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C, O, S and Sr isotope studies on the genesis of Fe-carbonate and barite


mineralizations in the Attepe iron district (Adana, Southern Turkey)
S- uayip Kupeli, M. Muzaffer Karadag, Ahmet Ayhan, Adnan Doyen, Fetullah Ark
Department of Geology, Selcuk University, 42031 Selcuklu, Konya, Turkey
Received 10 July 2005; accepted 18 December 2005

Abstract
The Attepe district consists of Precambrian, LowerMiddle Cambrian, Upper CambrianLower Ordovician and
Mesozoic formations. It contains several iron deposits and occurrences. Three types of iron-mineralizations can be
distinguished in the area; (i) Sedimentary Fe-sulde in Precambrian bituminous metapelitic rocks, and Fe-oxides in
Precambrian metasandstones (SISO), (ii) vein-type Fe-carbonate and oxides composed of mainly siderite, ankerite and
hematite including barite in LowerMiddle Cambrian metacarbonates of the Caltepe Formation (HICO), (iii) karstic
Fe-oxides and hydroxides essentially in the LowerMiddle Cambrian metacarbonates and the unweathered Fecarbonates (KIO). The latter type is more widespread and located at the upper parts of the most important mineable
iron deposits like Attepe deposit.
Oxygen-, carbon-, sulfur- and strontium-isotope studies have been performed on siderites and barites in the veintype ores, and on calcites in the recrystallized Caltepe Limestones to investigate the sources and formation mechanism
of primary ore-forming constituents. The d13C values of siderites and calcites in limestones of the Caltepe Formation
range from 10.10% to 8.20%, and from 0.8% to 2.30%. Both carbonate minerals show d18O values between
17.5018.30% and 16.2023.00%, respectively. The d13C and d18O isotopic variations do not indicate any direct or
linear relations between siderites and limestones. However, it is possible that the carbon and oxygen isotopic
compositions of carbonate minerals could be changed to some extent, when limestones were subjected to hydrothermal
processes or thermal alterations during metamorphism.
The isotopic values of barites display 32.4038.30% for d34S and 12.2014.70% for d18O. The strontium isotope
ratios (0.7171690.718601) of barites and the sulfur isotope compositions of barites and pyrites suggest that there are
no direct linkages of ore-forming compounds neither with a magmatic source nor with sedimentary pyrite formations
in the Precambrian bituminous shales of the Attepe formation.
According to the eld observations and the stable isotope data, siderites and ankerites should be formed by
interaction between iron-rich hydrothermal uids and Caltepe limestones, whereas isotope ratios of barites indicate
that they were formed by mixing of sulfur-rich meteoric waters and deeply circulated hydrothermal solutions.
r 2006 Elsevier GmbH. All rights reserved.
Keywords: Attepe iron deposits; Barite; Siderite; Carbonate host rocks; C, O, S and Sr isotopes; Turkey

Corresponding author. Fax: +90 332 2410635.

E-mail address: aayhan@selcuk.edu.tr (A. Ayhan).


0009-2819/$ - see front matter r 2006 Elsevier GmbH. All rights reserved.
doi:10.1016/j.chemer.2006.01.001

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1. Introduction
The Attepe mining district located in the west of the
Eastern Taurus Belt comprises the most important
iron deposits and mines in the KayseriAdana Region
(Fig. 1).
Archaelogic data indicate that historical usage of
the iron in Anatolia went back to 2500 BC, covering
the Hittite, Lydia, Roman, Byzantinian and nally
Ottoman civilization periods (Kutlay, 1971; Cihnioglu
et al., 1994). In the Attepe Region, a few ancient
mining remnants were also found by geologists and
mine workmen, but the major iron production in the
Attepe district was initiated in the late 1970s, especially
between 1977 and 2005, about 30 million tons of ore,
with grades of 4058% Fe, has been mined. This
corresponds to about 30% of the total Turkish iron

production in that period. In the study area, besides the


economic iron deposits represented by the mixing of the
SISO and KIO-type ores, there are small-sized and
noneconomic Precambrian sedimantary pyrite, magnetite and hematite occurrences, which are also important
due to being the oldest metallic mineralizations in
Turkey.
The general geological properties of the study area on
a regional scale were interpreted by Ozgul (1976).
Meanwhile some detailed geological, mineralogical,
petrographical and geochemical characteristics of the
iron ore deposits and prospects in the Attepe district
were described in a few papers (Henden and Onder,
1980; Unlu and Stendal, 1986; Ayhan et al., 1992;
Ayhan and Kupeli, 1991; Kupeli, 1999; Colakoglu and
Sezerer-Kuru, 2002). The hypotheses on the genesis
of the iron deposits discussed by some authors range

