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Origin of galena and sphalerite mineralization in the Koru Volcanics, Biga

Peninsula, Turkey: Insights from MELTS modelling and SUPCRT calculations

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DOI: 10.1080/00206814.2012.744441

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Origin of galena and sphalerite mineralization in the

Koru Volcanics, Biga Peninsula, Turkey: insights from
MELTS modelling and SUPCRT calculations
a b a a
Demet Kiran Yildirim , Attila Kilinc , Fikret Suner , Mustafa Kumral , Gokce K.
c a
Ustunisik & Murat Budakoglu
a
Department of Geological Engineering, Istanbul Technical University, Istanbul, 34469,
Turkey
b
Department of Geology, University of Cincinnati, Cincinnati, OH, 45221-0013, USA
c
Department of Geosciences, Stony Brook University, Stony Brook, NY, 11794-2100, USA
Version of record first published: 30 Nov 2012.

To cite this article: Demet Kiran Yildirim , Attila Kilinc , Fikret Suner , Mustafa Kumral , Gokce K. Ustunisik & Murat
Budakoglu (2012): Origin of galena and sphalerite mineralization in the Koru Volcanics, Biga Peninsula, Turkey: insights from
MELTS modelling and SUPCRT calculations, International Geology Review, DOI:10.1080/00206814.2012.744441

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 International Geology Review
iFirst, 2012, 1–12

Origin of galena and sphalerite mineralization in the Koru Volcanics, Biga Peninsula,
Turkey: insights from MELTS modelling and SUPCRT calculations
Demet Kiran Yildirima*, Attila Kilincb , Fikret Sunera , Mustafa Kumrala , Gokce K. Ustunisikc and Murat Budakoglua
a
Department of Geological Engineering, Istanbul Technical University, Istanbul 34469, Turkey; b Department of Geology, University of
Cincinnati, Cincinnati, OH 45221-0013, USA; c Department of Geosciences, Stony Brook University, Stony Brook, NY 11794-2100, USA
(Accepted 8 October 2012)

Tertiary volcanism (34.3 ± 1.2 Ma and 0.4 ± 0.7 Ma) in NW Turkey produced lead + zinc bearing trachyte, latite, dacite and
Downloaded by [American Museum of Natural History] at 12:41 26 March 2013

rhyodacite tuffs, and agglomerates, as well as basaltic andesite, andesite, dacite, and rhyolite lavas. The primary objective of
this study is to develop quantitative models for the evolution of magmas that produced these rocks and for the dissolution,
transport, and deposition of disseminated ore as sphalerite and galena vein deposits. Our petrogenetic modelling using the
MELTS algorithm (Ghiorso, M.S., and Sack, R.O., 1995, Chemical mass transfer in magmatic processes IV: a revised and
internally consistent thermodynamic model for the interpolation and extrapolation of liquid-solid equilibria in magmatic
systems at elevated temperatures and pressures: Contributions to Mineralogy and Petrology, v. 119, p. 197–212) indicates
that the ore-bearing volcanic rocks reflect mixing of a basaltic andesite parental magma with a rhyolite magma. In addition,
our aqueous geochemistry modelling using the SUPCRT indicates that controlling parameters of the vein deposits were
pH = 5.3–9.2, f O2 = 10−55 –10−46 at 150◦ C and S = 10−3 molal. At 250◦ C, compared with 150◦ C, the mineral stability
field is more oxidized, yet the pH range is not significantly different (pH = 5.8–9.8, f O2 = 10−34 –10−43 ).
Keywords: Koru Volcanics; galena; sphalerite; magma mixing; fractional crystallization; MELTS algorithm; SUPCRT
algorithm

