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, JUNE 2014, 65, 3, 241—253 doi: 10.2478/geoca-2014-0014
Introduction
Paleosols from fluvio-lacustrine settings in Central Anatolia
are still unknown. What we know about them is limited to
some contributions from Atabey et al. (1998), Küçükuysal
(2011), Küçükuysal et al. (2012). However, much more at-
tention was devoted to the Mediterranean paleosols around
Adana and Mersin in the south of Turkey. Paleosols and re-
lated calcretes are widespread throughout Turkey, for exam-
ple, in Southern Anatolia in Adana (Kapur et al. 1987, 1990,
1993, 2000; Atalay 1996), in Mersin (Eren 2007; Eren et al.
2008; Kadir & Eren 2008; Eren & Hat
l
po˘glu-Ba˘gc
l
2010;
Eren 2011) and in Central Anatolia in K
l
r ehir (Atabey et al.
1998; Gürel & Kadir 2006, 2008) in Cappadocia and in An-
kara (Küçükuysal 2011 and Küçükuysal et al. 2012). The age
of the calcretes in Southern Anatolia was determined by ESR
and TL (Özer et al. 1989; Atalay 1996) and in Central Anato-
lia by ESR (Küçükuysal et al. 2011).
Paleosols have been thought to be very complex structures,
but they are actually just soils formed on a landscape of the
past (Kraus 1999). According to the paleopedological point of
view of Retallack (2001), soil has a definition of a material
forming the surface of a planet or similar body and altered in
place from its parent material by physical, chemical or bio-
logical processes. Due to their structures and properties, as
Morozova (1995) summarized, paleosols provide complex in-
formation about (i) soil processes shaping the soil profile itself
during pedogenesis in the warm interglacials and interstadials,
Mineralogical, geochemical and micromorphological
evaluation of the Plio-Quaternary paleosols and calcretes
from Karahamzal
l
, Ankara (Central Turkey)
CEREN KÜÇÜKUYSAL
1
and SELIM KAPUR
2
1
General Directorate of MTA, Geological Research Departement, Building G, Room: 204, 06800 Çankaya, Ankara, Turkey;
kucukuysal09@yahoo.com.tr
2
Çukurova University, Department of Soil Science, 01330 Balcal
l
, Adana, Turkey; kapurs@cu.edu.tr
(Manuscript received September 13, 2013; accepted in revised form March 11, 2014)
Abstract: We present the mineralogical, micromorphological, and geochemical characteristics of the paleosols and
their carbonates from Karahamzal
l
, Ankara (Central Turkey). The paleosols include calcretes of powdery to nodular
forms and alternate with channel deposits. The presence of pedofeatures, such as clay cutans, floating grains,
circumgranular cracks, MnO linings, secondary carbonate rims, traces of past bioturbation and remnants of root frag-
ments are all the evidence of pedogenesis. Bw is the most common soil horizon showing subangular-angular blocky to
granular or prismatic microstructures. Calcretes, on the other hand, are evaluated as semi-mature massive, nodular,
tubular or powdery forms. The probable faunal and floral passages may also imply the traces of life from when these
alluvial deposits were soil. The presence of early diagenetic palygorskite and dolomite together with high salinization,
high calcification and low chemical index of alteration values are evidence of the formation of calcretes under arid and
dry conditions.
δ
13
C compositions of the carbonates ranging from —7.11 ‰ to —7.74 ‰ VPDB are comformable with the
world pedogenic carbonates favouring the C4 vegetation; likely
δ
18
O compositions of the carbonates are between —3.97 ‰
and —4.91 ‰ which are compatible with the paleosols formed under the influence of meteroic water in the vadose zone.
Key words: Calcrete, paleosol, Central Anatolia, Plio-Quaternary, stable isotope, Aridity.
(ii) natural processes which characterize the transition to cold
semicycles (glacial stages) and (iii) diagenetic processes.
Therefore, paleosols and paleosol carbonates are widely used
as sources of evidence for paleoclimatology studies. Paleosol
carbonates – the calcretes or caliches – are very important
materials for interpreting especially the semi-arid to arid cli-
matic conditions of the past (James 1972; Goudie 1973, 1983;
Tucker 1991). This study uses the definition of calcretes de-
fined by Wright & Tucker (1991) that calcrete is a near sur-
face, terrestrial accumulation of predominantly calcium
carbonate, which occurs in a variety of forms from powdery to
nodular to highly indurated, resulting from the cementation
and displacive/replacive introduction of calcium carbonate
into soil profiles, bedrock and sediments in areas where va-
dose and shallow phreatic groundwaters become saturated
with respect to calcium carbonate. The mineralogical and
chemical composition of pedogenic phyllosilicates, which
form in a soil through alteration of detrital clays or by primary
precipitation, are strongly controlled by the chemical activity
of the soil solution, which in turn is influenced by the amount
and seasonality of rainfall (Buol et al. 1997; Tabor 2002). This
relationship clearly manifests the sensitivity of clay minerals
to the climatic conditions at the time of formation. The
geochemical characteristics of the paleosols and their carbon-
ates are clearly important proxies revealing the climatic his-
tory of the soil. The recent studies on paleosol geochemistry
(Nesbitt & Young 1982; Maynard 1992; Retallack 1997,
2001; Sheldon & Tabor 2009) stated that different proxies
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based on geochemical analyses can be used to infer the pe-
dogenic processes revealing the effect of chemical weather-
ing in paleosols.
The study area is in the south of Ankara around Karaha-
mzal
l
village. The paleosol section with calcretes of low- to
medium maturity begins to be visible around Lake Mogan
towards Kulu, Konya. All the way along the Konya road, red
coloured paleosols with calcretes could be recorded. There-
fore, the areal distribution of this paleosol continues towards
the southern part of Ankara. Towards southern Turkey, pa-
leosols become more reddish with calcretes of medium- to
high maturity level. These paleosols from the southern part
are well-studied, and this points to a strong need for such
studies of Central Anatolian paleosols.
