Chem.

Erde 63 (2003), 163–182

Urban & Fischer Verlag
http://www.urbanfischer.de/journals/chemerd

Mineralogy and Chemistry of Biotites

from Eastern Pontide Granitoid Rocks, NE-Turkey:
Some Petrological Implications for Granitoid Magmas
F. Aydin1,*, O. Karsli2, and M.B. Sadiklar1
1
Department of Geol. Engineering, Karadeniz Technical University, Trabzon, Turkey
2
Department of Geol. Engineering, Karadeniz Technical University, Gumushane, Turkey

Received: 27. 11. 2002 · Accepted: 05. 02. 2003

Abstract
The Eocene Zigana Granitoid in the northern zone and the Middle-Upper Eocene Dolek
and Saricicek Plutons in the southern zone of the Eastern Pontides (NE-Turkey) consist of
different rock series ranging in composition from intermediate to felsic compositions
containing from <1% to 9% of biotite. The biotites are Mg-rich (XFe = Fe2+/Fe2+ + Mg) =
0.28 – 0.49) in the southern zone plutons and Mg- to Fe-rich (XFe = Fe2+/Fe2+ + Mg) =
0.33 – 0.78) in the northern zone pluton. They coexist with K-feldspar, plagioclase,
quartz, amphibole, pyroxene, low titanium magnetite, minor ilmenite ± titanite. Biotites
have been buffered by the Ni-NiO. The plutons equilibrated under low oxygen fugacities
(LogfO2) ranging from –16.01 to –20.23 bars for Dolek and Saricicek, and –16.70 to
–17.90 bars for Zigana.
EPMA indicate that the composition of biotite is related to the mineral assemblages of
Dolek, Saricicek and Zigana biotites as a consequence of chemistry of the magma and the
physical conditions during crystallization. The biotite compositions were used to discrim-
inate the tectonic setting of the plutons. The intrusions appear to be related to calc-alka-
line to high-K calc-alkaline orogenic suites. Furthermore, Mg[6]-Fetot substitution has
played a significant role during the crystallization of the biotites.

Key words: biotite, oxygen fugacity, Eastern Pontides, Dolek, Saricicek and Zigana
Plutons

* Corresponding address:
F. Aydin, Dept. of Geol. Engineering, Karadeniz Technical University, TR-61080 Trabzon, Turkey
Tel.: ++90-462-3773508; Fax: ++90-462-3257405; e-mail: faydin@ktu.edu.tr

0009-2819/03/63/02-163 $ 15.00/0
164 F. Aydin et al.

Introduction
Biotite is a common hydrated ferromagnesian silicate in most mafic, intermediate and
felsic plutonic rocks. Igneous biotite covers a wide range of crystallization conditions and
reacts very sensitively to changes in the physico-chemical conditions such as oxygen and
halogen fugacities, temperature, pressure and chemical composition of the magmas
(Speer 1984). Hence, they provide valuable petrogenetic information about the physico-
chemical conditions of plutonic magmas during crystallization (Albuquerque 1973;
Neiva 1981; Lalonde and Bernard 1993; Lalonde et al. 1996). They also clearly reflect
the nature and tectonic environments of their host magmas (Abdel-Fattah 1994 and
1996). Chemical compositions of biotites of the plutons from Eastern Pontides have not
been determined so far and important petrogenetic information about physico-chemical
conditions of granitic rocks from the Eastern Pontides are absent.
This study is aimed at three topics: Firstly, to determine the occurrence, structural
formulae, crystal chemistry and crystallization conditions such as oxygen and water
fugacities of the biotites from the Eocene Dolek, Saricicek and Zigana Plutons. Secondly,
to interpret, whether the chemical composition, mineral paragenesis, oxygen and water
fugacity of the biotites in different zones of Eastern Pontides change or not. Lastly, to
discriminate the tectonic settings of the plutons by using the biotite compositions.