Introduction
The Koru area is located in the Serbo-Macedonian metal-
logenic belt that extends from Serbia through Greece and
Bulgaria and into the Biga Peninsula, which is located
46 km northeast of Çanakkale. Barite-bearing Pb–Zn
deposits that crop out in Biga Peninsula are typical exam-
ples of the Pb–Zn deposits hosted in the Tertiary volcanic
rocks within this region. The geology of the area com-
prises Eocene andesitic lavas and tuffs (Akçaalan andesite,
Taa), Oligocene sub-volcanic rhyolite lavas, domes, and
felsic tuffs intruded by silicic stocks or dikes (Adadağı
pyroclastics, Tad), Miocene felsic lavas (Dededağ dacite,
Tdd), and Plio-Quaternary mafic lavas (Karaömerler basalt,
Tkb) (Figure 1). These units are overlain by Quaternary
alluvium. (Bozkaya and Gökçe 2001).
Pb–Zn mineralization in the region is commonly asso-
ciated with andesite, dacite, and rhyolite volcanism and
mainly hosted by the Oligocene Adadağı pyroclastics con-
sisting of porphyritic, locally massive, autobrecciated, and
flow-banded rhyolite lavas and domes (Bozkaya 2001).
Ore minerals occur in veins ranging from a few mm to
about 3 cm in width and show two types of mineralization
including stockwork ore veinlets in the upper parts and ore
veins along the fault zones in a WNW–ESE direction in
the lower parts (Bozkaya 2001). Ore minerals are domi-
nated by galena, sphalerite, pyrite, ± haematite, and minor
amounts of chalcopyrite, whereas gang minerals are mainly
dominated by quartz, barite, and calcite.
Due to a complicated geologic history of sphalerite and
galena vein deposits, considerable efforts have been made
to understand their origin, transport, and deposition in
this area. Previous research concentrated on the geological
characteristics and genesis of the Pb–Zn deposits (Gjelsvik
1956; Dinçer 1958; Tolun and Baykal 1960; Alpan 1968;
Ünal 1992; Andıç and Kayhan 1997); remote-sensing iden-
tification of alteration zones on a regional scale (Yanagiya
and Sato 1989); trace element and REE geochemistry
of surrounding rocks; and fluid inclusion and oxygen,
hydrogen, sulphur, and lead isotopes studies (Bozkaya and
Gökçe 2001, 2002, 2008). Despite the general agreement
regarding the depositional styles of the deposits (vein,
stockwork, massive, and stratiform), the processes that pro-
duced these deposits are not well understood. Nevertheless,
most researchers agree that hydrothermal activity produced

*Corresponding author. Email: kirand@itu.edu.tr

ISSN 0020-6814 print/ISSN 1938-2839 online

© 2012 Taylor & Francis
http://dx.doi.org/10.1080/00206814.2012.744441
http://www.tandfonline.com
 2 D.K. Yildirim et al.

LA
SU
IN

E26°28’45”
LAPSEKI

E26°41’40”
N Gureci
PE
LU
I BO L ES Sahinli
EL EL Beyçayir
G
AN N40°15’45”
RD Umurbey Study Area
DA
DEDE DAGI
Hacigelen
N40°10’20” Koru Balciar N
Harmancik
CANAKKALE
Kocalar 0 km 5
H 17 a3 H 17 b4

H 17 b4
H 17 a3
Downloaded by [American Museum of Natural History] at 12:41 26 March 2013

Damlali Karaömerler

25

Eskikisla
- + 45
1
2

Akçaalan 3
- +
A Kirilmis T. A′

15
H 17 d2

H 17 c1
Asmali Koru

Hacigelen
Biberler

H 17 d2 H 17 c1
W Seferli D.
750 Mandrira D. Koru D. Tesbih D.
Kirilmis T.
W
500
Kuyutasi 750
500
250
250
0
0
A
A′

Quaternary Alluivium Oligocene Adadag ˘ pyro-

clastics (Tad)
Plio- Karaomerler M. Eocene Akçaalan N
Quaternary basalt (Tkb) andesite (Taa)

Miocene Dededag ˘ 0 1 km
dacite (Tdd)
15 Strike and dip
of bedding Working mine
Abandoned mine Main road 1 Eskikisla deposit
– Normal fault
+ Stabilized 2 Tahtalikuyu deposit
Silica-rich zones road
Fold axis 3 Ikinci Viraj deposit
Stream