The purpose of this study is (i) to explain the field charac-
teristics of Plio-Quaternary paleosols and calcretes in Kara-
hamzal
l
, Central Anatolia, (ii) to reveal their mineralogical
compositions with their micromorphological properties de-
fining the Pedogenic and diagenetic features and (iii) to
present oxygen and carbon isotope analysis of the carbonates
to emphasize their potential to reconstruct the climatic con-
ditions during the Plio-Pleistocene in the region. In this re-
spect, we employed mineralogical, micromorphological,
geochemical and stable isotopic proxies all together to de-
fine the characteristics of the paleosols and also to evaluate
the Plio-Quaternary paleoclimates in Central Anatolia.
Materials and methods
The Karahamzal
l
site in Ankara was selected as the most
appropriate setting to study paleosol development for obtain-
ing high resolution and reliable proxy data. The paleosols
were investigated on the basis of colour changes and mot-
tling revealing the horizon developments. The calcrete mor-
phologies and the contact relationships between calcretes
and the paleosols were also recorded during the field studies.
22 samples from paleosols and their carbonates (calcretes)
were collected from the newly exposed fresh surfaces of our-
crops/road cuts and also by means of drilling operations.
The drilling operation for Karahamzal
l
section was accom-
plished from the ground to a depth of 27 m. The soil colours
were determined by the Munsell Colour Scale in the field un-
der moist conditions. The thin sections of the Karahamzal
l
samples were prepared according to Retallack (2001) and
Fitzpatrick (1993) at the Thin Section Preparation Laboratory
in the Department of Geology at the University of Western
Ontario, Canada. 15 appropriate samples were selected and
analysed for their palinological compositions by Dr. Zühtü
Bat
l
. The mineralogical analysis was conducted by the X-Ray
Diffraction equipment at the Department of Earth Sciences
in the University of Western Ontario and Scanning Electron
Microscope at the Central Laboratory, Middle East Technical
University. Randomly-oriented powdered samples and the
clay-fraction samples were mounted on glass slides and
scanned using a Rigaku diffractometer (45 mA, 160 kV),
equipped with Co-K
α radiation. Randomly-oriented samples
were scanned from 2° to 42° 2
Θ, using a step size of 0.02° 2Θ,
and a scan rate of 10° 2
Θ/min; and air-dried and ethylene
glycol solvated samples were scanned from 2° to 32° 2
Θ, us-
ing a step size of 0.01° 2
Θ, and a scan rate of 1° 2Θ/min.
Combined procedures of Thorez (1976), Jackson (1979),
Brindley & Brown (1980), Tucker (1988) and Moore & Rey-
nolds (1989), were followed during the preparation of the
randomly-oriented powder and the saturated slides (for the
clay minerals) for x-ray diffraction. Ca, K and Mg-saturated
and glycerol solvated slides were prepared for each soil clay-
size sample and x-rayed at room temperature, whereas the
K-saturated samples were also x-rayed after heating to 300 °C
and 500 °C. Isotope analysis (
δ
13
C and
δ
18
O analyses of the
carbonates) was performed at the Laboratory for Stable Iso-
tope Science in the Department of Earth Sciences at the Uni-
versity of Western Ontario. A multiprep device coupled to a
VG Optima dual inlet stable isotope ratio mass spectrometer
was used for this procedure. For the determinations of the
geochemical compositions of the paleosols and their carbon-
ates, the ICP-AES technique was employed by ACME Labo-
ratories, Canada. The soil properties under the microscope
were all defined in the Soil Laboratories of the Soil Science
Department of the Çukurova University. Selected Au-Pd
high vacuum coated samples were studied under the scan-
ning electron microscope in the Central Laboratory of the
Middle East Technical University by a QUANTA 400F Field
Emission Scanning Electron Microscope at 1.2 nm resolu-
tion. The Energy Dispersive X-ray Spectrometer (EDX) was
also employed to obtain the chemical analysis of the specific
locations on the undisturbed samples.
Geological setting, paleosol/calcrete description
and the depositional environment
The study area is located in the southwest of Ankara, near
the Karahamzal
l
village (39°16’30.56” N and 32°57’30.70” E)
(Fig. 1A). The geology of the area was obtained by the field
studies conducted by Akçay et al. (2008). The stratigraphic
section drawn in this study combines both this study and the
field descriptions of this paper. The geological map of the
study area is given in Fig. 1B. The oldest unit is the
Dizilita lar Formation of the Paleocene—Early Eocene,
which is composed of turbiditic conglomerate, sandstone,
claystone and resifal limestone blocks. The Çayraz Forma-
tion of the Middle Eocene unconformably overlies the
Dizilita lar Formation. It was deposited as conglomerate and
sandstone in shallow marine and deep marine environments
of turbiditic conglomerate-limestones. Conformable above,
the I
·
ncik Formation was deposited as an alternation of
evaporitic, continental conglomerate, sandstone, mudstone
at the bottom and gypsum-anhydrite and mudstone at the
middle, cross-laminated conglomerate and sandstones at the
top. The evaporitic unit of this formation is called the Sekili
evaporate member. The age of the formation is Late Eocene—
Oligocene. The Central Anatolian Group, which has a wide-
spread occurrence in the region, was unconformably overlain
by the Late Eocene—Oligocene units. This formation consists
of conglomerate, sandstone, mudstone, gypsum, anhydrite
and limestone – ignimbrite intercalations. It is a continental
unit of Middle Miocene-Pliocene age. The coeval I
·
nsuyu
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Formation was a product of a lacustrine environment where
carbonate deposition was high. The Kozakl
l
Limestone
Member was deposited as lacustrine limestone of the Late
Miocene age. The Gölba
l
Formation of Pliocene age uncon-
formably overlies the Miocene units and is formed from allu-
vial fan and fluvial deposits. The youngest units in the study
area are the Quaternary alluvium deposits (Fig. 1B).