Geology, petrography and mineralogy

Previous works (Ketin 1966; Bektaş et al. 1995, 1999) have shown that the Eastern
Pontides (EP) can be divided into three zones such as the northern, southern and axial
zones, which differ in their rock types (Fig. 1). The architecture of the EP is framed by a
belt of Paleozoic to Late Eocene granitoidic rocks (Çoğulu 1975; Güven 1993; Karsli et
al. 2002) (Fig. 1). The Zigana, Dolek and Saricicek Plutons are part of the complex,
which outcropped during Early to Late Eocene (Karsli 2002; Karsli et al. 2002) (Fig. 2).
In the northern zone, the Eocene Zigana Granitoid intruded into Mesozoic and Ceno-
zoic volcanics in the northern zone of the Eastern Pontides, and is a calc-alkaline to
slightly high-K calc-alkaline, I-type and a reversely zoned body (Karsli and Sadiklar
1996, 1997) (Fig. 3). The Dolek and Saricicek Plutons, in contrast to its northern counter-
part, cut the Early Eocene basaltic and andesitic rocks and is a slightly calc-alkaline to
high-K calc-alkaline, I-type and unzoned body (Karsli et al. 2001; Karsli 2002). Crystal
fractionation and magma mixing processes are very effective in the evolution of their
magmas (Karsli et al. 2001, 2002; Karsli 2002). The plutons occur within an arc setting
which was active during the Upper Cretaceous (Çoğulu 1975; Güven 1993; Bektaş et al.
1995; Yilmaz and Karsli 1997; Yilmaz et al. 1997; Bektaş et al. 1999; Yilmaz 2002).

Fig. 1. Simplified geological maps of the Eastern Pontides showing granitoidic plutons [Modified
from Gedik et al. (1992)]. 1: Paleozoic granitoidic rocks; 2: Liassic volcanics; 3: Malm-Lower
Cretaceous volcanics; 4: Upper Cretaceous and Paleocene volcanics; 5: Paleocene to Late Eocene
plutonic rocks; 6: Eocene volcanics; 7: Miocene volcanics; 8: Plio-Quaternary volcanics; 9: Post
Eocene terrigeneous units; NAF: North Anatolian Fault; NEAF: Northeast Anatolian Fault.
Mineralogy and Chemistry of Biotites 165
166 F. Aydin et al.
 Mineralogy and Chemistry of Biotites 167

According to the QAPF classification (Streckeisen 1976), the Zigana Plutons range in
composition from granite and granodiorite in the outer to monzodiorite in the inner zones.
Quartzmonzodiorite is a transitional rock between these two zones (Fig. 4a). In the
southern zone, the unzoned Dolek and Saricicek Plutons are modally classified as granite,
granodiorite, monzonite and quartzmonzonite. The intrusions are rich in elliptically-shaped
mafic microgranular enclaves (30 cm to 1 mm in size); their modal mineralogy ranges from
diorite to quartz monzodiorite (Fig. 4b). In both zones, medium grained rocks can be

Fig. 3. Simplified geological and zonation map of the northern part of the Zigana Pluton (Karsli
et al. 2002). 1: Monzodiorite; 2: Quartzmonzodiorite; 3: Granite and granodiorite; 4: Volcanic
rocks; 5: Samples containing minor biotite; 6: Samples selected for microprobe analyses; 7: Loca-
tion of other samples.

Fig. 2. Geological map of the Dolek and Saricicek Plutons (Karsli, 2002)
Fig. 4. Q-A-P modal classification of the Zigana, Dolek and Saricicek Plutons. Symbols: Filled
triangular = monzodiorite; crosses = quartzmonzodiorite; filled stars = granite and granodiorite in
Zigana; crosses = host rocks; filled stars = enclaves in Dolek and Saricicek.
 Mineralogy and Chemistry of Biotites
169
Fig. 5. Microscopic and back-scattered electron images of biotites from the
plutons. Photo A is from Zigana; B and C are from Dolek and Saricicek.
170 F. Aydin et al.

assigned to the I-type category because of their essential mineralogical assemblage plagio-
clase, quartz, K-feldspar, amphibole, biotite, pyroxene and Fe-Ti oxides ± sphene and
apatite as accessory mineral (Fig. 5). This paragenesis is nearly identical in modal composi-
tion. The southern plutons have coarser grain size than the northern ones (Fig. 5A, B).

Analytical techniques
Polished thin sections of the biotite-hosting granitoidic rocks were studied in detail by
optical methods prior to analysis of the mineral phases. Chemical analyses of the biotites
were carried out using the CAMECA-SX-51 electron microprobe at the Mineralogical
Institute of Heidelberg University. Natural and synthetic oxides and silicate standards
were used. The correction procedures were performed with CAMECA’s PAP software
for on-line data reduction. Operating conditions were 15 kV and 20 nA with a counting
time of usually 10 s. The biotites were selected from the granitoid samples by binocular
microscopy. Ferrous and ferric iron contents were determined by wet chemical analysis
(Hey 1982). Whole rock chemical analyses were performed by means of ICP in the labo-
ratory of the ACME in Canada and XRF in the geochemical laboratory of the Min. Insti-
tute of Heidelberg University.