Figure 1. Simplified geological map and major structural lineaments of Koru volcanic region [modified from Bozkaya and Gokce 2001].
 International Geology Review
by Tertiary volcanics was responsible for the deposits.
Some investigators have suggested that the disseminated
ore was initially brought to the near surface by Tertiary
volcanic rocks, followed by dissolution and precipitation
of sphalerite and galena by sulphur and chloride-bearing
hydrothermal solutions (Bozkaya and Gökçe 2008). Earlier
temperature of mineralization determined by fluid inclu-
sions in sphalerite ranges from 120 to 160◦ C (Bozkaya
and Gökçe 2002). However, recent communication with
Bozkaya indicates that the temperatures may be as high
as 350◦ C, which is also consistent with our fluid inclu-
sion study. Bozkaya and Gökçe (2008) suggested that Pb,
Zn, Cu, and S in sulphide minerals were leached from the
volcano-sedimentary units and redeposited.
Downloaded by [American Museum of Natural History] at 12:41 26 March 2013
This work attempts to answer two questions: (1) are
the lavas ranging in composition from basaltic andesite to
rhyolite and containing disseminated lead and zinc miner-
alization genetically related to each other and (2) what are
 geochemical parameters in terms of P, T, f O2 , pH, and
the
S that controlled the deposition of Pb and Zn as galena
and sphalerite? Both questions are critical to understand the
origin, transport, and deposition of ore minerals in the Koru
region.
Mineralogy of Koru volcanic rocks
Bozkaya and Gökçe (2008) gave a detailed description of
the mineralogy of the Koru volcanic rocks and presented
data on ore microscopy and sulphur and lead isotopes on
sphalerite and galena. The following is a brief description
of our petrographic analysis of the Koru Volcanics includ-
ing Eocene Akcaalan andesite (Taa), Oligocene Adadagı
pyroclastics (Tad), Miocene Dededag dacite (Tdd), and
Plio–Quaternary Karaomerler basalt (Tkb).
The hypo-hyaline porphyritic basaltic andesite from
the Koru region shows mainly glomeroporphyrtic texture.
The characteristic mineralogy consists of plagioclase,
hornblende, orthopyroxene, clinopyroxene, biotite, and
(A)
10 μ
(D)
10 μ
Figure 2. Thin section images under cross-polarized light showing major mineralogy and important textures of Koru volcanic rocks.
3
±quartz as phenocrysts and microlitic feldspar and Fe–Ti
oxides as microphenocrysts (Figure 2A). Plagioclase
shows mostly reverse and oscillatory zoning which may
be due to magma mixing or temperature fluctuations in the
magma. Secondary calcite and epidote have been observed
in plagioclase phenocrysts. Chlorite and epidote are typical
alteration products of pyroxenes. Opaque minerals are
generally observed in spaces among plagioclase and mafic
crystals, suggesting their late crystallization. Typically,
quartz crystals show embayment indicative of disequi-
librium with the melt. This is also common in magma
mixing.
The porphyritic andesites exhibit glomeroporphyrtic,
intersertal, subophitic, and ophitic textures (Figures 2B
and 2C). The characteristic mineral assemblage consists
of plagioclase, clinopyroxene, orthopyroxene, ±sanidine,
and ±quartz as phenocrysts and feldspar and Fe–Ti oxides
as microphenocrysts in the groundmass. Extensive oscil-
latory zoning in plagioclase phenocryts are very common
features of the Koru andesites. Mineral inclusions are often
observed in the rims as well as in the cores of plagioclase
phenocrysts. Chlorite, epidote, and muscovite are common
secondary alteration minerals.
Porphyritic trachyandesite and trachydacite show glom-
eroporphyritic and trachytic flow textures (Figures 2D and
2E). Major minerals are plagioclase, sanidine, clinopy-
roxene, biotite, hornblende, quartz, and Fe-oxides as phe-
nocrysts and microlitic feldspars, clinopyroxene, mica,
quartz, and Fe-oxides as microphenocrysts. Chlorite and
muscovite are common secondary alteration minerals.
The characteristic mineralogical composition of the
porphyritic rhyolites includes plagioclase, sanidine, quartz,
±biotite, and ±hornblende as phenocrysts and Fe–Ti
oxides as microphenocrysts (Figure 2F). Quartz crys-
tals show embayment. The presence of hydrous minerals
including biotite and amphibole in the andesites, dacites,
and rhyolites suggests that their parental magmas must
contain some dissolved water.
(B) (C)
10 μ 10 μ
(E) (F)
10 μ 10 μ
 4 D.K. Yildirim et al.

Bulk chemistry of the Koru volcanic rocks
We present 28 analyses of the Koru volcanic rocks
(Table 1), ranging in composition from basaltic andesite
to rhyolite in the total alkali-silica diagram (Figure 3).
Bulk chemical analysis of the samples was carried out
by the X-ray fluorescence (XRF) method using a Rigaku
3070 spectrometer at the Department of Geology of the
University of Cincinnati. For the XRF analyses, 0.7 g of
ignited sample was fused with 3.5 g of LiBO4 and a
few crystals of ammonium iodide (Mewe 1994). Chemical
compositions presented in Table 1 are reported on an
anhydrous basis; therefore, no water content is reported.
Analytical standards used in the XRF analysis include
AGV1, BCR1, BHVO1, BIR1, G2, JA2, JA3, JB1a, JB2,
Downloaded by [American Museum of Natural History] at 12:41 26 March 2013
linear trends (decrease in TiO2 , Al2 O3 , MgO, CaO, and
FeO∗ and increase in K2 O with increasing SiO2 con-
tent), which may be interpreted as either due to fractional
crystallization of the basaltic andesite (TY109) or due
to magma mixing between basaltic andesite and rhyolite.
Before quantitatively testing either of these two processes
by the use of the MELTS algorithm (Ghiorso and Sack
1995), the initial conditions of the Koru magmas in terms
of pressure (P), temperature (T), oxygen fugacity (f O2 ),
and water content (wt.% H2 O) need to be constrained.
Calculations using the MELTS algorithm
To test whether the selected parental basaltic andesite

