences of the Ypresian.
The Ypresian is twelve meters thick, and contains
three deposits sequences, SD5, SD6 and SD7, which
develop a very intense and various silicification.
The fifth deposit sequence, SD5, has four
parasequences: PS10, PS11, PS12 and PS13. The first
one, PS10, starts by gray phosphate limestone with a
grainstone packstone texture, rich on coprolites.
Above this term, appear coarse coprolitic phosphates
with a grainstone texture and topped by gray
calcareous marl. The second one, PS11, begins by fine
to average phosphates sandy with a grainstone texture
showing calcification and silicification at the base.
The sandy phosphates contained are interbeded with a
discontinuous rognon bank siliceous phosphate. The
rognon shows the same texture as the phosphate
cashing. Phosphatic grains and coprolites dominate
with a packstone grainstone texture. The top of this
parasequence is marked by plastic green clay marl,
includung centimeter nodules. These nodules develop
concretions forms named menilites forms.
The third parasequence, PS12, is represented by
two terms, the first is phosphatic calcareous with a
packstone texture and average to fine brown to slightly
yellow marl and coprolites phosphates at the top.
These phosphates contain silicified coprolites and
shark’s teeth of the species Otodus Obliquus. White
and green laminar marly limestones represent the last
term contained coprolites.
The last parasequence, PS13, starts with middle to
fine sandy phosphates, rich in coprolites, passing
progressivly to coarse sandy coprolitic phosphate.
Laminar siliceous marls represent the top of this
parasequence.
The sixth deposit sequence, SD6, is subdivided by
three terms; the first is coprolitic calcareous phosphate
with a packstone to grainstone texture. It contains
silicified phosphates including nodules. The second is
yellow marl phosphates with a packstone to grainstone
texture. This parasequence is ended by a term of white
silicified marl phosphate; these marls contain green
clay and yellow sandy marl, which is called Boujniba
formation.
The seventh deposit sequence, SD7, represented by
three terms: phosphatic calcareous marl, at the base,
with a packstone texture containing debris and
coprolites; it is marked by laminar zonation and
bioturbation. The second term is coarse sandy
phosphates with a grainstone texture. The last term is
siliceous marls.
4.1.4 Deposit sequences of the Lutetian.
The gradual vanishing of phosphate levels marks
the transition to Ypresian-Lutetian. The cessation of
phosphate sedimentation is replaced by carbonate
sedimentation. The Lutetian is subdivided in two
deposits sequences: SD8 and SD9. The phosphate
series it protected of erosion by the limestone bank of
Thersites. These depositional sequences are
subdivided into six parasequences: three in SD8,
PS16, PS17, and PS18, and three in SD9, PS19, PS20
and PS21.
The deposit sequence SD8 is characterized by the
progressive cessation of phosphate sedimentation.
Parasequence PS16 contains two terms at the base it is
limestone with horizontal strata contained poached
phosphate rich on debris of coprolites, the second term
is white plastic marl contained calcite geods
interbedded with chert. Parasequence PS17 is
represented by the end of the phosphate sedimentation
(discontinuous phosphate levels), it is composed by
two terms: at the base a thin phosphate level and the
second is yellow to white plastic marl with beds of
cherty limestone. Parasequence PS18 characterized by
a dominance of yellow to white marl, containing geods
calcite with the presence of lenses of flint, silicified
phosphates and silicified geods.
The deposit sequence SD9 is distinguished by
proliferation of carbonate sedimentation and on rich
gastropods (Thersites) and bivalves. Parasequence
20
PS19 shows two terms at the base silicified limestones
rich in Thersites and the second term is plastic
siliceous and calcitic marls contain limestone levels to
Thersites. Parasequence PS20 is shows at the base
silicified limestone Thersites overlain by siliceous and
calcareous marl plastics, including lenticular and
continuous levels of flint. Parasequence PS21 is
characterized at the base by rich silicified limestones
rich on lamellibranchs, above comes siliceous plastic
marls.
4.2 Mineralogy and geochemistry
4.2.1 Mineralogy
Studied samples are siliceous, silicified rocks;
these are siliceous limestone, siliceous phosphate and
siliceous marls. The phosphate mineral present in the
samples is carbonate fluorapatite (francolite)
identified by X-ray diffraction (XRD) analysis. It is
the apatite species in marine phosphorite (Bentor,
1980; McArthur, 1985; Abed & Fakhouri, 1996).
