Figure 1. Location map
ANKARA
DENÝZLÝ
0
150
300
450 km
Güney
Baklan
Çardak
Bozkurt
Honaz
Sarayköy
Buharkent
Babadað
Pamukkale
D E N ÝZ L Ý
Kýzýlcabölük
Tavas
Serinhisar
0
10
20 km
Buldan
Kocabaþ
Dereçiftlik
K
K aklýk
N
GEOLOGICA CARPATHICA, 53, 2, BRATISLAVA, APRIL 2002
109—116
CLAYS IN DENIZLI REGION
(SOUTHWESTERN ANATOLIA), TURKEY
YAHYA ÖZPINAR, METE HANÇER and BARIS SEMIZ
Department of Geological Engineering, Pamukkale University, Kinikli, Denizli, Turkey
(Manuscript received October 4, 2001; accepted in revised form December 13, 2001)
Abstract: In this region, marine, continental and lacustrine clay deposits which are used as a raw material in the cement
sector were investigated. It is seen that Upper Cretaceous-Upper Eocene shales representing marine deposition are found
in Malidagi in economic quantities. However, their Na
2
O % and K
2
O % contents are higher than in other clays. The
Oligocene aged Bayiralan clay representing marine deposition have abundant magnesian minerals. Because of its high
MgO % content, this clay is not suitable cement standard. The areal extent of the Upper Miocene-Lower Pliocene Kizilburun
clays represented fine sediments in the floodplain are widely situated. These may be used in cement sector, but they have
reserve and environmental problems. The red coloured clays belonging to the Pliocene Sakizcilar Formation are sutitable
for cement standard. To decreasing the transportation costs of the Denizli cement factory, the Malidagi clay and Sakizcilar
clay may be used together in different proportions. If the Malidagi and Sakizcilar clays may be used, the contents of K
2
O %
and Na
2
O % will decrease.
Key words: petrographic properties, different clay occurrences, suitable cement standard.
Introduction
The first studies related to a large part of the Denizli region
(Nebert 1958) describe the geology of the region in general
(Fig. 1). The stratigraphical features of the Denizli Neogene
sediments were investigated by Taner (1973, 1974). im ek
(1982) contributed the features of geothermal areas. The clay
occurrences in the Neogene sediments were investigated by
Ovayurt (1984) and Özpinar et al. (1995), Gürel (1997), Özpi-
nar & Hançer (2000a,b,c) for possible use as a raw material in
the cement sector. Sun (1990), Konak et al. (1990), Sözbilir
(1994), Özpinar (1987, 1988, 1994) studied stratigraphical and
structural features of Denizli and its surrounding areas. Al-
tunel & Hancock (1993) studied the Quaternary tectonics of
the Pamukkale travertine. Okay (1989) divided the Honaz
Mountain into several tectonic units differing from each other
in term of their depositional conditions, stratigraphy, metamor-
phism, rock types and structural positions.
Geological settings
At the basement of the studied area, the Upper Cretaceous-
Upper Eocene Malidagi Formation is situated (Figs. 2, 3). The
Malidagi Formation consists of laminated clay, laminated
sandy clay, laminated silty clay, and intercalated sandstone
and marl. This unit is autochthonous and is overlain by the Ju-
rassic-Cretaceous Çökelez Limestone with a tectonic bound-
ary (Fig. 4). The Çökelez Limestone is overlain by the Karete-
pe mélange with a tectonic boundary. The Karatepe mélange
rocks are mainly composed of basic and ultrabasic rocks and
huge blocks of crystalline limestones. The Karatepe mélange
body was emplaced in this region in the Upper Cretaceous
(Campanian).
Fig. 1. Location map.