JB3, JG1a, JG2, JG3, JGB1, JR1, JR2, QLO1, RGM1, W2,
JCH1, JSD1, JSD2, and JSD3. Relative precision based on
repeated analysis of the standards in Table 1 is computed
as 1% of the amount present.
In the total alkali versus silica (TAS) diagram
(Figure 3), the least differentiated composition, TY109, is
a basaltic andesite which was used as the parental com-
position. Scatter in the rhyolite compositions is due to the
alteration of rhyolite to chlorite and clay minerals. Harker
diagrams for the Koru Volcanics (Figure 4) generally show
magma (TY109) is capable of generating the rest of the dif-
ferentiated lava under fractional crystallization or magma
mixing, the initial conditions of the Koru parental magma
(P, T, f O2 , and wt.% H2 O) must be known. Our strategy
is to carry out a number of computations using the MELTS
algorithm with a range of pressure (500 bars to 4 kbars),
oxygen fugacity (quartz-fayalite-magnetite (QFM) − 2 to
QFM + 2), and water content (0.5–3 wt.%) conditions until
the computed melt composition matches the composition
of the Koru volcanic rocks.

Table 1. Chemical composition of the Koru volcanic rocks in terms of weight percentage of oxides reported on an anhydrous basis. Rocks
were analysed by the XRF method. Standard deviation indicates the analytical precision based on the repeated analyses of standards.

Sample number SiO2 TiO2 Al2 O3 FeO∗ MnO MgO CaO Na2 O K2 O P2 O5 Total

I53 75.40 0.16 12.41 0.79 0.04 0.04 0.06 0.39 10.17 0.02 99.47
I50 73.72 0.18 13.09 1.94 0.06 0.32 0.03 0.11 9.35 0.03 99.43
T37 68.06 0.27 17.75 2.54 0.06 0.80 0.06 0.21 9.13 0.02 98.91
E12 71.70 0.24 14.00 1.61 0.00 0.01 0.08 0.88 9.78 0.03 98.33
E13 69.78 0.25 14.43 1.33 0.06 0.13 2.07 2.57 5.34 0.58 96.54
K58 75.31 0.23 12.76 0.59 4.43 0.33 0.24 0.31 8.52 0.14 102.85
K72 72.02 0.18 12.80 2.49 0.05 0.25 0.39 0.20 9.69 0.82 98.90
TY107 67.67 0.49 14.93 3.72 0.08 2.13 2.84 3.22 4.85 0.13 100.05
TY108 71.00 0.42 14.19 3.13 0.08 1.70 1.83 4.49 2.98 0.17 99.99
TY109 55.57 0.93 16.11 7.33 0.12 6.09 7.89 2.58 2.44 0.26 99.32
TY114-II 61.17 0.77 15.43 6.20 0.13 4.06 5.04 2.99 3.64 0.20 99.63
TY118-I 67.18 0.58 15.08 4.37 0.10 3.04 1.50 3.50 4.20 0.13 99.67
TY118-II 66.96 0.58 15.37 4.76 0.11 1.89 0.35 3.14 6.42 0.14 99.70
TY97 69.70 0.47 14.45 3.21 0.07 1.78 1.87 3.97 4.30 0.17 99.98
TY98 64.47 0.56 16.40 4.48 0.12 2.49 3.00 3.89 4.25 0.20 99.87
K57 71.67 0.29 14.21 1.21 0.01 0.02 0.46 0.94 7.51 0.03 96.35
K60 70.79 0.33 15.03 2.07 0.08 0.41 1.50 4.05 5.20 0.09 99.55
K61 67.75 0.46 17.04 2.85 0.09 0.85 1.02 4.12 4.95 0.14 99.28
K63 72.64 0.19 13.59 1.69 0.03 0.15 0.10 0.86 10.05 0.03 99.33
K73 74.10 0.28 12.29 2.78 0.04 0.10 0.11 0.37 9.06 0.05 99.19
TY105 67.49 0.46 15.21 3.32 0.08 1.39 3.29 3.64 4.31 0.15 99.33
TY106 63.03 0.67 17.09 5.45 0.13 2.36 2.78 3.70 3.54 0.22 98.96
TY113 70.67 0.40 16.63 2.33 0.09 0.37 1.55 2.46 5.25 0.06 99.81
TY117 70.84 0.43 15.21 3.50 0.07 1.13 0.25 2.18 5.55 0.09 99.24
TY96 70.70 0.46 14.85 3.20 0.08 1.39 1.26 2.95 4.23 0.17 99.29
U91 67.21 0.48 15.18 3.69 0.09 1.62 2.95 3.47 4.83 0.17 99.68
U92 64.83 0.60 16.27 4.42 0.11 2.28 3.16 4.06 3.59 0.19 99.49
U93 60.91 0.73 17.60 5.52 0.20 2.23 5.92 3.98 2.47 0.25 99.80
Standard deviation 0.03 0.01 0.03 0.02 0.00 0.03 0.00 0.02 0.00 0.00
 International Geology Review 5

16

14

12
Trachydacite

Na2O+K2O (wt. %)
10
Rhyolite
Trachyandesite
8

4 Basaltic Andesite
Andesite
2
Downloaded by [American Museum of Natural History] at 12:41 26 March 2013

0
35 40 45 50 55 60 65 70 75 80
SiO2 (wt. %)

Figure 3. Total alkali (Na2 O + K2 O wt.%) vs SiO2 (wt.%) diagram (Le Bas et al. 1992) for the Koru volcanic rocks.