The road cut located in the Karahamzal
l
village is the sam-
pling site of this study (Fig. 2A). The studied section which is
39 m deep is in the continental rock units of the Gölba
l
For-
mation which is composed of grey, red and brown coloured,
unconsolidated, poly-origin conglomerate, sandstone and
mudstone. The soil features (e.g. soil horizons, soil structures
and traces of biological activity) of the reddish brown
mudrocks are the attributes designating the paleosols with cal-
cretes. Küçükuysal (2011) stated that the presence of pedofea-
tures, such as clay cutans, floating grains, circumgranular
cracks, MnO linings, secondary carbonate rims, traces of past
bioturbation and remnants of root fragments clarify that the
studied reddish alluvial deposits are paleosols and the carbon-
ate concretions are their calcretes. The paleosol layers have
sharp upper contacts with the overlying channel deposits
(Fig. 2B). The calcretes are massive, nodular, tubular and
powdery in form and show downward transitional gradations
(Fig. 2A). In total a 39 m succession is recorded in the study
area (Fig. 3). Red-brownish coloured fine grained mudstones
with carbonate accumulations alternate with channel deposits.
The columnar section defines the stratigraphic relation of
the lithologies with their field observations, soil morphologies
and Munsell Colours (Fig. 3). The lowermost unit is the
Fig. 1. A – Map of Turkey showing the location of Ankara and
Karahamzal
l
; B – Geological map of the study area representing
the positions and the ages of the lithological units and the location
of the Karahamzal
l
section (Dönmez et al. 2008).
Fig. 2. A – Field view of the studied section in which red coloured
alluvial deposits together with calcrete formations alternating the
channel conglomerates; B – Field view of the paleosols with sharp
upper contacts with the channel deposits (the hammer is 33 cm long).
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Fig. 3. Columnar section of Karahamzal
l
section with field descriptions and soil
properties.
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Mio-Pliocene Evciler Basalt (Dönmez et al. 2008), where un-
conformably above this unit, brownish red coloured mud-
stones/paleosols alternate with channel deposits up to 4 m
depth. However, the paleosols are divided into 3 separate
groups in terms of their macrostructures through the section.
The first group from bottom to 13 m depth has almost only
subangular blocky ped structure with a relatively low amount
of faunal and floral passages. The recorded Munsell colours
of the units within this range are 5YR 7/2 and 5YR 6/3. Cal-
cretes have sharp upper contact and transitional lower contact
with the old soils. Their poorly developed profiles include
calcretes varying from powdery to nodular (Fig. 3). From
13 m to 4 m depth, the second group of paleosols was deter-
mined with both subangular blocky and prismatic ped struc-
tures. They become more reddish relative to the lower levels
and still show alternation with channel deposits (Fig. 3).
This group of paleosols has more faunal and floral passages
with respect to the lower paleosols but illustrates the same
contact features. The Munsell colours observed within this
range for paleosols and their carbonates are 7.5YR 8/2,
2.5YR 3/4, 5YR 7/2, 7.5YR 7/3 and 5YR 6/3. At the top of
the section, paleosols become more reddish in colour with
subangular blocky, prismatic and also granular structural
units. Faunal and floral passages are the largest within this
range. The Munsell colours recorded area 5YR 5/3, 7.5YR 5/3,
2.5YR 4/4, 5YR 6/3, 7.5YR 6/3 (Fig. 3). The youngest unit
is the recent soil deposit observed with red colour and high
carbonate accumulation. The age of the calcretes in this suc-
cession was interpreted as Plio-Quaternary based on the strati-
graphic position of the paleosols and the comparative age of
the underlying volcanic unit together with the stratigraphically
coeval paleosols in Bala, where the calcretes were dated as
Middle Pleistocene (Küçükuysal et al. 2011) (Fig. 3).
Results
Mineralogy
Almost all of the paleosol samples contained quartz and
feldspar as the detrital non-clay component. However, calcite
and dolomite are oppositely present. Non-clay minerals
(quartz, feldspar, calcite and dolomite) were identified within
a size fraction of less than 63 µm. Quartz was determined by
the presence of 2 prominent peaks at 4.27 Å and 3.34 Å. Feld-
spars, however, were determined by the most intense peak at
3.2 Å. Calcite was determined with a sharp and intense peak at
3.03 Å and dolomite with 2.89 Å. According to the peak in-
tensities of the minerals on the XRD diagrams of the Karaha-
mzal
l
section, the relative amounts of the non-clay minerals
and the total amount of clay minerals within the bulk compo-
sition were calculated according to the method of Gündo˘gdu
(1982) (Table 1). According to this method, the intensity fac-
tors of 0.35, 0.74, 1.62, 1 and 14.63 were used for quartz
(3.34 Å), calcite (3.04 Å), feldspar (3.18—3.20 Å), dolomite
(2.89 Å) and total clay minerals (4.53 Å), respectively. Quartz
is present throughout the section, but it shows a decreasing
trend towards the upper part of the section and reaches almost