Occurrence and mineral assemblage of biotite

Modal compositions of the Zigana, Dolek and Saricicek Plutons are shown in Tables 1
and 2. Orthoclase, plagioclase, quartz and amphibole always accompany to the biotite.
Sphene, apatite, magnetite and ilmenite are present as accessory minerals. Biotites (0.6–8%)
are usually 50–700 µm in size and vary form prismatic (blade and rectangle) to euhedral in
the Dolek and Saricicek Plutons, while biotite (4–9%) from the inner to the outer zone
(<1%) replacing magnesio-hornblende (2–8%) and clinopyroxene (6–10%) are smaller
irregularly shaped flakes and well-developed plates in the Zigana Plutons. Blade forms of
the biotites are always absent in the northern part (Fig. 5B). Although clinopyroxene
replacing magnesio-hornblende and actinolite are common magmatic processes, the replace-
ment of biotite by amphibole is rare in the Dolek and Saricicek Plutons. Fe-Ti oxides form
abundant inclusions in biotites in all plutons (Fig. 5C). Textural relationships of the plutons
suggest that these mineral parageneses are magmatic and equilibrium assemblages.

Biotite chemistry
Representative compositions are shown in Tables 3 and 4. For the Zigana biotites,
they vary from Mg-rich (inner zone) to Fe-rich biotite (towards outer zone) with XFe =
Fe2+/Fe2+ + Mg) = 0.33 – 0.78 (Fig. 6a). In the inner zone of the Zigana, biotites have high
TiO2 contents (4.47–5.26 wt%), and so their colours change from yellowish-brown to
reddish-brown. Towards the outer zone, TiO2 contents of biotite decrease to 2.56 wt%.
The biotites of Dolek and Saricicek, in contrast to its northern counterpart, generally do
not show differences in chemical composition and are classified as Mg-rich biotite with
XFe = Fe2+/Fe2+ + Mg) = 0.28 – 0.49 (Fig. 6b). TiO2 contents range from 3.36 to 6.50 wt%.
K atoms per formula units (apfu) of the biotites change from 1.67 to 1.83 in Zigana, and
1.50 to 1.70 in Dolek and Saricicek Plutons.
Fig. 6. Biotite classification diagram plotting Al/Al+Si versus Fe2+/Fe2++Mg.
 172
Table 1. Whole-rock chemical and modal composition of rocks from the Zigana Granitoid.

Zigana
–––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––

F. Aydin et al.
Monzodiorite containing Quartzmonzodiorite containing Granodiorite to Granite
hornblende, biotite hornblende, biotite containing hornblende
and pyroxene and minor pyroxene and minor biotite
–––––––––––––––––––––––––––––––––––––– –––––––––––––––––––––––––––––––––––––––––––––––– –––––––––––––––––––––––––––
Sample No J26 J7 G10 J21 G8 J19 G36 M7 J18 M5 G71 J4