1.5 24
(A) (B)
20
1.2

16
Al2O3 (wt.%)
TiO2 (wt.%)

0.9
12
0.6
8

0.3
4

0 0
55 60 65 70 75 80 55 60 65 70 75 80
SiO2 (wt.%) SiO2 (wt.%)
8 12
(C) (D)

6 9
MgO (wt.%)

CaO (wt.%)

4 6

2 3

0 0
55 60 65 70 75 80 55 60 65 70 75 80
SiO2 (wt.%)
SiO2 (wt.%)

15 8
(E) (F)
7
12
6
FeO* (wt.%)

5
K2O (wt.%)

9
4
6 3

2
3
1

0 0
55 60 65 70 75 80 55 60 65 70 75 80
SiO2 (wt.%) SiO2 (wt.%)

Figure 4. Major oxide variation diagrams in terms of (A) SiO2 vs TiO2 , (B) SiO2 vs Al2 O3 , (C) SiO2 vs MgO, (D) SiO2 vs CaO, (E)
SiO2 vs K2 O, and (F) SiO2 vs FeO∗ for the Koru volcanic rocks.
 6 D.K. Yildirim et al.

P = 500 bars P = 1000 bars

f O2 = QFM + 1 fO2 = QFM + 1
(A) (B)
16 16

14 14

Na2O + K2O (wt.%)

12 12
Na2O + K2O (wt.%)

10 10

8 8

6 6

4 4

2 2

0 0
35 40 45 50 55 60 65 70 75 80 35 40 45 50 55 60 65 70 75 80
Downloaded by [American Museum of Natural History] at 12:41 26 March 2013

SiO2 (wt.%) SiO2 (wt.%)

P = 3000 bars
fO2 = QFM + 1
(C)
16

14

12
Na2O + K2O (wt.%)

10

0
35 40 45 50 55 60 65 70 75 80
SiO2 (wt.%)

Figure 5. Comparison of calculated melt composition (filled diamonds) at (A) P = 500 bars, (B) P = 1000 bars, and (C) P = 3000 bars
under closed system isobaric fractional crystallization of parental basaltic andesite with composition of the Koru volcanic rocks (open
circles) in SiO2 vs Na2 O + K2 O space. Best agreement between computed melt calculation and composition of the Koru volcanic rocks
is attained at P = 1000 bars.

In order to constrain the initial pressure of the parental Comparison of calculated melt composition with compo-
basaltic andesite magma (TY109), we calculated the com- sition of the natural rock for various oxygen fugacities in
positions of melts generated at 500, 1000, and 3000 bars MgO vs FeO∗ (total FeO) diagrams indicates that the best
(Figure 5). These figures show that andesite, trachyan- match between the computed compositions and the Koru
desite, and trachydacite compositions can be generated volcanic rocks is attained at QFM + 1 (Figure 6B). Melts
from the basaltic andesite parental magma at 1000 bars generated at QFM − 2 have much higher FeO∗ values
total pressure (Figure 5B). In addition, the computations for given MgO than the natural compositions (Figure 6A).
at 1000 bars can produce the mineral assemblages which For two log units above the QFM buffer (at QFM + 2),
agree with the identity and order of crystallization observed computed melts have much lower FeO∗ values for given
in thin sections. Calculations at 500 bars generated the MgO compared to the natural compositions (Figure 6C).
whole spectrum of rocks reasonably well, yet the com- Therefore, the oxygen fugacity of the initial system is set
puted compositions have a higher total alkali value than the to QFM + 1.
natural lavas (Figure 5A). Simulations at higher pressures Having constrained the initial pressure and oxygen
(3000 bars) can only produce part of the spectrum of rocks fugacity of the Koru volcanic rocks at 1000 bars and
in Koru region (basaltic andesite to trachydacite) but not QFM + 1, our final step is to evaluate the role of vari-
much of the rhyolites (Figure 5C). Consequently, the initial ous water contents on derivative compositions plotted in
system pressure is set to 1000 bars. the SiO2 vs K2 O space. Figure 7 shows calculated melt
Figure 6 shows the compositions of melts generated at composition at 1000 bars and QFM + 1 with 0.5, 1, and
buffer conditions of QFM − 2, QFM + 1, and QFM + 2. 2 wt.% water contents. Calculated melt composition at
 International Geology Review 7