a constant value close to the upper levels. Its abundance varies
Sample Quartz Calcite Feldspar Dolomite
Clay Total
U13
4.1 0.0 0.0 52.3
43.6
100.00
U12
11.9 0.0 0.0 0.0
88.1
100.00
U11
8.5 0.0 0.0 0.0
91.5
100.00
U10
2.6 1.7 0.0 66.3
29.4
100.00
U8
6.4 2.2 0.0 4.1
87.3
100.00
U7
3.0 0.0 0.0 46.9
50.1
100.00
U6C
3.9 0.0 0.0 49.1
47.0
100.00
U6S
6.6 0.0 5.8 0.0
87.6
100.00
U5
6.1 0.0 5.2 29.8
59.0
100.00
U4
6.2 0.0 11.2 19.5
63.0
100.00
U3
9.5 0.0 5.5 0.0
85.0
100.00
U2
5.2 0.0 0.0 33.2
61.5
100.00
U1
7.1 0.0 3.6 0.0
89.2
100.00
A1
6.3 0.0 0.0 43.1
50.6
100.00
A2
11.2 0.0 4.2 0.0
84.6
100.00
A3
6.6 0.0 0.0 49.3
44.0
100.00
A4
7.4 0.0 0.0 17.6
75.0
100.00
A5
8.8 3.4 0.0 0.0
87.7
100.00
A6
8.7 3.7 0.0 37.0
50.6
100.00
A7
8.1 0.0 9.9 0.0
82.0
100.00
A14
9.8 0.0 3.4 0.0
86.8
100.00
A15
6.4 0.0 0.0 23.7
69.9
100.00
K-1
4.4 3.5 11.2 8.3
72.6
100.00
K-2
4.3 6.4 9.0 4.6
75.6
100.00
K-4
4.8 0.0 3.7 57.7
33.7
100.00
K-5
3.3 0.0 6.7 29.3
60.7
100.00
K-6
5.0 3.5 8.4 0.0
83.1
100.00
K-9
3.3 0.0 6.5 21.6
68.5
100.00
K-12
5.0 25.5 10.7
0.0 58.8
100.00
K-13
4.9 3.0 8.1 3.9
80.1
100.00
K-15
4.5 3.7 7.7 4.6
79.5
100.00
K-16
2.8 0.0 10.7 0.0
86.4
100.00
K-19
5.6 0.0 0.0 0.0
94.4
100.00
K-21
4.6 0.0 7.9 5.4
82.1
100.00
K-24
5.5 0.0 7.5 0.0
87.0
100.00
K-27
5.5 3.4 0.0 5.7
85.3
100.00
K-30
3.9 12.8
8.1
6.9 68.2
100.00
K-33
4.2 11.3
7.9
4.2 72.4
100.00
K-35
5.0 3.3 7.7 0.0
84.1
100.00
K-37
4.3 2.9 6.9 0.0
85.9
100.00
K-39
4.1 3.2 7.1 0.0
85.6
100.00
K-40
4.5 4.0 0.0 0.0
91.5
100.00
K-41
0.0 3.1 43.9 0.0
53.0
100.00
Table 1: Semi-quantitative analysis of bulk composition of samples
from the Karahamzal
l
section.
from 2.6 to 11.6 %. Dolomite appears in the lower parts of the
section at a very low quantity and then is absent at some lev-
els. However, it shows an increasing trend towards the upper
part of the section where calcite is absent. The abundance of
dolomite varies from a maximum of 66.3 % to a minimum of
3.4 %. Dolomite is found with calcite only at the bottom of the
section. This trend was checked and confirmed by XRD and
also by the staining test under the microscope. Feldspars, like
calcite, are much more abundant at the bottom of the section
and occur at lower values close to the upper levels. Their
abundance ranges from 3.4 % to 11.2 % through the section.
Total clay mineral amounts gathered from XRD diagrams are
generally higher than 40 %. The minimum value for clay min-
eral abundance is 33.7 % and the maximum is 94.4 %.
The clay-fraction of the studied samples of Karahamzal
l
section reveals the presence of smectite, chlorite, kaolinite,
illite and palygorskite in a decreasing order in the Karahamzal
l
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section. Smectite, the dominant clay mineral found in the
section is present in all samples including K-41 (the basaltic
body). It was identified by the 12 Å—14 Å peaks which shift
to 17 Å by ethylene glycol solvation. Mg-saturation and
glycerol solvation techniques yield detailed information on
the type of the swelling clay minerals, where the smectite
peak at 14.2 Å remains stable at 14.2 Å—14.3 Å reflections
(Küçükuysal 2011). This behaviour is typical of the beidel-
lite type smectite minerals (Thorez 1976). This was also con-
firmed by Ca-saturation at relative humidity of 54 % and
Ca-saturation with glycol solvation treatments. The smectite
of this section has a 14.2 Å reflection at Ca-saturation at rel-
ative humidity of 54 % which shifts to 17 Å peak by Ca-sat-
uration and glycol solvation. Smectite collapsed to 10.1 Å
reflection
by
K-saturation
and
heating
treatments
(Küçükuysal 2011). Kaolinite and chlorite are the two clay
minerals present in all samples except the basaltic rock (K-41)
underlying the paleosols. Kaolinite and chlorite have some
reflections overlapping each other. However, as Thorez
(1976) stated, chlorites have strong d(001) at 14 Å and
d(003) at 4.7 Å peaks, which do not occur in kaolinites.
Also, heating to 550 °C for an hour causes dehydroxylation
of the hydroxide sheet which is seen as an increase in the in-
tensity of the d(001) reflection of chlorites (Moore & Rey-
nolds 1989). Heating to 550 °C in K-saturated samples or in
unsaturated samples causes the collapse of kaolinite where
chlorite would still have the 14 Å and 7.3 Å reflections.
Illite is the easiest to differentiate from others. Its basal re-
flections are stable with all treatments and heatings. Therefore,
10 Å d(001) remains constant throughout the saturations. It is
almost absent in the lower section samples but appeared with
its 10 Å reflection in the upper section samples at low quan-
tity. The other mineral present in the clay fraction of the sam-
ples is palygorskite. It is easily recognized with its 10.4 Å
—10.5 Å reflection. This peak collapses to 10.1 Å by heating
to 550 °C. To overcome the peak-wise confusion on the pres-
ence of palygorskite with illite, SEM studies were also carried
out to reveal its fibrous morphology and particular interwoven
crystal orientation (Fig. 4). The presence of palygorskite is in-
dispensably valuable in paleoclimatic studies where it is ac-
cepted as proxy data for the reconstruction of the paleoclimate
of the region in this study.