CHEMICAL ANALYSES+
SiO2 56.08 52.82 52.91 53.66 57.12 62.71 60.24 56.15 59.06 67.04 68.89 71.36
TiO2 0.53 0.61 0.61 0.58 0.57 0.36 0.45 0.56 0.39 0.33 0.32 0.30
Al2O3 20.23 21.88 20.84 21.41 19.55 16.83 18.89 18.64 17.29 15.76 15.22 14.81
FeOt 5.89 7.18 6.74 6.69 4.85 3.99 5.32 5.70 2.44 3.03 3.01 3.19
MnO 0.08 0.11 0.10 0.11 0.08 0.06 0.07 0.05 0.03 0.03 0.05 0.07
MgO 4.29 5.13 4.80 5.18 2.95 2.03 3.16 3.13 1.44 1.06 1.02 1.11
CaO 6.00 7.54 6.53 6.59 5.56 5.54 4.22 6.52 7.59 3.44 3.30 2.17
Na2O 2.06 1.99 2.07 1.91 3.78 4.38 3.73 4.21 5.05 4.11 3.55 3.60
K2O 3.87 3.55 3.84 3.79 3.22 2.81 4.37 3.65 3.29 3.45 3.58 4.24
P2O5 0.06 0.05 0.08 0.04 0.20 0.08 0.10 0.12 0.10 0.09 0.08 0.07
LOI 0.87 1.10 1.25 1.65 1.55 1.32 1.16 2.13 1.53 0.76 0.96 0.75
Total 99.96 101.96 99.77 101.61 99.43 100.11 100.71 100.86 98.21 99.10 99.98 101.67
MODAL ANALYSES
Quartz 3 2 3 3 6 12 8 6 7 27 28 30
K-Feldspar 18 12 13 15 10 7 24 15 10 17 20 22
Plagioclase 58 67 58 58 67 70 56 70 73 51 45 40
Biotite 7 5 9 7 4 3 2 2 <1 <1 <1 1
Amphibole 6 7 5 5 5 5 3 4 5 4 5 6
Pyroxene 7 6 9 10 4 1 4 2 1 – – –
Mag.-Ilm. 1 1 3 2 4 2 3 1 4 1 2 1
Q (%) 4 2 4 4 7 13 9 7 8 28 30 33
A (%) 23 15 18 20 12 8 27 16 11 18 22 24
P (%) 73 83 78 76 81 79 64 77 81 54 48 43
+
Major oxide analyses were determined by ICP & XRF
t
Toplam iron as FeO
Table 2. Whole-rock chemical and modal composition of rocks from the Dolek and Saricicek Plutons.

Dolek and Saricicek

–––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––
Granite to Granodiorite Quartzmonzonite Quartzmonzodiorite
–––––––––––––––––––––––––––––––––––– –––––––––––––––––––––––––––––––––––––– –––––––––––––––––––––––––––––––––––––
Sample No Sc5 Sc10 Sr2 Dk4 Ks8 Sc14 Sr36 D24 Id2a D7 E20 Pe9

CHEMICAL ANALYSES+
SiO2 64.29 64.57 65.33 63.12 60.50 60.83 60.51 60.12 59.83 59.82 57.11 58.67
TiO2 0.64 0.63 0.65 0.56 0.66 0.73 0.66 0.70 0.76 0.77 0.82 0.70
Al2O3 15.34 15.75 15.67 15.63 16.18 16.04 16.58 16.79 15.75 16.40 16.60 15.33
FeOt 5.38 5.27 5.24 5.20 6.36 6.31 6.3 6.12 6.39 6.69 8.04 7.33
MnO 0.10 0.10 0.09 0.09 0.12 0.12 0.10 0.12 0.16 0.10 0.15 0.15
MgO 2.15 2.20 2.23 2.14 3.02 2.82 2.80 2.65 2.92 3.06 3.70 4.03
CaO 4.39 4.54 3.90 4.35 5.08 5.40 5.45 5.53 5.15 5.65 6.67 6.77
Na2O 3.13 3.36 3.29 3.09 3.16 3.55 3.20 3.49 2.99 3.37 3.21 3.60
K2O 3.26 3.27 3.47 4.16 3.5 2.72 3.30 3.14 4.02 2.94 2.63 1.64

Mineralogy and Chemistry of Biotites

P2O5 0.14 0.15 0.12 0.13 0.14 0.14 0.19 0.14 0.14 0.14 0.17 0.16
LOI 0.88 1.11 0.73 0.60 1.10 1.10 0.84 0.90 1.70 0.80 0.70 1.08
Total 99.70 100.95 100.73 99.07 99.76 99.76 99.93 99.70 99.97 99.74 99.80 99.46
MODAL ANALYSES
Quartz 25.5 26.1 28.8 22.4 17.2 17.6 16.8 16.5 12.0 17.1 11.6 13.1
K-Feldspar 19.7 23.6 31.2 17.7 30.1 28.0 25.6 32.4 11.7 20.2 14.3 12.7
Plagioclase 39.2 36.7 32.5 43.1 40.3 48.0 45.2 35.2 50.7 48.1 55.6 57.3
Biotite 7.2 3.5 2.4 3.5 7.5 0.8 0.8 0.6 9.3 4.5 8 4.1
Amphibole 5.1 6.5 4.4 9.7 3.2 4.0 11.2 10.7 – 7.6 3.2 7.6
Pyroxene – 0.4 – 0.8 – – – – 11.9 – 0.8 1.0
Mag.-Ilm. 2.9 2.4 0.4 2.0 1.7 0.9 0.4 4.0 4.0 2.3 4.8 3.9
Sphene – 0.3 – 0.8 – 0.4 – 0.6 0.4 – 0.2 0.3
Epidote – – – – – – – – – 0.2 0.7 –
Chlorite 0.4 0.5 0.3 – – 0.3 – – – – 0.8 –
Q (%) 31 30 31 27 19 19 19 18 16 19 14 16
A (%) 23 27 34 21 35 30 29 38 16 22 18 15