P = 1000 bars P = 1000 bars

(A) fO2 = QFM–2 (B) fO2 = QFM+1
8 8

7 7

6 6
FeO* (wt.%)

FeO* (wt.%)
5

4 4

3 3

2 2

1 1

0 0
0 1 2 3 4 5 6 7 0 1 2 3 4 5 6 7
MgO (wt.%) MgO (wt.%)
Downloaded by [American Museum of Natural History] at 12:41 26 March 2013

(C) P = 1000 bars

fO2 = QFM+2
8

5
FeO* (wt.%)

0
0 1 2 3 4 5 6 7
MgO (wt.%)

Figure 6. Comparison of calculated melt composition (filled diamonds) at (A) f O2 = QFM − 2, (B) f O2 = QFM + 1, and (C)
f O2 = QFM + 2 with composition of the Koru volcanic rocks (open circles) at 2 wt.% H2 O and P = 1000 bars in MgO vs FeO∗
space. Initial system f O2 is best defined at QFM + 1.

P = 1000 bars and f O2 = QFM + 1 produce compositions
similar to those of Koru parental magmas at a water content
of 2 wt.% (Figure 7C). Computations with less than 2 wt.%
produce derivative melts with higher K2 O for given silica
content compared to the natural lavas (Figures 7A and 7B).
This sets the water content of Koru magma to 2 wt. %.
Results of MELTS calculations demonstrate that the
initial system parameters of Koru parental magma are as
follows: P = 1000 bars, f O2 = QFM + 1, and water
content = 2 wt.%. Having constrained the initial state of
the system, our next step is to calculate magma evolu-
tion under (a) isobaric fractional crystallization and (b)
isobaric–isenthalpic magma mixing conditions.
We first tested whether crystal fractionation under
constant pressure of 1000 bars produces the liquids
whose composition matches those of Koru volcanic rocks.
Figure 8 shows the comparison of melts generated under
fractional crystallization of parental basaltic andesite with
2 wt.% H2 O at 1000 bars and buffer conditions of
QFM + 1 with compositions of the Koru volcanic rocks
in SiO2 vs TiO2 , SiO2 vs Al2 O3 , SiO2 vs FeO∗ , SiO2 vs
MgO, SiO2 vs CaO, and SiO2 vs K2 O Harker diagrams.
During crystallization, as the silica content increases, resid-
ual liquids decrease in TiO2 , Al2 O3 , MgO, CaO, and
FeO∗ (Figures 8A–8D, and 8F) and increase in K2 O
(Figure 8E). These linear trends reflect the crystallization
of olivine, orthopyroxene, plagioclase, clinopyroxene, and
Fe–Ti oxides. Although these trends match to the identity
of crystallized minerals observed in thin sections, there are
discrepancies in SiO2 vs Al2 O3 , SiO2 vs MgO, and SiO2
vs FeO∗ diagrams (Figures 8B, 8C, and 8F). The Koru
volcanic rocks have higher Al2 O3 and higher MgO and
FeO∗ than the calculated compositions, especially in the
trachydacite compositions. Furthermore, fractional crystal-
lization cannot produce composition of Koru rhyolites.
Realizing that the fractional crystallization conditions
cannot produce the entire compositional diversity of the
Koru Volcanics, we then tested the hypothesis that magma
mixing involving basaltic andesite and rhyolite is responsi-
ble for generating the entire spectrum of the Koru volcanic
rocks. Figure 9 clearly shows that this process is capable of
generating the entire compositional spectrum of the Koru
 8 D.K. Yildirim et al.

P = 1000 bars P = 1000 bars

(A) f O2 = QFM + 1 fO2 = QFM + 1
(B)
H2O = 0.5wt.% H2O = 1wt.%
12 12

10 10

8 8
K2O (wt.%)

K2O (wt.%)
6 6

4 4

2 2

0 0
55 60 65 70 75 80 55 60 65 70 75 80
SiO2 (wt.%) SiO2 (wt.%)

P = 1000 bars
Downloaded by [American Museum of Natural History] at 12:41 26 March 2013

(C) fO2 = QFM + 1

H2O = 2wt.%
12

10

8
K2O (wt.%)

0
55 60 65 70 75 80
SiO2 (wt.%)

Figure 7. Comparison of calculated melt composition (filled diamonds) at (A) 0.5 wt.% H2 O, (B) 1 wt.% H2 O, and (C) 2 wt.% H2 O with
composition of Koru volcanic rocks (open circles) at P = 1000 bars and f O2 = QFM + 1 in SiO2 vs K2 O space. Best agreement between
computed compositions at P = 500 bars and f O2 = QFM + 1 and the Koru volcanic compositions is at 2 wt.% H2 O.