The peak intensities of the clay minerals in the Karaha-
mzal
l
section were used to quantify the amounts of smectite,
chlorite, kaolinite, illite and palygorskite. The method of
Biscaye (1965) was followed during the calculation of the
relative amounts of the clay minerals (Table 2). According to
this method, 1, 1, 2, 0.5 and 1 are used as intensity factors
for kaolinite (7 Å), chlorite (14 Å), illite (10 Å), smectite
(17 Å) and palygorskite (10.4 Å), respectively. Smectite
shows enrichments and depletions. Its highest content is al-
most 100 % at the bottom of the section but it shows deple-
tion up the section reaching almost an abundance of 8.7 %.
Kaolinite and illite, the detrital phases, plot almost the same
trends on the diagrams. Kaolinite abundance ranges between
3.2 % and 25.6 %; similarly illite has 4.3 % to 38.9 % abun-
dance through the section. Chlorite, the other detrital mineral
found in the section, shows an opposite trend with respect to
kaolinite and illite. Its lowest value is 11.1 %, whereas it is
Smectite Chlorite Palygorskite Kaol.
Illite SUM
%
U-13
68.9 16.2
0.0
9.5 5.4
100.0
U-12
– –
–
–
–
–
U-11
– –
–
–
–
–
U-10
22.4 17.9
37.3 13.4 9.0
100.0
U-8
19.5 16.1
16.1 20.7
27.6
100.0
U-7
29.5 17.6
13.2 20.3
19.4
100.0
U-6S
44.5 21.1
0.0 16.7
17.6
100.0
U-6C
43.6 23.6
0.0 18.2
14.5
100.0
U-5
45.4 26.4
6.2 11.5
10.6
100.0
U-4
53.1 25.5
0.0 11.2
10.2
100.0
U-3
8.7 14.2
47.2 15.7
14.2
100.0
U-2
27.8 27.8
0.0 19.4
25.0
100.0
U-1
15.6 17.7
15.6 30.2
20.8
100.0
A-1
41.7 25.0
5.8 14.2
13.3
100.0
A-4
31.3 20.5
22.3 17.0 8.9
100.0
A-5
14.8 15.1
19.4 20.6
30.1
100.0
A-6
28.4 18.2
11.9 17.5
23.9
100.0
A-7
23.3 20.9
8.7 22.7
24.4
100.0
A-14
32.9 21.7
4.7 21.7
19.0
100.0
A-15
43.9 21.9
8.8 16.7 8.8
100.0
K-1
20.3 51.1
10.5
9.0 9.0
100.0
K-2
34.1 33.0
8.8 11.0
13.2
100.0
K-5
40.9 34.1
6.8
9.1 9.1
100.0
K-6
21.2 15.4
13.5 26.9
23.1
100.0
K-9
42.5 30.0
7.5 10.0
10.0
100.0
K-12
23.1 20.5
0.0 25.6
30.8
100.0
K-13
22.2 11.1
5.6 22.2
38.9
100.0
K-15
47.1 17.6
11.8 11.8
11.8
100.0
K-16
0.0 84.6
0.0 15.4 0.0
100.0
K-19
30.0 20.0
13.3 10.0
26.7
100.0
K-21
36.7 23.3
10.0 10.0
20.0
100.0
K-24
33.3 27.5
11.8 11.8
15.7
100.0
K-27
40.7 25.9
7.4 11.1
14.8
100.0
K-30
44.9 29.0
0.0 14.5
11.6
100.0
K-33
37.5 18.8
0.0 18.8
25.0
100.0
K-35
69.0 13.8
6.9
3.4 6.9
100.0
K-37
57.4 19.7
6.6
3.3
13.1
100.0
K-39
64.9 17.5
7.0
3.5 7.0
100.0
K-40
67.7 16.1
6.5
3.2 6.5
100.0
K-41
100.0 0.0
0.0 0.0
0.0
100.0
Table 2: Semi-quantitative analysis of clay fraction of samples
from the Karahamzal
l
section.
Fig. 4. SEM image on the bridge-like morphology of palygorskite
fibres in paleosols of the Karahamzal
l
section.
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84.6 % at maximum in the section. Palygorskite plots exactly
an opposite trend line to smectite and chlorite. The best line
for palygorskite abundance through the section shows an in-
creasing trend towards the top of the section. It starts with
4.7 % abundance and reaches a maximum of 47.2 %. The
dolomite stochiometry study was done by Küçükuysal
(2011) and the dolomites were evaluated as low to moderate
for Ca-rich types and secondary dolomites.
Micromorphology
The cementing material of the paleosols is fine grained
carbonate mineral, the size of which possibly suggests rela-
tively rapid precipitation. The grains are formed from mineral
and rock fragments. They have subangular to subrounded
edges implying that the source of those clasts is not so far
away from their provenance. The carbonate nodules are also
common in the calcretes of the Karahamzal
l
section. The
mineral and rock fragments, voids and dissolution channels
are surrounded by carbonate minerals which are a typical
feature of calcretes (Fig. 5A). Manganese dioxide coatings
also rim some grains and also occur as dense compound in-
fillings (Fig. 5B) and loose discontinuous clusters within the
voids (Fig. 5C). Cracks and faunal passages in the calcretes
are filled by coarse grained carbonate minerals. Carbonate
nodules, as distinctive features of paleosols and their carbon-
ates, and some voids are surrounded by carbonate minerals
having distinct sharp and angular edges as dog-tooth cement.
The presence of root fragments was also observed within the
paleosols (Fig. 5D).
Calcretes developed within the reddish-brown coloured pa-
leosols in the Karahamzal
l
section have a distinct similar co-
lour to the paleosols as a primary feature which can easily be
interpreted as being part of the soil profile. The arrangement
of the peds within the lower horizons of the Karahamzal
l
suc-
cession integrates from a subangular blocky to prismatic struc-
ture. The peds are bound by angular and subrounded surfaces.