Fig. 1. Simplied geological map of the Attepe mining district; locations of the iron deposits and occurrence (after Kupeli, 1991).

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from hydrothermal, to hydrothermalmetasomatic to


sedimentary processes. So far, there was no investigation
on the isotope geochemistry of the iron mineralization in
the Attepe Region.
The purpose of this study is to determine the isotopic
compositions of primary minerals such as siderites and
ankerites (d13C, d18O ), barites (d34S, d18O, 87Sr/86Sr)
and pyrites (d34S) and their host rocks to be able to
explain the origin and formation of these minerals.

2. Geologic setting and mineralization


The formations in the Attepe district are grouped into
two main tectonic sections described as Geyikdag and
Bozkr units extending in NESW direction, and
covered by the Lower Miocene sediments (Fig. 1). The
Geyikdag Unit essentially consists of Precambrian
bituminous metapelitic rocks, metasiltstone and metasandstones, LowerMiddle Cambrian metacarbonates,
Upper CambrianLower Ordovician metapelitic rocks
and metasiltstone intercalated with calc-schists and
nodular limestones, and Mesozoic metaconglomerates.
The latter overlays the metamorphic basement with an
angular unconformity. All formations have been metamorphosed under lower grade of greenschist facies
conditions and polydeformed by the Prealpine and
Alpine orogeneses. Besides these autochthonous/paraautochthonous (?) metasedimentary rocks, the Bozkr
Unit comprises ophiolitic rocks, intruded by diabasic
dyke systems. The ophiolites of the Bozkr unit is
assumed to be emplaced to the region in the Upper
Cretaceous (Senonian) time, as a result of the compressional tectonic regime related to the closing of the NeoTetyhs Ocean during the Late CretaceousPaleocene
period of the Alpine orogenic system (Ozgul, 1976;
Tekeli, 1980).
Based on the geological and mineralogical data, the
iron ores in the Attepe Region are subdivided into three
types: (i) Precambrian sedimentary Fe-sulfide and
oxides (SISO) observed only at the basement of the
Attepe formation in the eastern portion of the Attepe
iron deposit; (ii) Upper PaleoceneLower Eocene
hydrothermal, hydrothermalmetasomatic Fe-carbonate
and oxides (HICO); and (iii) Middle EoceneRecent
karstic Fe-oxi-hydroxides (KIO).
The isotope studies were focussed on the HICO-type
iron ores and their host rocks (except two samples from
the SISO-type iron ores) in the area and this type of ore
is observed in all units except in the Lower Miocene
rocks of the sedimentary cover series. Economic iron
deposits occur essentially as veins and irregular-shaped
hydrothermal and karstic ore bodies in the LowerMiddle Cambrian, shallow-marine and sometimes
dolomitic metacarbonates of the Caltepe Formation
with a thickness of 220 m, and also occur as a few