All of these formations at the basement are overlain with an-
gular disconformity by the Oligocene “Karadere Formation”
represented by alluvial fan and deltaic deposits. This unit is
represented by conglomerates, sandstone and siltstone. Karad-
ere Formation is conformably overlain by the Oligocene
MECC ‘01
DENIZLI
DENIZLI
Kizilcabölük
Babadag
110 ÖZPINAR, HANÇER and SEMIZ
“Bayiralan Formation”, made up of sandstone, marl, limestone
and claystones deposited in a shallow sea environment. These
formations at the basement are overlain with angular discon-
formity by the Upper Miocene-Lower Pliocene “Kizilburun
Formation” represented by conglomerate, sandstone, siltstone
and clay formed in alluvial fan and lacustrinal fluvial environ-
ments. The Kizilburun Formation is conformably overlain by
the Lower Pliocene “Sazak Formation” made up of limestone,
travertine, sandstone and clay representing lacustrine environ-
ment sediments. The Sazak Formation is conformably overlain
by the Pliocene Sakizcilar Formations made up of sandstone,
marl, silty claystone and clay representing alluvium fan and
lacustrine sediments. There are small clay deposits in Quater-
nary alluvium. One of these is found in the area of the south-
westhern part of Karapinar village.
Method of study
The purpose of this paper is to report the results of detailed
study of clay in the Belevi, Yoku ba i, Kaklik, Gürleyik and
Kocaba (Denizli regions) and its surrounding area (Fig. 1). In
this study, an area of about 178 km
2
was mapped in detail
(1 : 25,000 scale). Then about 8 km
2
of the Malidagi area was
mapped on a scale of 1 : 500, an about 12 km
2
of the Kizilbu-
run-Gürleyik, Kizilburun-Kaklik, Kizilburun-Belevi areas was
mapped on a scale of 1 : 2000. 683 specimens obtained from
drilling hole and opened channel were examined by micro-
scope, XRD, DTA, XRF and SEM. The clay minerals were
determined by XRD and DTA (26 samples) and electron mi-
croscope (8 sample). The chemical analyses of the clays were
carried out by XRF in the Denizli Cement Factory Laboratories,
Turkey. The raw mix prepared by iron ore, limestone and Mal-
idagi shale was heated at different temperatures. At 1250 °C,
1350 °C and 1400 °C, the free lime amount was determined
and mineralogical structure was obtained by X-ray patterns.
Results and discussion
In the clays the following petrographical properties were
identified by microscope, XRD and DTA methods (Figs. 5, 6
and 7).
The laminated clay, laminated sandy clay and laminated
silty clay of the Malidagi Formation investigated under the mi-
croscope contain quartz (3—15 %), calcite (2—10 %), albite (2—
5 %), muscovite (0—2 %), opaque minerals (2—5 %), iron ox-
ides (5 %), chlorite (5 %) and clay minerals (65—90 %). From
one location to other, the shale includes silty and sandy materi-
al made up of quartz, calcite and albite. The results of XRD
were the same with as results of polarizing microscope, which
contains quartz, calcite, albite chlorite, montmorillonite and il-
lite (Fig. 5a). In the laminated clay rocks, illite was obtained in
abundance. Dark green laminated clay contains chlorite with
illite and montmorillonite. In the gray laminated clay, chlorite
was not obtained.
Oligocene Bayiralan clay contains abundant illite and a
small amount of montmorillonite, as well as quartz, feldspar,
dolomite, calcite, chlorite, clinochrysotile and opaque miner-
als (Fig. 5b). It can be seen that magnesian minerals such as
chlorite, clinochrysotile have a negative effect on the chemical
compositions of the clays.
Fig. 2. Simplified geological map of investigated area.
N
CLAYS IN DENIZLI REGION, TURKEY 111
Fig. 3. Generalized tectono-stratigraphic section of the investigated area.
112 ÖZPINAR, HANÇER and SEMIZ
Fig.
4.
Simplified
geological
maps
and
locations
taking
specimens
and
their
columnar
sections.
Malidagi
shale
(A)
,
In
the
Denizli
cement
factory
clay
area,
Kizilburun
Kaklik-2
clay
(B)
.