Through the upper levels of the succession, the shapes of the
peds change to subangular blocky and to granular, where pri-
mary peds are more or less similar in size, and secondary
smaller ones indicate more advanced physical soil formation
than the lower layers. In general, the microstructure of the pa-
leosols within the Karahamzal
l
succession are subangular
blocky to granular and prismatic (Fig. 5E). The peds of the pa-
leosols (measure of the degree to which adjacent faces are
moulds of each other) are also well accommodated in the
lower levels of the succession, but vary from partial to unac-
commodated towards the upper parts of the succession.
One of the important pedofeatures in paleosols of the
Karahamzal
l
section are the clay coatings, clay skins or the
so called clay cutans (Fig. 5F). The coatings are found as il-
luviated clay features in the paleosol matrix. Polysynthetic
quartz grains, feldspar surfaces with weathering features,
rock fragments of volcanic origin, cherts, clastic sedimentary
rocks, basaltic and metamorphic rocks are observed as float-
ing grains in thin sections. Other pedofeatures observed are
the coatings and infills of MnO
2
along with carbonate miner-
als. Additionally, the secondary carbonate linings are also
accepted as important features of paleosols and their carbon-
ates. The Karahamzal
l
succession is a good example for pa-
leosols and calcretes, both having secondary carbonate rims
around floating grains, voids and carbonate nodules. This
fabric feature indicates the presence of pedogenic formation
in the calcretes of the Karahamzal
l
succession. The geomet-
ric relationship of the U-shaped voids within the calcretes of
the Karahamzal
l
succession directly implies the evidence of
the presence of past bioturbation. This is a prime phenome-
non for classifying the calcretes of the study as beta calcretes
according to Tucker (1991).
Geochemistry
The mineralogical and chemical compositions of the pa-
leosols are strongly controlled by the geochemistry of the
soil solution. Therefore, the geochemical characteristics of
the paleosols and their carbonates can be employed as im-
portant proxies revealing the climatic history of the soil. The
studies on paleosol geochemistry (Retallack 1997, 2001;
Sheldon & Tabor 2009) stated that different proxies based on
geochemical analyses can be used to infer the pedogenic pro-
cesses revealing the effect of chemical weathering in paleo-
sols (Table 3 in Küçükuysal et al. 2012). The whole rock
geochemical analysis of the samples from the Karahamzal
l
section is already listed in Table 7.2 in Küçükuysal 2011
(p. 151). In this context, salinization should reflect the pref-
erential removal of sodium relative to potassium in the sur-
face horizons, where The Na
2
O/K
2
O ratio of salinization
ranges from 0.1 to 0.41 for the Karahamzal
l
samples (Fig. 6).
The increase towards the upper horizons is evidence of eva-
poration indicating a consequent water movement in the pa-
leosols. Salinization for the arid-climatic conditions should
be greater than 1, however, in this case, it reaches a maxi-
mum of almost 0.6 without passing a reference standard
(Fig. 6). Calcification reflected in the (CaO + MgO/Al
2
0
3
) ra-
tio has a minimum value of 0.6 and maximum of 15.9. It is
high in calcretes and low in paleosol levels throughout the
section with increasing calcification values towards the sur-
face (Fig. 6).
The other paramater is the clayeyness suggesting a clay
accumulation rate varying from 0.14 to 0.22 which can be re-
garded as almost constant throughout the profile with a de-
pletion trend towards the top of the section in calcrete
horizons (Fig. 6). The plot of relative base loss vs. depth re-
flects the removal of mobile cations from the surface horizons
and their accumulation at depth. Relative base loss values for
the Karahamzal
l
section range from 0.06 to 1.28 documenting
the medium to high weathering of the paleosols and the leach-
ing of carbonates throughout the section (Fig. 6). Leaching
values are consistent with the earlier studies in that it is high in
paleosol levels and very low in calcrete levels. The values of
leaching for the Karahamzal
l
Section range from 0.43 to 2.92
(Fig. 6). Normally leaching values are expected to be greater
than 2 in well-drained soils with Na and K concentrations
well correlated with the leaching trends. This is the case for
the Karahamzal
l
section since it is seasonally well-drained;
the leaching values in paleosols are high. In arid conditions,
the leaching values decrease leading to the precipitation of
calcium and magnesium carbonates.
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To measure the degree of chemical weathering, a value
can be obtained by calculating the chemical index of alter-
ation (CIA) of the section in terms given by Nesbitt &
Young (1982) using molecular proportions of some ele-
Fig. 5. Photomicrographs: A – of two almost parallel void spaces surrounding a rock fragment and filled with sparry carbonate including
MnO
2
clusters; B – dense and continuous infilling of MnO
2
within a void space and around a feldspar fragment within a calcrete sample of
the Karahamzal
l
succession; C – clusters of broken/beaded MnO
2
coatings within a void space in a calcrete sample from the Karahamzal
l
succession with probable organic infill; D – plant parts and faecal excrements within the U-11 paleosol sample of Karahamzal
l
succession;
E – Subangular blocky microstructure and well accommodated ped structure of the paleosols within the Karahamzal
l
succession; F – pedo-
feature of clay coatings.
ments. The higher the value, the more intense is the weather-
ing. The CIA values of paleosols range from 73.42 to 82.97
for the Karahamzal
l
section (Fig. 6). This suggests that the
paleosols were affected intensively by weathering. Another
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measure for the chemical index of alteration is CIA-K which
omits the K addition. This value ranges from 80.70 to 92.6
for soils which are very similar to CIA values (Fig. 6). Con-
sidering 50 as CIA and CIA-K standard for paleosols, the
studied paleosol samples are greater than 50, implying a high
degree of chemical weathering for paleosols. The Mg index
is also used to assess the weathering affect on paleosols and
is calculated as 35 to 63.4 for paleosols, which are almost
consistent with the CIA and CIA-K values (Fig. 6).