Other minerals are present which include quartz, opal
(Amorphous, Cristobalite and Tridymite), and calcite
also traces of secondary clay and dolomite are present
in some samples.
Fig.4: X-ray diffractogram of siliceous samples of the Ouled Abdoun phosphate Basin (Morocco).
4.2.2 Geochemistry
4.2.2.1 Major elements.
The X-ray diffraction (XRD) analysis shows major
peaks 3.34Å and 4.26Å, which agree with varieties of
minerals (crystalline and microcrystalline or fibrous
forms of quartz). In contrast, the opal type silica shows
intense and large peaks 4.10Å, 4.33Å and 2.50 Å,
which are either an opal CT (opal-Cristobalite
Tridymite) or an opal T (Tridymite).
The diffractogram of flint dominant mineral phase
is the quartz showing by peaks 4.26 Å, 3.34 Å and 2.88
Å and the second phase is a clay represented by peaks
10.4 Å (Fig. 4A). Siliceous limestone, the dominant
minerals paragenesis, are the quartz with peak areas
4.26 Å, 3.34 Å and calcite with peak 3.03 Å, The
second phase found a fluorapatite carbonate with
peaks ranging from 2.79 Å, 2.69 Å and 2.62 Å (Fig.
4B.). For siliceous phosphate, two phases are
determined (Fig. 4C): the first is the quartz, and the
second is the fluorapatite carbonate. The peaks of
these phases are similar to the others diagrams. In
diffractogram of siliceous marls, the dominant
minerals phases are the quartz with peaks ranging 4.26
Å, 3.34 Å, and the second phase is the calcite with
peak 3.03 Å (Fig. 4D).
Major elements data indicate that the siliceous and
silicified facies are composed of SiO2. The majority
of samples contain relatively average to high of SiO2
concentrations (8.03% to 70.03 for non-phosphatic
21
term and 0.08 to 6.2% for phosphatic term). Non-
phosphatic term is generally low of CaCO3
concentrations (0.91 to 9.65%), P2O5 between 0.09
and 14.47% and MgO between 0.07 and 10.17%. Most
analyzed samples have Al2O3, Fe2O3, K2O and
Na2O concentrations of <3.61%. In phosphatic
calcium terms components are CaCO3 ranging
between 7.16 to 95,12%, phosphorus contents, such as
P2O5, show large variations among the studied
samples ranging from 5.82 to 39.85%, Magnesium
contents, such as MgO, are generally low except in
sample11 which contains up to 34.27% of MgO due to
the presence of dolomite or clay. Concentrations of
aluminium, such as Al2O3 which represent the detrital
fractions in the studied samples are relatively low
except in the sample 11 that contains up to 15.63%
(Murray et al., 1992). The Fe2O3, K2O and Na2O
concentrations are generally low except in the sample
Silicification occurs in nature from the deep sea to
the surface (Millot, 1960, 1964). This author
emphasizes that the silicification (chert, chalcedony...)
is the product of crystal growth from solutions that
contain natural silica. For him (Millot, 1960), the
silicification associated with limestones are a little
difficult to interpret, because of the contrast between
the conditions of solubility of carbonates and silica,
opposition that promotes mutual replacements and
erases the witnesses primary structures. On the other
hand, pure water, in equilibrium with the partial
pressure of atmospheric C02 and calcite, has a pH of
8.4, which is the critical area for the solubility of silica.
When the pH turn down, the calcite is dissolved which
silica deposits. Establishment of epigenisis and
replacement is observed in silicified limestones (Thiry
et al, 1988; Sharma and Clayton 1965).
Petrographic observations of the siliceous and
silicified samples from the Ouled Abdoun basin have
revealed that phosphatic grains described as “peloids”
are fragments of phosphatic mudstone, which is intact
to partially silicified because they, sometimes, contain
bone fragments and silicified coprolite. The absence
of concentric structure within the phosphatic
mudclasts and the absence of phosphatic cements in
the phosphorites also support the reworked origin of
the phosphatic grains, and the presence of border
silicification around phosphatic grains is of early
silicification. The presence of bone fragments into
some silicified phosphatic and filling silicifed
phosphatic in bone cavities that is comparable to the
matrix of the silicified phosphatic and siliceous
mudclasts suggests that the bioclasts are also of
reworked origin and derive from similar phosphatic
mudstones, rich in silica.