Volcanics. To further test the goodness of the fit between
the calculated melt composition and the composition of
Koru volcanic rocks, we plotted SiO2 vs TiO2 , SiO2 vs
Al2 O3 , SiO2 vs FeO∗ , SiO2 vs MgO, SiO2 vs CaO, and
SiO2 vs K2 O diagrams where both the calculated melt com-
positions and the rock compositions are shown (Figure 10).
Good agreement between calculated melt composition and
composition of natural rocks of Koru Volcanics further
support the magma-mixing model. Therefore, we conclude
that at P = 1000 bars, f O2 = QFM + 1, and 2 wt.% water,
mixing of basaltic andesite and rhyolite can explain the
petrogenesis of disseminated ore-bearing volcanic rocks.
In other words, disseminated Pb and Zn deposits were
transported to the near surface by these magmas.
Geochemistry of ore-forming solutions through
SUPCRT calculations
Although we agree with previous investigators that
hydrothermal activity produced by Tertiary volcanics is
responsible for the origin of Pb and Zn deposits in the
Koru area, the stability of galena and sphalerite in vein
deposits in terms of pressure, temperature, oxygen fugacity,
pH, and total sulphur content in the H–S–O system has
never been quantitatively evaluated. This requires applica-
tion of thermodynamics of aqueous geochemistry. It is our
objective to provide new data to fill this gap in understand-
ing of formation of galena and sphalerite vein deposits in
the Koru area. The first step in such calculations using
the SUPCRT software is to calculate the stability fields of
aqueous H2 S, HS− , S−2 , SO−2 −
4 and HSO4 at 150 and

250◦ C, S = 10−3 molal, as a function of pH and f O2 .
SUPCRT algorithm (Johnson et al. 1992) has been
used to calculate standard molal thermodynamic proper-
ties of magnetite, haematite, pyrite, pyrrhotite, barite, as
well as ionic and aqueous species in the system H–O–
S to constrain the stability limits of sphalerite, galena,
magnetite, haematite, and barite at 500 bars, 150◦ C, S
−3
= 10 molal sulphur in terms of oxygen fugacity and
pH. The combined data for seven minerals, eight ions,
and four aqueous complexes provided quantitative pre-
dictions of aqueous speciation and mineral solubility as
functions of temperature, pressure, pH oxidation state, and
sulphur content of ore-forming fluids. The master equation
that SUPCRT uses in the apparent standard molal Gibbs
free energy of a species, G0a,i,P,T at a given pressure and
temperature is
 International Geology Review 9

1.5 24
(A) (B)
20
1.2

16

Al2O3 (wt.%)
TiO2 (wt.%)
0.9
12
0.6
8

0.3
4

0 0
55 60 65 70 75 80 55 60 65 70 75 80
SiO2 (wt.%) SiO2 (wt.%)

8 12
(C) (D)

6 9
Downloaded by [American Museum of Natural History] at 12:41 26 March 2013

MgO (wt.%)

CaO (wt.%)
4 6

2 3

0 0
55 60 65 70 75 80 55 60 65 70 75 80

SiO2 (wt.%) SiO2 (wt.%)

15 8
(E) (F)

12
6
FeO* (wt.%)
K2O (wt.%)

9
4
6

2
3

0 0
55 60 65 70 75 80 55 60 65 70 75 80
SiO2 (wt.%) SiO2 (wt.%)

Figure 8. Comparison of melts generated from isobaric fractional crystallization of basaltic andesite with 2 wt.% H2 O at 1000 bars and
f O2 = QFM + 1 (filled diamonds) with compositions of the Koru volcanic rocks (open circles) in (A) SiO2 vs TiO2 , (B) SiO2 vs Al2 O3 ,
(C) SiO2 vs MgO, (D) SiO2 vs CaO, (E) SiO2 vs K2 O, and (F) SiO2 vs FeO∗ .

16
Gi,P,T
0
= Gf0,i,Pr ,Tr − Si,P
0
r ,Tr
(T − Tr ) + (a (T − Tr − T ln (T/Tr ))
14  
bTTr2 − c
12
− (T − Tr )2
+ Vi,P
0
r ,Tr
(P − Pr ) ,
2TTr2
Trachydacite
Na2O + K2O (wt.%)