AB
CLAYS IN DENIZLI REGION, TURKEY 113
Fig. 5. X-Ray diffractograms of Malidagi shale (a), Bayiralan clay (b), Kizilburun clay (c), red colour clay of the Sakizcilar Formation
(d), and Quaternary clay (e). Chl – Chlorite, il – Illite, Al – Albite, Ca – Calcite, Q – Quartz, M – Montmorillonite, d – Dolomite,
Clk – Clinochrysotile, f – Feldspar, S – Sanidine.
The Upper Miocene-Lower Pliocene Kizilburun clay con-
tains illite, montmorillonite, quartz, feldspar (albite, sanidine),
dolomite, chlorite (Fig. 5c). One of these clay occurrences
named Kaklik—2 has been used in the Denizli cement factory
since 1986, but it may be used up in one or two years. Silty,
sandy and gravelly levels and grains in clay levels and/or beds
cause changing of chemical compositions.
The mineralogical composition of the Pliocene Sakizcilar
clay is same as the Kizilburun clay (Fig. 5d) but they are red in
colour and they are found with intercalated thin limestone lay-
ers. On the other hand, the bottom of some locations of the Sak-
izcilar Formation has very thick marl levels. But owing to the
fact that the marls have some problems such as high MgO%,
they are not suitable for the cement sector (Table 1). Quaterna-
ry clays contain illite, quartz, calcite, dolomite, albite and
chlorite (Fig. 5e).
Malidagi shale was examinated by DTA analyses method.
According to differential thermal curves, illite shows a loss of
adsorbed water at about 100 °C, montmorillonite and chlorite
show a loss of adsorbed water at 100 °C (Fig. 6). The first en-
dothermic peak shows between about 100 °C and 300 °C.
These peaks appear after the loss of crystal water from the clay
minerals. The dehydroxylations of illite, montmorillonite and
chlorite begin at 400 °C. The loss of hydroxyls from illite be-
gins at about 400 °C and may continue to about 900 °C. In il-
lite dehydration appears at about 550 °C. In montmorillonite, a
second endothermic peak appears at about 600 °C. The third
endothermic peak appears between about 870 °C and 877 °C.
The third endothermic peak shows the structural change. The
last endothermic peaks between about 1197 °C and 1292 °C
show the melting point. Both phases persist up to 1292 °C.
After doing detailed mapping of the promising areas such as
the area of Kaklik-2, Belevi, Gürleyik, Malidagi (Figs. 5, 6, 7)
were taken orderly specimens. A total of 683 specimens were
taken from the whole studied areas for chemical and petro-
graphical investigations. The results of average chemical anal-
ysis from the clay occurrences are given in Table 1.
The values of high SiO
2
%, Al
2
O
3
%, Fe
2
O
3
% and total alka-
li (Na
2
O % + K
2
O %) are seen in the Malidagi shale (Table 1)
and the values of low SiO
2
%, Al
2
O
3
%, Fe
2
O
3
%
and total al-
kali (Na
2
O % + K
2
O %) in Kizilburun-Kaklik-2 clay. On the
other hand, the value of high CaO % is seen in the Kizilburun
Kaklik-1 clay (Table 1) and the value of low CaO % seen in
the Malidagi clay. It can be seen that sandstone and siltstone
intercalated beds in the shale have a negative effect on the
chemical composition of the shale.
400
200
0
10
30
θ
Cps
2
50
40
20
il
Ca
M
Chl
+
M
il
Chl
Clk
Chl
Clk
+
Clk +
Ca
Q
Q
Ca
Ca Q
Q
Ca
Ca
Q
Q
+M
il
d
d
d+
+
f
Q
500
300
0
10
30
θ
Cps
2
20
40
M
Chl
il
Chl
Chl
il M
Al
Q
Chl
Q
Al
Ca
il M
Ca Q
Q
Ca
Chl
Q
Q
Ca
+
+
+
+
180
100
0
20
θ
Cps
2
40
50
10
30
d
M
Q
+ Ca
M
Q
Q
Q
Q
d
Ca
Ca
Ca
M
Ca
Ca
f
100
200
0
10
30
θ
Cps
2
50
40
20
il
Ca
Q
Ca
Q
+Ca
Q
Q
Ca
Ca
Q
Q
Ca
il
il
400
200
0
10
30
θ
Cps
2
50
20
40
Al
Q
Ca
Ca
d+Q
Ca
il
il+Ca
Q
Ca
Chl
d
Q
d
Ca
Chl
Ca
Q
il
Chl
il
Al
a
b
c
d
e
114 ÖZPINAR, HANÇER and SEMIZ
Because of the marine deposits, decrease and increase of the
chemical composition of the Malidagi shale is regular. Where-
as cross bedding of gravel and sand is found in the Kizilburun
clays. Owing to the thickness and length of gravel and sand
cross bedding, the chemical composition of the Kizilburun
clays changes from one location to the other in an irregular
way (Fig. 4).