11 which contains up to 24.88, 5.64 and 6.87,
respectively.
4.2.2.2 Trace elements.
Distributions of trace elements in the siliceous and
silicified samples phosphate are: Strontium shows
high concentrations up to 825.47mg/kg compared to
other trace elements. This is quite common in the
phosphorites from the Middle East–North Africa
phosphate belt (Baioumy, 2011). For phosphatic term
of trace elements shows of Sr: 214.24 to 825.47mg/kg;
of Cu: 10.45 to 25.46mg/kg; of Mn: 6.24 to
79.97mg/kg and of Cd: 2.73 to 145.47mg/kg. For non-
phosphatic term of trace elements shows of Sr: 45.64
to 643.52mg/kg; of Cu: 11.10 to 76.83 mg/kg; of Mn:
7.11 to 109.78mg/kg and of Cd: 0.49 to 148.36mg/kg.
V. DISCUSSION AND CONCLUSIONS
In general, the microscopic observation showing
that the phosphatic grains, coprolites and skeletal
fragments are silicified partially or totaly and the
cavities filled by microcrystalline quartz indicating
silicification, the same observations were made by Al-
Shereideh, et al., (2010) in the study of Jabal Kabid
phosphorite deposits in Southeastern Jordan, as a
result of diagenetic silicification.
The origin of the silica has been less discussed.
Authors suggest a high proliferation of siliceous test
organisms in subtidal environments, favoured by up-
welling currents (Sugitani et al., 1998). It is probably
the case in the Ouled Abdoun basin where siliceous
rocks are hosted by phosphate deposits.
Strong reflections at the peaks 4.32-4.10 Å and
lower at 2.5 Å find are the Opal CT. These reflections
are characteristic of cristobalite and tridymite (Jones
et al., 1971; Froehlich, 1974). The others peaks of
Cristobalite are not easy to identify. The strong
disorder of the structure of the opal is characterized by
very low reflection of tridymite (2.06, 1.63, 1.45 and
1.20 Å) (Ostroumov et al, 1999). The peaks 4.10 and
2.51 Å corresponding to an opal C is different with
silica glass 4.23 Å (Ostroumov et al., 1999; De Jong et
al., 1987). The formation of the opal is favoured by the
pore-water, rich in silica, marks this early diagenetic
stage; the same conclusions were drawn by Jourani in
1988, in the study of the diagenetic evolution of the
Meskala phosphates Bouabout deposits.
Samples riche in calcium often contain high
content of strontium (Chaudhuri et al., 1987), show
changes during digenesis, since high content of
strontium which are remarkable in the most open
marine area (Pascal, 1984). Wadjinny has also noted,
in 1979, that in the Ouled Abdoun and the Ganntour
23
basins, the values of strontium (Sr) are high in sandy
phosphate facies, phosphate nougat (facies nougat),
dolomite and the chert. The results of Mg agree with
the conclusions drawn by Boujo (1976) and Mouflih
(1991). These authors attribute the presence of this
mineral to a detrital fraction in the presence of
magnesian clays or the presence of dolomite.
Chambionnat (1963) considers that copper (Cu) is one
of the most important traces elements of Moroccan
phosphates. The copper values explain that the origin
is from sediments formed near the coast. Frequently
Cu and Mn are associated to organic materials. These
results of geochemical study agreed with
interpretation and conclusions of Shereideh, et al.,
(2013) about calcitization of phosphate grains from
the upper part of Amman formation, Southeast Irbid,
Jordan.
Relationship between SiO2 and major and trace
elements in the siliceous and silicified facies reveal
that these elements were precipitated by direct
syngenetic, epigenetic and authigenetic processes. The
silicificaltion was taken place in the reduced and
slightly oxidized environment, due to the rising of
upwelling currents which allow to the proliferation of
some organisms as radiolarians and sponges.
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