173
P (%) 46 42 35 52 46 51 52 44 68 59 68 69
174 F. Aydin et al.

Crystallization conditions of biotite

The major element compositions and structural formulas of the biotites and the
compositions of the magnetites and K-feldspars are given in Tables 3 and 4. A number of
authors (Verhoogen 1962a, b; Taylor 1964; Buddington and Lindsley 1964; Albuquerque
1973) have suggested that Ti4+, Al[6] and Fe3+ are the most important elements to be
considered in the understanding of petrogenetic problems for granitic rocks. Those of Ti4+
and Fe3+ depend mostly on temperature of crystallization and oxygen fugacity (ƒO2),
while Al[6] is a variable that depends especially on the Al activity.

Table 3. Representative and average analyses of biotites from the Zigana Pluton.

Zigana
–––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––
Biotites from Monzodiorite containing Biotites from
biotite, hornblende and pyroxene Quartzmonzo-
diorite contain-
ing hornblende
––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––– ––––––––––––––––
Sample No J26 (n = 6)* J7 (n = 9)* G10 (n = 12)* J21 (n = 15)* J19 (n = 14)*

MICROPROBE ANALYSES
SiO2 36.34 ± 1.53 36.81 ± 0.32 36.92 ± 0.30 37.33 ± 0.29 33.96 ± 1.29
TiO2 4.15 ± 0.45 4.10 ± 0.27 4.36 ± 0.44 5.26 ± 0.43 2.56 ± 0.76
Al2O3 12.76 ± 0.52 13.13 ± 0.30 12.76 ± 0.21 12.65 ± 0.18 14.80 ± 1.60
Cr2O3 0.01 ± 0.01 0.02 ± 0.02 0.01 ± 0.02 0.01 ± 0.01 0.03 ± 0.04
**Fe2O3 2.06 ± 0.07 1.89 ± 0.07 4.08 ± 0.07 6.84 ± 0.07 6.99 ± 0.07
**FeO 16.81 ± 0.07 15.47 ± 0.07 13.95 ± 0.07 9.89 ± 0.07 9.90 ± 0.07
MnO 0.29 ± 0.06 0.25 ± 0.04 0.27 ± 0.05 0.10 ± 0.04 0.59 ± 0.46
MgO 13.30 ± 0.71 13.67 ± 0.53 13.06 ± 0.43 14.13 ± 0.41 8.20 ± 2.95
CaO 0.03 ± 0.03 0.02 ± 0.02 0.02 ± 0.02 0.03 ± 0.07 0.04 ± 0.03
Na2O 0.15 ± 0.02 0.15 ± 0.02 0.15 ± 0.05 0.24 ± 0.06 0.11 ± 0.08
K2O 9.12 ± 0.26 9.15 ± 0.23 9.03 ± 0.29 9.24 ± 0.38 7.99 ± 1.45
Total 95.02 94.66 94.61 95.72 95.17

STRUCTURAL FORMULAE on the BASIS of 24 (O,OH)

Si 5.69 5.76 5.82 5.80 5.57
Alt 2.36 2.42 2.37 2.31 2.86
TiVI 0.49 0.48 0.52 0.61 0.32
Fe3+ 0.24 0.22 0.48 0.80 2.10
Fe2+ 2.20 2.02 1.84 1.28 1.36
Mn 0.04 0.03 0.04 0.01 0.08
Mg 3.11 3.19 3.07 3.27 2.00
Ca 0.005 0.003 0.003 0.005 0.007
Na 0.05 0.05 0.05 0.07 0.04
K 1.82 1.83 1.82 1.83 1.67
Fet/(Fet+Mg) 0.44 0.41 0.43 0.39 0.63

* All values are given as average with standard deviation. n = the number of analyses
** Ferric and ferrous iron were determined by wet chemical analyses
 Mineralogy and Chemistry of Biotites 175

Previous works (Wones and Eugster 1965; Dodge et al. 1969; Albuquerque 1973;
Barriere and Cotten 1979; Neiva 1981) have pointed out that the Fe3+ contents and
Fetot/(Fetot + Mg) ratios provide at least relative information about the oxygen fugacity
during crystallization. According to Wones and Eugster (1965) water fugacity (ƒH2O) can
be calculated if the oxygen fugacity (ƒO2), temperature and pressure of equilibration for a

Table 4. Representative and average analyses of biotites from the Dolek and Saricicek Plutons.