The average value of MgO % in the Bayiralan clay is higher
than in the other clays and the average value of MgO % is
10.46 %. In the Kizilburun Belevi clay and Sakizcilar marl,
the values of MgO % are 7.23 and 5.09 % respectively and
these values are higher than the Portland cement standard. The
modulus of silica is between 2.72 and 3.61. The high values of
the modulus of silica are seen in the Kizilburun Gürleyik clay,
Sakizcilar marl and Bayiralan clays (Table 1). These are 3.61 %,
3.37 % and 3.22 %, respectively. They are higher than the
Portland cement standard values (the modulus of silica values
is suitable between 1.9 and 3.2 and accepted values are be-
tween 2.2 and 2.6 at Turkish cement factories).
The modulus of aluminum is between 0.99 and 1.99. The
high values for modulus of aluminum of 1.99 is seen in Mal-
idagi clay. The low value for modulus of aluminum of 0.99 is
seen in the Bayiralan clay. The standard values for modulus of
aluminum are between 1.0 and 4.0. The suitable and accepted
values in Turkish cement factories are between 2.2 and 2.6.
Owing to their higher MgO % contents the Bayiralan clay and
Table 1: The results of chemical analyses of total 683 clay specimens from different clay occurrences in studied area.
Channel and drilling
Spe.
Numb.
SiO
2
Al
2
O
3
Fe
2
O
3
CaO
MgO
SO
3
Na
2
O
K
2
O
LOI
TOT.
SM
AM
Malıdağı clay
299
53.54
13.19
6.51
8.19
3.37
0.01
0.99
2.46
9.41
98.07
2.78
1.99
Bayıralan clay
11
35.24
5.72
5.8
17.9
0
10.46
1.21
0.50
0.77
21.05
98.70
3.22
0.99
Kızılburun Belevi
44
36.31
8.20
5.14
21.35
5.09
0.07
0.29
1.34
21.86
99.84
2.72
1.59
Kızılburun Kaklık-2
55
35.19
7.31
4.29
23.94
3.74
0.01
0.39
1.01
23.82
99.72
3.03
1.70
Kızburun Kaklık-1
(Yokuşbaşı)
77
39.15
7.85
5.25
19.19
4.16
0.01
0.55
0.93
19.90
99.71
2.90
1.49
Kızılburun Gürleyik
159
49.95
7.93
5.88
13.13
3.41
0.48
0.99
1.51
13.85
97.13
3.61
1.34
Sakızcılar clay
17
46.64
10.29
6.10
13.90
3.54
0.02
0.48
1.37
14.39
96.78
2.86
1.64
Sakızcılar Marl
13
41.37
6.62
5.77
17.37
7.23
0.3
0
0.38
0.84
19.83
99.54
3.37
1.14
Alluvium clay
8
41.93
9.50
5.76
15.02
4.93
0.37
0.96
1.84
15.79
96.13
2.80
1.64
Total
683
Fig. 6. Differential thermal curves of shale (Malidagi) samples. TG curves show the changing weight % of the samples dependent on the in-
crease of temperature (disappearing weight % on the sample up to 1000 °C shown on the thermograms). DDTA curve show the derivative
of DTA curve.