deposits in the Mesozoic metaconglomerates of the


Karakzolugu Formation of the Geyikdag Unit. In any
case, the HICO-type iron ores are always accompanied
by the KIO-type iron ores.
When only the HICO-type mineralization is taken
into consideration, the iron deposits in the Attepe
district are represented by carbonate-bounded veins and
irregular-shaped masses, or lenses of hydrothermalmetasomatic-type siderite hosted by ankeritic zones and
veins or irregular-shaped masses of hydrothermal-type
barite-bearing hematite and small vein-type magnetite.
The geological data show that the HICO-type ores
were entirely controlled by tectonic structures, and
formed in a period soon after the Mesozoic, probably
during the PaleoceneLower Eocene period. Primary
ore minerals in this type are composed of Fe-carbonates
and Fe-oxides represented by sideriteankerite and
hematitemagnetite, respectively. Some features of
mineralizations are presented as follows:
(a) Siderite has a pure mineralogical composition
observed within the metacarbonates of the Caltepe
formation throughout the district, while siderites
associated with tetrahedrite, pyrite, chalcopyrite,
marcasite, calcite, dolomite and quartz minerals
occur only in the form of fracture llings in the
bituminous shale of the Attepe formation including
sedimentary pyrites and magnetite at the eastern
portion of the Attepe iron deposit.
(b) Ankerite commonly associated with dolomite,
calcite and quartz as gangue minerals, essentially
observed at the peripherical sites of the primary
orebodies in the metacarbonates of the Caltepe
formation throughout the district.
(c) Hematite with barite, and minor amount of
quartz, and calcite gangue minerals occur in all
units throughout the district.
(d) Magnetite with minor amounts of pyrite, quartz
and chlorite observed in the Precambrian rocks of
the Attepe formation.
The carbonate-hosted primary ore bodies (HICO)
were altered into the KIO-type ores by means of the
meteoric waters rich in carbonic acid related to weathering and multiphase endokarstication processes being
effective contemporaneously from the beginning of the
Middle Eocene to Recent time, and redeposited in the
karstic cavities.

3. Isotope geochemistry
3.1. Sampling and analytical techniques
A total of 51 samples representing barite, siderite,
ankerite, pyrite in ore bodies, and calcite minerals in the

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calcareous and pelitic host rock samples from seven


important iron deposits (Attepe, Kzl, Uyuzpnar,
Kartalkaya, Elmadag, Magaradere and Degirmendere)
and one iron occurrence (Magaradere) in the Attepe
(Mansurlu-Feke-Adana) district were selected for the
oxygen-, carbon-, sulfur- and strontium-isotope analyses.
Because the iron deposits and occurrences in the study
area underwent heavy weathering and multiphase
endokarstic processes which were resulted, in some
places, total oxidation of iron-carbonates and oxide
minerals and, the formation of secondary iron oxyhydroxide minerals, so that it was difcult to obtain
unaltered ore samples. Only a restricted number of
samples were taken from unweathered parts of the iron
deposits or occurrences.
Euhedralsubhedral coarse-grained barite, siderite
and pyrite samples were hand-picked under a binocular
microscope; massive barite, carbonate and ne-grained
siderite samples were also checked for contamination by
thin section optical microscopy and by X-ray difractometry. Before running isotopic analyses, separated
barite samples were puried by repeated treatments
(499%) with a HClHF mixture in order to remove
carbonates, silicates and metal oxide-bearing impurities.
The carbon, oxygen, sulfur and strontium isotope
analyses (compositions of the selected specimens) were
performed at the Activation Laboratories Ltd. of
Ontario, Canada.
For the Sr isotope analyses six pure barite samples
were dissolved in a mixture of HF, HNO3 and HClO4.
Before the decomposition, all samples were spiked with
a 85Rb84Sr mixed solution. Rb and Sr were separated
using conventional cation-exchange techniques. The
analyses were performed on a Finnigan MAT 261
8-collector mass-spectrometer in static mode. All
measured Sr isotopic ratios were normalized to
a 88Sr/86Sr ratio of 8.37521. The precision of measurements are presented in Table 2 for each sample
as 2 sigma mean standard deviation. During the
period of this work, the weighted average of 15
SRM-987 Sr-standard runs yielded 87Sr/86Sr ratio of
0.71026270.000011 (2s).
Approximately 25 mg of powdered siderite and
limestone samples for the C-isotope analyses was
digested with anhydrous phosphoric acid in a Y-tube
reaction vessel at 25 1C. The evolved CO2 was cryogenically distilled from the reaction vessel into a 6 mm Pyrex
tube and ame sealed. The CO2 gas was then inlet to the
ion source of a VG SIRA-10 stable isotope ratio mass
spectrometer and analyzed for the 13C/12C ratio.
Internal lab standards (Lublin carbonate) were run at
the beginning and end of each set of samples (typically
20) and were used to normalize the data as well as to
correct for any instrument drift. The internal lab
standard was periodically calibrated against the NBS