Weathering trends can be displayed on an Al
2
O
3
—
CaO+Na
2
O—K
2
O (A-CN-K) triangular plot of Nesbitt &
Young (1984, 1989). Rollinson (1993) summarized the
trends on an A-CN-K triangular diagram as follows: Initial
stages of weathering form a trend parallel to the CN-A side
of the diagram, whereas advanced weathering shows a
marked loss in K
2
O as compositions move towards the
Al
2
O
3
apex. The trend follows mixing lines representing the
removal of alkalis and Ca in solution during the breakdown
of first plagioclase and then potassium feldspar and ferro-
magnesian silicates. Deviations from such trends can be used
to infer chemical changes resulting from diagenesis or meta-
somatism (Nesbitt & Young 1984, 1989). The paleosols of
the Karahamzal
l
section plot a trend line on the A-CN-K tri-
angular diagram (Fig. 7). The paleosols show a weathering
trend line slightly parallel to the CN-A side of the diagram
with a small deviation towards the loss of K. This implies the
very early stages of diagenesis.
Stable isotope geochemistry
Stable isotope results are measured relative to a standard,
VSMOW or VPDB. They are expressed with delta notation
(
δ) in parts per thousand (‰ or per mil). The isotopic com-
position of carbonates in the Karahamzal
l
section exhibit a
narrow range in
δ
13
C composition from —7.11 ‰ to —7.74 ‰
and a relatively narrower range in
δ
18
O composition from
—3.97 ‰ to —4.91 ‰ (Table 3). Upward lower values in
δ
13
C
were observed at the U10, U6C, A1, A6 and A15 levels, but
δ
13
C was enriched in the U7 and A3 levels of calcretes of the
Karahamzal
l
section. An almost parallel trend to
δ
13
C is ob-
served in
δ
18
O composition through the section in that it
Fig. 6.
Molecular
weathering
ratios
calculated
and
chemical
index
of
alteration
values
of
the
Karahamzal
l
paleosols
and
carbonates.
Fig. 7. Karahamzal
l
samples on the A-CN-K triangular plot of Nes-
bitt & Young (1984, 1989).
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shows upward depletions and enrichments at the same levels
with
δ
13
C except U6. Therefore, it can be mentioned that a
good covariance is observed between
δ
13
C and
δ
18
O values
of carbonates in the Karahamzal
l
section. The ranges of sta-
ble isotope values are typical of a meteoric vadose environ-
ment (James & Choquette 1990). The measured carbon
isotope compositions of calcretes are close to the isotope val-
ues typical for the soil carbonate formed from organic CO
2
produced predominantly by C4 vegetation cover and support
a pedogenic or shallow groundwater origin (Bajnoczi et al.
2006). The
δ
18
O values are also in the range of normal conti-
nental soil carbonate (Cerling 1984) and do not indicate pre-
cipitation from evolved groundwater. The
δ
18
O enrichment
at the top of the section is well-correlated with the water
evaporation process. The increase in
δ
13
C and
δ
18
O values of
carbonates implies an increase in the temperature. Such an
arid and warmer climate favour the increase in C4-vegetation
flora together with greater input of atmospheric CO
2
into the
profile and results in higher
δ
13
C
carbonate
and
δ
18
O
carbonate
(Cerling 1984; Alam et al. 1997; Andrews et al. 1998).
δ
13
C
δ
18
O
δ
18
O
Sample VPDB
VSMOW
VPDB
U-5
–7.4 26.4 –4.4
A-4
–7.7 26.2 –4.6
U-7
–7.3 26.2 –4.6
U-6c
–7.6 26.3 –4.4
A-6
–7.6 26.3 –4.5
U-2
–7.6 26.4 –4.4
A-15
–7.8 25.7 –5.0
A-1
–7.7 26.5 –4.2
A-3
–7.1 26.8 –3.9
U-10
–7.7 25.9 –4.9
U-13
–7.5 26.0 –4.7
Table 3:
δ
13
C and
δ
18
O isotope compositions of the samples from
the Karahamzal
l
section.
Evaluation of the proxies
Palygorskite has a general increasing pattern up to the sec-
tion indicating increasing aridity (Fig. 8). At the same time,
smectite shows a general decreasing pattern towards the top
(Fig.
8). Dolomite, similar to palygorskite has a general in-
creasing trend towards the top of the section, becoming abun-
dant in the calcrete levels (Fig.
8). As smectite decreases in
amount, palygorskite becomes enriched, possibly suggesting
the smectite weathering as one of the sources of Mg for the pa-
lygorskite formation (Fig.
8). It is also somewhat true for do-
lomite (for the formation of dolomite, Mg is also needed)
abundance that where the amount of smectite decreases, dolo-
mite becomes abundant. Therefore, this trend also implies that
smectite may also be one of the Mg sources for dolomite for-
mation. In addition, scanning electron images of the palygors-
kites in the Karahamzal
l
section show that palygorskites cover
the dolomites and form bridge-like structures (Fig.
4). This
also confirms the formation of palygorskite from the soil solu-
tion enriched in Mg. Dolomites are generally found within the
pore spaces with rhombohedral forms and covered with pa-
lygorskites implying that they were formed before palygors-
kite formations. It is possible to accept that the secondary
minerals, palygorskite and dolomite were formed during the
process of paleosol development by modification due to the
compaction-derived diagenesis. Under normal pedogenic
circumcitances, presence of such mineral may be utilized for
the paleoclimatic reconstructions. Their relative abundances
through the section may well indicate the climatic conditions
during the soil development (Fig.
8).