0,5
0,2
0,4
200
600
1000
1400
0
0
0,2
0,4
90
96
102
-0,1
582°C
693°C
763°C
905°C
870°C
905°C
1177°C
99°C
TG
1290°C
1197°C
87%
TG/%
DDTA/uv/mg/min
DTA/uv/mg
T°C
0,6
0,2
0,4
200
600
1000
1400
0
0,2
92
TG/%
DDTA/uv/mg/min
DTA/uv/mg
96
102
0,1
0
-0,15
100°C
690°C
877°C
69%
1292°C
1490°C
T°C
TG
a
b
b
a
Sakizcilar marl were excluded. The values of modulus of the
investigated area clays are within the Turkish Standard.
According to the results of the investigations, shales suitable
as a raw material for the cement sector occur in Denizli (Tur-
key). They are found in abundance in the Malidagi and Honaz
mountain region. So, in the Turkish cement manufacturers’ as-
sociation laboratory, the raw mix prepared by iron ore, lime-
stone and Malidagi shale was heated at different temperatures
such as 1250 °C, 1350 °C and 1400
°C. At these temperatures
the free lime amount was determined and the mineralogical
structures were obtained by X-ray patterns (Fig. 7). The
amounts of free lime at 1250 °C, 1350 °C and 1400 °C are
24.11 %, 4.78 % and 2.56 %, respectively (Figs. 7, 8).
According to Fig. 7a, in normal clinker, the C
3
S peak forms
at 52 degree and the C
2
S peak forms at 31—32 degrees. As can
be seen in Fig. 7a, C
2
S and C
3
S peaks did not form, because
clinkerization of the raw mix did not take place until 1250 °C.
It is understood that the peak of free lime found at 37—38 de-
grees is higher than the normal clinker. As a result, it can be
seen that clinkerization is not completed.
According to Fig. 7b, the peak of free lime found at 37—38
degrees is higher than the normal clinker. Respecting normal
clinker, free lime is higher than 2 %. Because of high free
lime, clinkerization was not completed at about 1350 °C.
According to Fig. 7c, free lime is still found in the clinker at
a level of 2.65 %. It is understood that clinkerization had not
CLAYS IN DENIZLI REGION, TURKEY 115
Fig. 7. X-ray diffractograms of clinker samples burnt at about 1250 °C (a), 1350 °C (b) and 1400 °C (c), respectively. C
3
S – tricalcium silicate
(Ca
3
SiO
5
), C
2
S – dicalcium silicate (Ca
2
SiO
4
), C
3
A – tricalcium aluminate (Ca
3
Al
2
O
6
), C
4
AF – tetracalcium aluminoferrite (Ca
4
Al
2
Fe
2
O
10
).
Speed of used up CaO in varies
temperature
0
5
10
15
20
25
30
1200
1250
1300
1350
1400
1450
Temperature 0
C
F
re
e
C
a
O
%
Fig. 8. Shown as a graphic of the speeds of consumption of CaO be-
tween 1250 °C and 1400 °C.
Oxide%
Raw
Material
CaO
SiO
2
Al
2
O
3
Fe
2
O
3
LOI
MgO
Limestone
52.18
2.06
0.57
0.41
42.2
0.83
Clay
7.72
54.49
13.08
6.29
22.0
3.47
Iron ore
2.9
16.01
5.37
67.74
4.89
1.44
Table 3: Chemical composition of clinker (Standard of lime –
95.95, modulus of silica – 2.2, modulus of hydraulic – 2.1, modu-
lus of aluminum – 1.33, C
3
S – 64.83).
Oxide %
CaO
SiO
2
Al
2
O
3
Fe
2
O
3
LOI
MgO
Clinker
66.55
21.51
5.46
4.084
0
2.2
Table 2: Chemical composition of raw materials (Modulus of sili-
ca – 2.3).
Conclusions
The following conclusions have been reached from the geo-
logical, petrographical and petrochemical investigation carried
out in the Denizli region.