19 International Standard. All results are reported in the


d13C% notation relative to the international PDB
standard. Precision (1 sigma) using this technique is
typically better than 0.2 per mil (n 10 internal lab
standards, 1s).
For the sulfur-isotope analyses of barite and pyrite
samples, pure BaSO4 and pure sulde samples were
combusted to SO2 gas under 103 Torr of vacuum.
The SO2 was inlet directly from the vacuum line to the
ion source of a VG 602 Isotope Ratio Mass Spectrometer (Ueda and Krouse, 1986). Quantitative combustion to SO2 was achieved by mixing 5 mg of sample with
100 mg of a V2O5 and SiO2 mixture (1:1). The reaction
was carried out at 950 1C for 7 min in a quartz glass
reaction tube. Pure copper turnings was used as a
catalyst to ensure conversion of SO3 to SO2. Internal
Lab Standards (Sea WaterBaSO4 and FisherBaSO4) were
run at the beginning and end of each set of samples
(typically 25) and were used to normalize the data as
well as to correct for any instrument drift. All results are
reported in the d34S% notation relative to the international CDT standard. Precision (1 sigma) using this
technique is typically better than 0.2 per mil (n 10
internal lab standards, 1s).
Siderite, ankerite, barite, calcite and silicate samples
for the oxygen analyses were reacted with BrF5 at
650 1C in nickel bombs following the procedures
described in Clayton and Mayeda (1963). The uorination reaction converts O in the mineral (s) to O2 gas,
which is subsequently converted to CO2 gas using a hot
C rod. All reaction steps are quantitative. Isotopic
analyses were performed on a Finnigan MAT Delta,
dual inlet isotope ratio mass spectrometer. The data are
reported in the standard delta notation as d18O%
deviations from V-SMOW. External reproducibility is
70.19% (1sigma) based on repeated analyses of the
internal white crystal standard (WCS). Our value for
NBS 28 is 9.6170.10% (1s).

3.2. Results
3.2.1. C- and O-isotope results of carbonates
Oxygen and carbon isotope compositions of the
Caltepe limestone, siderite and ankerite samples are
listed in Table 1 and plotted in Fig. 2. The siderite
samples have d13C isotopic values varying between
10.10% and 8.20% (with an average of 8.80%),
whereas limestone samples have d13C values ranging
from 0.80% to 2.30% (with an average of 0.56%). The
mean values of the d13C of carbonate minerals from the
Attepe Region points to a lightmoderate composition
for siderites and to a moderate composition for calcites.
The d18O values of the limestone and siderite samples
from the Attepe iron district vary from 16.20% to 23%
with a mean value of 19.10%, and from 17.50% to

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Table 1. Carbon and oxygen isotope results of the Caltepe limestone, siderite, ankerite and whole rock samples from the Attepe
iron district
Sample

Whole
rock

Location

d13C%
(PDB)

d18O% (V- Sample


SMOW)

Mineral

Location

d13C%
(PDB)

d18O% (VSMOW)

ATPY-1
ATPY-2
EDY-1
EDY-2
UY-1
MDY-1
DY-1
K1.Y2
K1.Y3
MDY-2
MDY-3
ATPY6
ATPY7
Mean
ATPY-4

1
1
7
7
5
8
3
2
2
8
8
1
1

20.20
18.70
18.80
19.10
20.30
23
16.18
17.90
20.50
17.70
16.90
16.80
21.90
19.08
14.60

AUS-1
AUS-2
AS-1
AS-2
AS-3
AS-4
AS-6
AS-8
AS-11
DS-1
DS-2
DS-3
DS-4
KS-1
Mean

Siderite
Siderite
Siderite
Siderite
Siderite
Siderite
Siderite
Siderite
Siderite
Siderite
Siderite
Siderite
Siderite
Siderite
n 14

1
1
1
1
1
1
1
1
1
3
3
3
3
2

0.60
0.80
0.90
0.60
1.20
2.30
1.10
0.60
1.80
0.30
1.66
0.70
0.80
0.56
15.90

9.70
10.10
8.80
8.70
8.70
8.90
8.40
8.90
8.20
8.60
8.50
8.50
8.70
8.30
8.80

17.60
17.50
17.90
18
17.90
18
18.30
18
18
18.30
18.20
18.20
18.30
18.30
18.04

ATPY3

Limestone
Limestone
Limestone
Limestone
Limestone
Limestone
Limestone
Limestone
Limestone
Limestone
Limestone
Limestone
Limestone
n 13
Graphitic
schist
Phyllite