Molecular weathering ratios of the paleosols and calcretes
of the Karahamzal
l
section display different trends. These val-
ues fluctuate between paleosol and calcrete levels. Calcifica-
tion and salinization are very similar in both and increase
towards the upper sections. This implies increasing aridity
with increasing temperature (Fig.
8). The chemical indexes of
Fig. 8. Interpretation of all proxy data from the Karahamzal
l
section
(grey areas show possible arid and dry periods).
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the alteration values of CIA-K are parallel to the alteration val-
ues of MgI. These values are high within the paleosol levels
(Fig.
8). The highest values are greater than 50 which suggest
the occurrence of a medium degree of weathering within the
paleosols. The alteration values only show a decreasing trend
at the top where recent soil is occupied (Fig.
8).
As Nesbitt & Young (1982) stated, chemical weathering is
mainly controlled by moisture and temperature. The stable
patterns of the element records of the Karahamzal
l
section
indicate that a wet climate occurs in enhanced chemical
weathering conditions during the pluvial periods, while a dry
climate favours the formation of calcretes during interpluvials.
There is a positive correlation between
δ
18
O and
δ
13
C val-
ues of the paleosol carbonates which indicates closed environ-
mental conditions (Fig. 8). These are also consistent with the
constant provenance values of trace elements (Küçükuysal
2011) suggesting that there was no additional influx to the
system during the deposition of the units in the Karahamzal
l
section. This leads to the development of sedimentary units
with similar characteristics.
Different generations of carbonates with almost stable
geochemical composition conditions were detected. The
δ
13
C values ranging around —7 ‰ indicate high input of
δ
13
C
from lower soil respiration rates in dry seasons which typi-
cally correlates with the vegetation cover dominated by C4
plants and are accompanied by higher
δ
18
C values due to
evaporation (Driese & Mora 1993).
It is clear in Figure 8 that if all proxies are compared, it is
possible to conclude that the dry and wet periods alternate
through the paleosol sequence, in which dry periods favour
an increase in palygorskite and dolomite with higher isotope
signatures, while wet periods favour an increase in smectite
and decrease in molecular weathering ratios (Fig. 8). It is
clear that the studied section shows an alternation from wet
to dry conditions led by pluvials and interpluvials favouring
the formation of red-brownish coloured paleosols and their
carbonates. All this evidence points to the view that the for-
mation of carbonates may have occurred under early diage-
netic conditions during the shallow burial of the paleosols
under arid and dry climatic conditions.
Brief summary of the Eastern Mediterranean
Quaternary climatic archives
Turkish continental records of Quaternary climates are
well listed in Nicoll & Küçükuysal (2012). Lake Van (Wick et
al. 2003; Litt el al. 2009), Eski Ac
l
göl (Woldring & Bottema
2003; Roberts et al. 2011) and Konya Basin (Fontugne et al.
1999; Roberts et al. 1999) have climatic archives through the
Quaternary while Lake Abant (Bottema et al. 1993—1994;
Roberts et al. 2011), Gölhisar (Eastwood et al. 1999) and
Sofular Cave (Göktürk et al. 2011) only passed the Ho-
locene. The Eastern Mediterranean continental climate ar-
chives like Lake Mirabad (Stevens et al. 2006; Roberts et al.
2011), Qunf Cave (Fleitmann et al. 2007), Lake Lisan (Bartov
et al. 2003; Kolodny et al. 2005), Jeita Cave (Verheyden et
al. 2002; Göktürk et al. 2011), Soreq Cave (Bar-Matthews et
al. 2003; Göktürk et al. 2011) and Lake Zeribar (Stevens et
al. 2001; Wasylikowa et al. 2006) also passed through the
Quaternary.
Like the isotopic covariance in the central and southern
Turkey with eastern Mediterranean Carbonates, this property
was also identified in the carbonates of southern Europe
(Sorbas Basin, Karlich Rhine Valley, Elsterian Loess, Hol-
steinian Paleosol, Carbonates from Crete) (Candy et al.
2012). The studied calcretes have the stable isotopic composi-
tions implying the formation controlled by the same environ-
mental factors. As Candy et al. 2012 suggested for the
Mediterranean carbonates, aridity appears to be the major con-
trol on both
δ
18
O and
δ
13
C values in the studied soil carbon-
ates with evaporation and CO
2
degassing. This is confirmed
with the low leaching values during the dry seasons favouring
the formation of carbonate rich soil and/or calcretes.
Conclusion
The pedofeatures determined in the alluvial deposits of the
studied section contribute to understanding the development
of the paleosols and the relevant formation of the calcretes in
the Karahamzal
l
section. This study reveals that there is a
consistency between the isotope values, the mineralogical
compositions, the geochemical and micromorphological
characteristics of the paleosols and calcretes throughout the
Karahamzal
l
section.
The microstructural units of the paleosols and calcretes
point the formation in the vadose zone of the depositional
environment, where the semi-mature dolomite bearing cal-
cretes with biological activity are also present. Considering
the age of the paleosols as Late Pliocene—Pleistocene, it is
possible to conclude that the calcretes in Karahamzal
l
section
formed almost at the same time as the calcretes in Bala, Cen-
tral Anatolia (Küçükuysal et al. 2012). Therefore, the cli-
mates of the Late Pliocene—Pleistocene in the Karahamzal
l
section favour the formation of the paleosols and their cal-
cretes during the fluctuations from arid and dry to humid
and wet conditions with mainly C4 vegetation.
Acknowledgments: This study is a part of a PhD Thesis
completed by the author, which was financially supported by
TÜBI
·
TAK under the Project of 106Y172. The author is
grateful to Prof. Dr. Fred J. Longstsaffe from the University
of Western Ontario, Canada, for his help during mineralogi-
cal and stable isotope analysis of the samples And last but
not the least Prof. Dr. Asuman Türkmeno˘glu has devoted
much effort on all occasions as the adviser of the thesis. The
reviewers of this manuscript are kindly acknowledged for
their constructive comments.
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