1. The average MgO % of Bayiralan clay is higher than in
the other clay occurrences, because magnesian minerals such
26°
30°
35°
40°
45°
50°
54°
+
+
+
+
+
+
+
+
+
+
26°
30°
35°
40°
45°
50°
54°
+
+
+
+
+
+
+
+
26°
30°
35°
40°
45°
50°
54°
+
+
+
+
+
+
+
+
+
+
+
+
+
+
+ +
+
a
b
c
Speed of consumption of CaO
in varies temperature
completely finished, at about 1400 °C. This situation may
have happened to the various proportions of poorly heated ma-
terial in the shale, which includes mineral such as quartz, albi-
te and chlorite. As a result of investigation, it was found that
the raw material mixing with the Malidagi shale had a clinker-
ization temperature of 1400—1450 °C.
At the end of this experimental study, the whole problems
were kept in view. For production of clinker, the raw mixing
material was prepared from iron ore, limestone and shale, in
Denizli cement factory (Table 2). Clinker was formed after us-
ing light green laminated clay and grey laminated clay. The
mixing ratio of raw materials and chemical analyses and the
chemical conclusions of clinker are given in Tables 2 and 3.
116 ÖZPINAR, HANÇER and SEMIZ
as chlorite, clinochrysotile are abundantly found. In addition,
the Sakizcilar marl has a high MgO % content. Both Bayiralan
clay and Sakizcilar marl are not suitable for the cement stan-
dard.
2. In this study, it is seen that economic clay beds are found
in Malidagi (Malidagi shale). The amount of their Na
2
O % and
K
2
O % contents are higher than the other clays and they con-
tain the various proportions of difficult to burn mineral such as
quartz, albite and chlorite. As conclusion, the shale of the in-
vestigated area is suitable for use as a raw material for the ce-
ment sector. But, it is proposed that the shale may be used by
mixing various proportions of the other clays found in the
neighbouring area.
3. The areal extent of the Kizilburun Formation is widely
spread over the Kaklik-1, Kaklik—2, Gürleyik and Belevi re-
gions (Figs. 2, 3 and 4). The Kizilburun clay may be used in
the cement sector, but its bedding sizes are small. The Kizilbu-
run Belevi clay and clay marl contain intercaleted sand and
gravel levels. The sand and gravels are generally include ser-
pentinized harzburgite, dunite, gabbroic and doleritic materi-
als, dolomitic limestone, quartzitic rocks and such as with
quartz, calcite, albite, sanidine minerals. These situations ef-
fect the chemical compositions. The same problems are found
in the Gürleyik region. It is proposed that the Kizilburun clays
may be selectively worked. The gravel levels may be thrown
away in the clay stock area. If the Kizilburun clays are selec-
tively worked, they may be used in the cement sector.
4. Clay is produced for the Denizli cement factory in the
Kaklik-2 region belonging to the Kizilburun Formation. The
clay production in this area may be stopped within one or two
years, because of limited reserves of clay. The Kaklik-1 Belevi
and Gürleyik clays belonging to the Kizilburun Formation
have sandy and gravelly levels like the Kaklik-2 clay which
this situation effects to change of chemical composition were
obtained.
5. The red coloured clays belonging to the Sakizcilar For-
mation are suitable for the cement standard so there is no re-
serve problem. Other clay occurrences are found long distanc-
es from the Denizli cement factory. The deviation of chemical
composition is low. Thin limestone beds intercalated in clay
may have caused the deviation of the chemical composition of
the clay.
6. To decrease the transportation costs of the cement factory,
the Malidagi shale and red coloured clay belonging to the Sak-
izcilar Formation located in the northern part of Belevi village
may be used together in different proportions. If the Malidagi
shale and Sakizcilar red coloured clays may be used, the con-
tents of K
2
O and Na
2
O will decrease.
Acknowledgments: This study is supported by Denizli Facto-
ry T.A. . I am grateful to Denizli Factory staff for their contri-
butions.
References
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Quaternary travertine of Pamukkale, Western Turkey, 2. Geo-
morph., Berlin—Stuttgart 94, 285—302.
Gürel H. 1997: Geological investigation of around the Kaklik—
Yoku ba i-Belevi (Denizli) districts, Denizli, PAÜ. M. Thesis,
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