13.30

13.50

KA-1

8.10

23.40

ATPY5

Phyllite

14

14.60

KA-2

6.80

22.84

KAY5

Schist

13.30

14.60

Mean

Sideritic
ankerite
Sideritic
ankerite
n2

7.45

23.12

1: Attepe iron deposit; 2: Kzl iron deposit; 3: Degirmendere iron deposit; 5: Uyuzpnar iron deposits; 6: Kartalkaya iron deposit; 7: Elmadag iron
deposit; 8: Magaradere iron deposit.

Fig. 2. Plot of the carbon and oxygen isotope results of the siderites from the Attepe iron district.

18.30% with a mean value of 18.04%, respectively.


Apart from some samples, there are, in general, no close
correlations between their isotopic values and sample
locations.
The plot of the results on a d13C versus d18O diagram
shows that the isotope values of both minerals fall into
two distinct ranges (Fig. 2). Siderite isotope data form a

homogenous group, while calcite data are scattered in a


large interval of d18O but within a narrow range of d13C.
It has to be discussed to what extent the depositional
conditions and the regional metamorphism inuenced
the oxygen isotope ratios of calcites. This variation in
isotopic composition should be related to gradual
changes in depositional conditions rather than to

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multiple sources for carbonate minerals. The Caltepe


limestone was deposited in a shelf environment lying on
Precambrian clastics and pelitic rocks, and was overlain
by Upper CambrianLower Ordovician pelitic rocks. At
the beginning of and after carbonate deposition, the
depositonal conditions should be more different than
during the main deposition period of carbonate. As a
result, the broad range in oxygen isotopic values and the
small range in carbon isotopic values of the Caltepe
limestones indicate that hydrothermal/metasomatic
uids being rich in oxygen and poor in carbon should
have caused the slight isotopic variation.

3.2.2. S-, O- and Sr-isotope results of barites and pyrites


Although barites occur as minor mineral, besides
siderites as the major primary ore mineral of the iron
deposits in the Attepe Region, their isotopic data
provided useful genetic evidences.
The d34S and d18O values of barite samples collected
from six different iron deposits and one occurrence
display ranges from 32.40% to 38.30% and 12.20% to
14.70%, respectively (Table 2).
The results cluster in three different areas on a d34S
and d18O diagram (Fig. 3). These areas are described as
B, EB and KAB-series in accordance with the related
deposits, among which three clusters of sulfur isotopes
could be distinguished; 32.4034.80% for the B-series
from the Magaradere occurrence, 35.9038.30% for
Table 2.

the EB-series from the Elmadag deposit and 34.50


35.70% for the KAB-series from the Kartalkaya deposit
(Table 2, Fig. 3).
The d34S values of samples (except two samples) from
the B and KAB-series are similar to each other, while
those of EB-series are slightly higher. This difference can
be partly attributed to the different mineral compositions of the assorted host rocks of the iron ores, but also
it must be considered that it may have resulted from
various chemical exchange reactions and small amounts
of transported materials with different isotopic values.
Whereas the Magaradere occurrence in Ordovician
shales is composed of predominantly primary hematite
and barite, the Elmadag deposit occurs mainly in the
LowerMiddle Cambrian Caltepe limestones, and the
Kartalkaya deposit in a fault zone is between Precambrian and Ordovician formations as well as the replaced
Caltepe limestones showing different mineral composition than those of the Magaradere occurrence.
87
Sr/86Sr compositions of barite samples taken from
ve different deposits and one occurrence fall within a
narrow range from 0.717169 to 0.718601 (Table 2).