Dolek and Saricicek

––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––
Biotites fom Granite Biotites from Quartz- Biotites from
to Granodiorite monzonite Quartz-
monzodiorite
–––––––––––––––––––––––––––––– –––––––––––––––––––––––––––––––– ––––––––––––––
Sample No Sr2 (n = 10)* Dk4 (n = 7)* D24 (n = 13)* Sr36 (n = 15)* Id2a (n = 11)*

SiO2 37.43 ± 0.55 36.95 ± 0.20 36.65 ± 0.33 36.63 ± 0.42 37.83 ± 1.10
TiO2 4.37 ± 0.62 4.69 ± 0.64 5.98 ± 0.54 5.93 ± 0.43 5.06 ± 0.72
Al2O3 11.96 ± 0.31 12.44 ± 0.25 13.04 ± 0.21 13.09 ± 0.45 12.15 ± 0.51
**Fe2O3 2.42 ± 0.05 3.03 ± 0.02 2.55 ± 0.04 2.61 ± 0.04 2.35 ± 0.03
**FeO 12.36 ± 0.07 15.44 ± 0.05 13.00 ± 0.05 13.28 ± 0.02 11.99 ± 0.08
MnO 0.21 ± 0.03 0.24 ± 0.02 0.22 ± 0.03 0.35 ± 0.03 0.13 ± 0.06
MgO 15.30 ± 0.45 12.80 ± 0.52 13.63 ± 0.37 13.38 ± 0.56 15.64 ± 0.61
Na2O 0.18 ± 0.01 0.11 ± 0.01 0.35 ± 0.06 0.28 ± 0.01 0.20 ± 0.01
K2 O 8.61 ± 0.30 8.96 ± 0.36 9.10 ± 0.26 8.78 ± 0.40 9.54 ± 0.53
Total 94.84 94.66 94.52 94.31 94.90

STRUCTURAL FORMULAE on the BASIS of 24 (O,OH)

Si 5.734 5.820 5.560 5.568 5.656
Alt 2.160 2.310 2.232 2.344 2.142
TiVI 0.504 0.561 0.682 0.678 0.570
Fe3+ 0.316 0.401 0.332 0.342 0.264
Fe2+ 1.612 2.031 1.696 1.746 1.498
Mn 0.026 0.035 0.028 0.044 0.016
Mg 3.494 3.013 3.082 3.032 3.486
Na 0.054 0.032 0.102 0.082 0.058
K 1.682 1.806 1.762 1.702 1.820
Fet/(Fet+Mg) 0.360 0.450 0.400 0.410 0.340

Table 5. Comparison of the Zigana, Dolek and Saricicek biotites and those of biotites in the magmatic
rock groups.

Magmatic Rock Groups FeOt [FeO+(Fe2O3x0.89981)] MgO Al2O3 FeOt/MgO

Anorogenic Alkaline Suites 30.60 4.40 11.20 7.04

Peraluminous Suites 22.10 6.30 18.90 3.48
Calc-Alkaline Suites 19.70 11.20 14.90 1.76
Zigana Granitoid 18.94 12.47 13.22 1.52
Dolek and Saricicek 15.81 14.15 12.54 1.12
176 F. Aydin et al.