10 where i and f represent species i and formation from ele-

Rhyolite

8
Trachyandesite ments, respectively; Pr and T r refer to pressure at 1 bar and
0
temperature at 298.15 K, respectively; Si,P,T is the standard
6 0
state entropy of species i at P and T; Vi,P,T is the volume
4
of species i; and a, b, and c are the constants in the heat
Basaltic Andesite
Andesite capacity equation. SUPCRT is capable of calculations in
2 the temperature range of 25◦ C to 500◦ C and the pressure
range of 1 bar to 5000 bars.
0
35 40 45 50 55 60 65 70 75 80 Since pressure has a minor effect on the solution chem-
SiO2 (wt.%) istry compared to the other variables, based on the pressure
constraints in MELTS calculations, pressure of 500 bars
Figure 9. Comparison of calculated melt composition gener- has been used for SUPCRT calculations. Using SUPCRT
ated by isobaric-isenthalpic mixing of parental basaltic andesite
and rhyolite (filled diamonds) with the composition of the Koru software, we first established
 a log f O2 –pH diagram at
volcanic rocks (open circles) in SiO2 vs Na2 O + K2 O diagram. 150◦ C and 250◦ C and S = 10−3 for the H–S–O system
 10 D.K. Yildirim et al.

1.5 24
(A) (B)
1.2 20

Al2O3 (wt.%)
TiO2 (wt.%)
16
0.9
12
0.6
8
0.3
4

0 0
55 60 65 70 75 80 55 60 65 70 75 80
SiO2 (wt.%) SiO2 (wt.%)
8 12
(C) (D)
Downloaded by [American Museum of Natural History] at 12:41 26 March 2013

6 9
MgO (wt.%)

CaO (wt.%)
4 6

2 3

0 0
55 60 65 70 75 80 55 60 65 70 75 80
SiO2 (wt.%) SiO2 (wt.%)

15 8
(E) (F)
7
12
6
FeO* (wt.%)
K2O (wt.%)

9 5
4
6 3
2
3
1
0 0
55 60 65 70 75 80 55 60 65 70 75 80
SiO2 (wt.%) SiO2 (wt.%)

Figure 10. Comparison of calculated melt composition generated by isobaric-isenthalpic mixing of parental basaltic andesite and rhyolite
(filled diamonds) with the composition of the Koru volcanic rocks (open circles) in (A) SiO2 vs TiO2 , (B) SiO2 vs Al2 O3 , (C) SiO2 vs
MgO, (D) SiO2 vs CaO, (E) SiO2 vs K2 O, and (F) SiO2 vs FeO∗ Harker diagrams.

and then superimposed the stability limits of galena, spha-
lerite, magnetite, haematite, and barite. The stability field
of ore and gangue minerals indicates that ore-forming solu-
tions straddle the HS− and SO−2 4 fields, indicating that
f O2 fluctuated between reduced and oxidized conditions
from 10−55 to 10−45 within the pH range of 5–9 at 150◦ C
(Figure 11A). Calculations at 250◦ C indicate that galena,
sphalerite, and barite are stable at pH between 5.8 and 9.8,
and f O2 between 10−43 and 10−35 (Figure 11B).
at P = 1000 bars, f O2 = QFM + 1, and 2 wt.% H2 O by
mixing basaltic andesite and rhyolite melts. These volcanic
rocks brought the Pb and Zn to shallow depths as dis-
seminated ore. Later, sulphur–oxygen–hydrogen-bearing
solutions dissolved and redeposited lead and zinc as galena
and sphalerite in fractures as vein deposits at pH 5–9, f O2
between 10−55 and 10−45 bars at 150◦ C and pH 5.8–9.8,
f O2 between 10−43 and 10−35 bars at 250◦ C.

Conclusions
This study demonstrates the conditions under which the
compositional evolution of the Koru Volcanics took place
Acknowledgements
The authors acknowledge Gary Ernst for critically reading the
manuscript. Barry Maynard and Tammie Gerke are thanked for
their assistance with X-ray fluorescence analyses at University of
Cincinnati.
 International Geology Review 11

(A) 35
HSO4- SO4–2
Hema
40 tit e
Bari
H2S te

45 hematite
SO –2
4
HS –
–log fO2, atm
50 Pb–Zn
insoluble

Pyrite

Ma rrho
55

Py
Pyrrhotite

gn tite
ett
ite
60
Downloaded by [American Museum of Natural History] at 12:41 26 March 2013

65

1 ppm Pb
1 ppm Zn

HS–
H2S
70
0 2 4 6 8 10 12
pH
(B) 25

HSO4- SO4–2

30 Hema
tit e
hematite
magnettite
35 Bari
te
–log fO2, atm

Pb–Zn
insoluble SO –2
4
40 HS –
Pyrite
Ma rhoti
Py

Pyrrhotite
gn
r
ett

45
ite
te
1 ppm Pb
1 ppm Zn

HS–
H2S

50
0 2 4 6 8 10 12
pH

Figure 11. SUPCRT diagram in terms of log f O2 –pH showing  the geochemical conditions of galena and sphalerite formation at (A)
150◦ C and (B) 250◦ C [modified from Cooke et al. (1998)] and S = 10−3 for the H–S–O system.

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