3.3. Discussion
3.3.1. Signicance of the C- and O-isotope results of
carbonates
The carbonates of magmatic-hydrothermal origin
were believed to have d13C values around 5% to

Sulfur and oxygen isotope compositions of the barite and pyrite samples from the Attepe iron district

Samples

Mineral

Locations

d34S (CDT)

d18O (SMOW)

87

B2
B3
B5
B10
B15
KB1
KB2
EB5
EB9
EB12
EB13
KAB1
KAB2
KAB5
UB2
DB1

Barite
Barite
Barite
Barite
Barite
Barite
Barite
Barite
Barite
Barite
Barite
Barite
Barite
Barite
Barite
Barite

T
T
T
T
T
2
2
7
7
7
7
6
6
6
5
3

32.40
34.70
34.80
34.30
34.80
35.50
36.60
35.90
36.20
37.80
38.30
34.60
35.70
34.50
36.60
35.30

13.70
13.60
14.10
13.50
13.40
13.70
13.70
14.70
13.30
13.20
13.20
12.20
12.80
12.70
12.90
13.20

0.718601713

0.718216713

0.718241713

0.717169712

0.718550710
0.718371712

Mean

n 16

35.50

13.37

ATP1
ATP2

Pyrite
Pyrite

23
22.30

Mean

n2

1
1

Sr/86Sr

22.65

T: Magaradere iron occurrence; 2: Kzl iron deposit; 7: Elmadag iron deposit; 6: Kartalkaya iron deposit; 5: Uyuzpnar iron deposit; 3:
Degirmendere iron deposit; 1: Attepe iron deposit.

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Fig. 3. Plot of the oxygen and sulfur isotope values of the barite samples from the Attepe iron district on a d18O versus d34S
diagram, (B: Magaradere iron occurrence; EB: Elmadag iron deposit; KAB: Kartalkaya iron deposit; KB: Kzl iron deposit; UB:
Uyuzpnar iron deposit; DB: Degirmendere iron deposit).

8%, while biogenic carbonates have often more


negative and varying d13C values (Ohmoto, 1972).
The mean value of the d13C in modern marine
carbonates is around 0%, whereas biogenically
reduced carbon compounds are isotopically light,
having a mean value around 25% (Hoefs, 1987). On
the other hand, the d13C values of carbonate rocks of
marine origin in Cambrian to Tertiary age are virtually
constant, and have values close to zero (Faure, 1986).
Carbon isotope compositions of the Caltepe limestones
are comparable with those of CambrianOrdovician
carbonate succession of Argentine Cordillera (Buggisch
et al., 2003), Lower Cambrian Lena River carbonates
from the Siberian Craton (Derry et al., 1994),
and Archean marbles of the Ruby Mountains (SW
Montana) (Brady et al., 1998). The values of d13C of the
studied area fall within the range expected for marine
carbonates.
The comparison of the Attepe results with various
source materials cited above indicate that the (CO3)2
of siderites in ore and in host limestone derived
from different sources. The (CO3)2 in calcite is similar
to that of marine carbonates, while that of siderites
is comparable to those of most early formed carbonate
minerals in hydrothermal veins (d13C values in the
range from 6% to 9%; Faure, 1986). A similar
carbon isotopic composition was also identied in
the Sierra Menera magnesitesiderite deposits (Northeast Spain) which were interpreted as hydrothermal
metasomatic deposits in the Late Ordovician dolomitic
formation of the Sierra Menera Unit (Fernandez-Nieto
et al., 2003), and in the Lombardy Valleys siderite
deposits (northern Italy) as stratiform orebodies in the

Lower Triassic terrigenous carbonate rocks, and in the


Permian volcanics, continental sequences and the
metamorphic basement as vein orebodies (Cortecci
and Frizzo, 1993). The latter deposits have a metasomatic origin.
Since there are no signicant differences in carbon
isotope composition between siderite and ankerite in the
study area, and the latter was formed in a peripheric
zone of the vein-type orebodies showing a succession
from a siderite core through the host limestones
displaying a hydrothermal aureole; both iron carbonates
are thought to be formed as a result of selective
replacement caused by inltration of Fe-bearing
uids.
Contrary to the large variations of d18O in limestones,
the d18O isotopic values of the siderites and ankerites
having negative d13C values are clustered into two
groups (Fig. 2). Thus, both iron carbonate minerals
have similar carbon, but different oxygen isotope ratios.
The latter showing lighter d13C values than those of
limestones indicate an additional carbon derivation
from another source with more negative values, which
could be related to the Precambrian graphitic schists
(15.90% per mil), and to the decomposition of organic
matters. These carbon constitutions should be formed
during alteration and mobilization of diagenetic pore
waters of the Precambrian rocks or after metamorphic
processes. Beside these, if the changes in the chemical
state of ore-forming uids were caused by reactions with
limestone, the d13C content might be changed (Ohmoto,
1972).
When compared with the Caltepe limestone, the
clustered oxygen isotope data of siderites and ankerites