Fig. 7. Relationship of Fe3+-Fe2+-Mg content of the biotites compared with buffered biotites from
Wones and Eugster (1965). Symbols are the same as those of Fig. 6.

mineral assemblage of biotite (Mg-rich) + K-feldspar + magnetite is determined. The

ternary diagram plotted from the compositions of biotites in terms of Fe2+-Fe3+-Mg shows a
buffer curve giving an estimate of the oxygen fugacity for the host magma. The biotites
have been buffered by Ni-NiO in the Zigana (Aydin et al. 1998), Dolek and Saricicek
Plutons (Fig. 7). Using equation 1 (Huebner and Sato 1970) and the equation 2 (Wones
1981), oxygen and water fugacities have been calculated. These equations are validated for
biotite compositions in the presence of Ni-NiO and Fe3O4-Fe2O3 buffers (Wones 1981).
The activities of Fe3O4 in magnetite and KAlSi3O8 in K-feldspar and the mole fraction
of Fe2+ in biotite (K2[Mg,Fe]6Si6Al2O20[OH]4) were calculated from using stoichiometric
results for the Zigana and the Dolek-Saricicek Plutons. Temperature and pressure values
for the Zigana, Dolek and Saricicek Plutons were calculated by Karsli et al. (2001, 2002).
These authors pointed out that the average Altot content in magnesio-hornblende is 0.86 in
the Zigana, and 0.93 in the Dolek and Saricicek Plutons. The common substitution of
hornblende in the Zigana Pluton is of the pargasitic type, while in the Dolek and Saricicek
Plutons it is edenitic to slightly pargasitic. Karsli et al. (2001, 2002) estimated that by
using the barometry of Schmidt (1992), P (kbar) = 4.76 Altot – 3.01, crystallization pres-
sures range from 0.6 ± 0.2 to 2.4 ± 0.4 kbar for the Zigana and from 0.45 ± 0.1 to 3.83 ±
0.7 kbar for the Dolek and Saricicek Plutons. Using the hornblende-plagioclase geother-
mometer (T= 0.667P – 48.98 + Y/-0.0429 – 0.008314 lnK) of Blundy and Holland
(1990), crystallization temperatures yield from 684 ± 13 to 642 ± 7 °C for the Zigana and
from 624 ± 6 to 755 ± 23 °C for the Dolek and Saricicek Plutons. The estimated values
can be accepted as crystallization temperature and pressure of biotites. Oxygen and water
fugacity calculations are based on the following equations:
 Mineralogy and Chemistry of Biotites 177

Log ƒO2 = A / T + B + C (P-1) / T [1]

Log ƒH2O = A / T + B + 3 Log Xbio + 0.5 Log ƒO2 - C (P-1) / T + Log a1 + Log a2 [2]

and applying the constants of the Ni-NiO buffer:

Buffer A B C Temp. range ( °C )

NiNiO –24930 9.36 0.046 600–1200 [1]

NiNiO 4819 6.69 0.011 600–1200 [2]

Where ƒH2O – water fugacity Xbio – mol fraction of Fe2+ in biotite (K2[Mg,Fe]6Si6Al2O20[OH]4)
ƒO2 – oxygen fugacity a1 – activity of KAlSi3O8 in alkali feldspar
T – temperature (°K) in Kelvin a2 – activity of Fe3O4 in magnetite
P – pressure (Kb) in kilobars

Oxygen fugacity (LogƒO2) of –16.70 to –17.90 bars and water fugacity (ƒH2O) of 518
to 860 bars were calculated for Zigana, whereas the LogfO2 of –16.01 to –20.23 bars and
water fugacity (ƒH2O) of 520 to 950 bars were calculated for Dolek and Saricicek
Plutons. When oxygen fugacity values are plotted in the Log ƒO2 – temperature (T °C)
diagram, the Zigana biotites follow a line parallel to the trend (solid oxygen-buffer curves
in Fig 8) defined for rocks crystallized under same buffer conditions, with oxygen
fugacity decreasing with temperature, as postulated by Best and Mercy (1967). This trend
of crystallization for the Zigana Plutons indicates that oxygen fugacity decreased during
crystallization of the rocks from the inner more mafic zone towards the outer more felsic
zone. Whereas the crystallization trend of the Dolek and Saricicek Plutons having lower
oxygen fugacity values was not oxygen-buffered because the solid buffers are crossed
(Fig. 8), suggesting that the biotites crystallized at differing oxygen fugacities. Low
oxygen fugacity values are also related to oxidation state of iron in magmatic system.
Mantle-derived magmas have lower oxidation state of iron than that of crustal-derived
magmas. This implies that mantle contribution (mafic component) are volumetrically
more in the southern part than crustal contribution (felsic component) on genesis of the
granitoid rocks.
The major and trace element contents and modal compositions of whole rocks have
been used to provide information on the tectonic settings of igneous rocks by several
authors (Pearce and Cann 1973; Floyd and Winchester 1975; Debon and Le Fort 1982;
Pearce et al. 1984). The biotite compositions can also be used to discriminate tectonic
settings of granitoids. When the biotites plotted on the Al2O3-FeOtot-MgO and Al2O3-
MgO plots (Figs. 9, 10) as postulated by Abdel-Fattah (1994, 1996), they fall in the field
of calc-alkaline to slightly alkaline orogenic suites. The biotites of Zigana, Dolek and
Saricicek compared with those of other calc-alkali series are more enriched in Mg (mean
12.47 to 14.90 wt%) but have lower FeOtot/MgO (Table 5). MgO contents of biotites are
higher in southern zone plutons (Dolek and Saricicek) than northern zone pluton
(Zigana). These dominantly point out Mg-Fe substitution, which play a significant role
during the crystallization of the biotites (Fig. 11a, b).
178 F. Aydin et al.