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falling into two different narrow intervals (Fig. 2) need


to be explained: Under which conditions were they
formed? If the limestones were effected simply by an
uniform hot iron-bearing solutions, siderites and ankerites have to have similar d18O isotopic composition with
the that of the Caltepe limestone, which is not the such
case in our samples. These differences may indicate two
different uids with different oxygen isotope composition or with different temperature, which dissolved the
calcite of host limestone and precipitated the siderite
and ankerite.
In addition, the results of the uid inclusion studies
carried out by Colakoglu and Sezerer-Kuru (2002)
indicate that two siderite generations at the Attepe iron
deposit are not in agreement with the above-mentioned
oxygene and carbon isotopic compositions of the siderites.
The d13C and d18O isotopic variations do not indicate
direct or linear relations between siderites, ankerites and
limestones. However, it is possible that the carbon and
oxygen isotopic compositions of carbonate minerals
might be changed to some extent, when limestones were
subjected to hydrothermal processes and thermal
alteration.
3.3.2. Signicance of the S-, O- and Sr-isotope results of
barites and pyrites
S- and O-isotope compositions of barite samples
taken from six different deposits and one occurrence are
similar to those of Cambrian seawater (about 31%) on
the evaporitic sulfur isotope curve suggested by Claypool et al. (1980).
Although the Attepe deposits are hosted by limestones of the Cambrian Caltepe formation, they were
formed epigenetically, possibly in a period of Upper
PaleoceneLower Eocene. When the S- and O-isotope
results are compared with those of younger source
materials, they are isotopically heavier than those of the
Permian to Tertiary seawater sulfates (d18O 712%,
d34S 1022%; Claypool et al., 1980) or barite from
active hydrothermal vents (e.g. d18O 7%, d34S 22%
for barite from Mariana through; Kusakabe et al.,
1990). Although the sulfur isotopic values in the
Attepe Region are close to the value of Precambrian
and Cambrian seawater (31%) on the evaporitic
sulfur isotope curve of Claypool et al. (1980), they
are much higher than those of the Silurian and
Devonian seawaters (2324%). The heavy d34S
values of the Attepe barite samples are comparable
to the d34S values of stratiform barite deposits from
the Iglesiente-Sulcis mining district in Sardinia
which appear to be of epigenetic character (Cortecci
et al., 1989) and from Late Proterozoic to Lower
Cambrian marine barite deposits of the Liulin in the
Quinling Region and Xinghuang in the Jiangnan Region
of South China (Wang and Li, 1991; Maynard and
Okita, 1991), which were deposited in deep, poorly

oxygenated and tectonically active marine basin (Clark


et al., 2004).
The d34S values of the Attepe barites are heavier
than those of Huyuk barites (average d34S value
of 29.60%), located in the Sultandag Region of western
Taurus mountains, which were assumed as stratiform
barites with sedimentary and diagenetic features and
their sulfate ions were supplied from coevel seawater
(Ayhan, 2001).
In addition, the sulfur isotope composition of the
Attepe barites is heavier than that of European stratiform suldebarite deposits of Devonian age (Anger
et al., 1966; Nielsen, 1979; Dejonghe et al., 1989). Heavy
d34S of barites of the studied area indicates that there
was no contribution by bacteriogenic processes in their
formation.
The mean values of sulfur isotopes of barites in ore
veins differ clearly from those of two sedimentary pyrite
samples from the Precambrian Attepe formation
(22.65%, Table 2). The d34S values of the pyrites fall
directly into the range of Late Proterozoic seawater
sulfate (Claypool et al., 1980).
The d18O values of barites in the study area ranging
from 12.20% to 14.70% with a mean value of
13.4% (Table 2) are similar to the isotopes of stratiform
barites in the Iglesiente-Sulcis mining district with
12.7015.60% (Cortecci et al., 1989) and to those of
sulfate dissolved in Late Proterozoic (Claypool et al.,
1980), and may reect a temperature gradient and/or
some effect of fO2 on the isotopic ratios (Wilson et al.,
2003). Three different clusters of d18O and d34S values of
the Attepe barites on the d18O versus d34S diagram
(Fig. 3) implies that the SO2
ions were derived by
4
mixing of different waters.
Two metapelitic samples from the Precambrian
formations have oxygen isotope composition of 13.50
and 14.60 per mil (Table 1). In addition to these, a
representative sample of schists belonging to the Upper
CambrianOrdovician Seydis-ehir Formation has a
similar d18O value (14.60 per mil). Their oxygen isotope
values are consistent with the hypothesis that the barites
were emplaced together with the iron minerals in the
metapelitic rocks. This isotopic similarity indicates that
the source of the oxygen in SO2
4 should be related to
these formations.
The 87Sr/86Sr values of the Attepe barites (from
0.717169 to 0.718601, Table 2) are higher than those
of many vein-type and stratiform barite deposits
(e.g.; Iglesiente-Sulcis, Italy, Cortecci et al., 1989; Apuan
Alp, Italy, Barbieri et al., 1982; Aberfeldy, Scotland,
Hall et al., 1991) and hydrothermal barite deposits
(Paytan et al., 2002). The given range displays an almost
homogenous isotopic composition and indicates that
Sr-bearing solutions (and probably also Ba) originated
from the same sources without a signicant isotopic
fractionation. The considerable barite mineral contents

ARTICLE IN PRESS
S. Kupeli et al. / Chemie der Erde ] (]]]]) ]]]]]]

of the iron deposits and occurrences in the Upper


CambrianLower Ordovician Seydis-ehir formation suggest that both the Ba and Sr ions could probably be
derived by heavy leaching of mainly from the Seydis- ehir
formation.

the Selcuk University in Konya. We thank Prof. Dr. A.


Gokce (Cumhuriyet University in Sivas), Prof. Dr. H.
Orhan (Selcuk University in Konya) and Prof. Dr. M.
Burhan Sadklar (Karadeniz Technical University in
Trabzon) for their constructive and critical reviews.

4. Conclusions
References
Data for stable isotope ratios of carbonate, sulfate
and sulde minerals from the Attepe iron district
provide a new approach to the probable sources of
ore-forming compounds and formation mechanisms.
The Sr isotope data reect no direct relation to
magmatic uids of a probable magmatic intrusion
beneath this part of the Taurides. The nearest igneous
intrusion, the Karamadaz Pluton at Yahyal (Kayseri
Central Turkey) and the Horoz Granitoid at the Pozant
(Adana Southern Turkey) intruded during Lower
PaleocenEocene time are located 40 and 90 km from
the study area, respectively. This conrms that the
hydrothermal convection caused by these intrusions did
not extend up to the Attepe Region.
Uneconomic barites in all deposits, here used only for
the genetic tracing of the iron deposits have high d34S
and d18O values and no direct relation with either a
probable magmatic source or sedimentary pyrite formations. This suggests that they may have been formed
by the mixing of hot waters containing Ba and Sr with
meteoric waters including SO2
ions. In addition to
4
these, the ore-forming compounds of barites could be
related to circulated hydrothermal waters activated
either during metamorphic processes or by a supposed
intrusion through Precambrian and Cambrian formations at the basement of the Geyikdag Units.
Variations in carbon and oxygen isotope compositions of carbonate minerals may have resulted from
various chemical exchange reactions and small amounts
of transported materials with different isotope values.
The Precambrian and Upper CambrianLower Ordovician rocks comprising black shales, schists, quartzites
leached by high saline uids are thought to be the main
sources of iron, barium, strontium and sulfur elements.
The available isotopic evidences as well as mineral
correlations between sulde-bearing and pure siderite
portions point to different phases of ore forming uids.
Siderites and ankerites are considered to be formed via
replacement of Caltepe limestones by mixing of hot
iron-rich saline hydrothermal uids with oxidized
meteoric waters.

Acknowledgments
This work is a part of the project supported by the
Scientic Research Project Division (BAP, 200315) of

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