Fig. 8. Stability of biotites of specific Fe/(Fe+Mg) values as a function of oxygen fugacity and
temperature at 2070 bars total pressure. Heavy lines represent contours of constant 100 Fe/(Fe+Mg)
values. Diagram from Wones and Eugester (1965). Explanations: Curves define solid oxygen
buffers corresponding to Fe3O4-Fe2O3 (HM, Myres and Eugster, 1983); SiO2-Fe2SiO4-Fe3O4 (QFM,
Berman, 1988) and Ni-NiO (NNO, Huebner and Sato, 1970). (: Trend of crystallization of the
biotites at assumed prevailing oxygen fugacities, i.e. the sample plotted area represents an oxygen
fugacities trend of crystallizing magmas. Symbols are the same as those of Fig. 6.
 Mineralogy and Chemistry of Biotites 179

Fig. 9. The positions of the

biotites on FeOtot-MgO-Al2O3
biotite discrimination diagram of
Abdel-Fattah (1994). Symbols
are the same as those of Fig. 6.

Conclusions
The biotite compositions from the northern and southern zones of the Eastern
Pontides display the following implications:
– The biotites are dominantly governed by Mg[6]-Fetot substitution and have a more Mg-
rich character in the southern zone of plutons than the northern.
– In the Zigana Pluton which is reversely zoned, biotites compositions vary from a Mg-
rich inner zone (mafic rocks) towards a Fe-rich outer zone (felsic rocks) of the pluton.
The lower ƒO2 as well as P and T in the inner relative to outer zone of the Zigana
Pluton suggest that mafic rocks having higher ƒH2O were crystallized at low level
magma chambers.
– The oxygen fugacity defined by the Ni-NiO buffer reaction, which is strongly tempera-
ture dependent, are lower in the southern zone. Low oxygen fugacity values suggest
that mantle contributions (mafic component) are volumetrically higher in the south part
than crustal contributions (felsic component) on genesis of the granitoid rocks. In addi-
tion, low ƒO2 and pressure values indicate that Sarıcicek and Dolek Plutons crystal-
lized at relatively a low level of the Pontide Crust.
– Biotite compositions depend largely upon the nature of magmas from which they have
crystallized and demonstrate that the plutons have typical arc related calc-alkaline to
slightly alkaline character.
 180
F. Aydin et al.
Fig. 10. The positions of the biotites on MgO-Al2O3 biotite discrimination
diagram of Abdel-Fattah (1994). Symbols are the same as those of Fig. 6. Fig. 11. The Mg[6] versus Fetot variation diagram of the biotites.
 Mineralogy and Chemistry of Biotites 181

Acknowledgments
The analytical works was supported by grants from DAAD. Prof. Dr. R. Altherr is thanked for
hospitality and free access to microprobe facilities at the Mineralogical Institute of Heidelberg
University. We are most grateful to the staff of Mineralogical Institute, Heidelberg University.
Finally, we thank Prof. Dr. Durmuş Boztuğ, from the Department of Geological Engineering at
Cumhuriyet University and Dr. Cüneyt Şen, from the Department of Geological Engineering at
Karadeniz Technical University, for their critical reviews, useful comments and some valuable
suggestions.

References
Abdel-Fattah MA (1994) Nature of biotites from alkaline, calc-alkaline, and peraluminous magmas. Jour Petrol
35, 525–541
Abdel-Fattah MA (1996) Discussion on the comment on nature of biotites in alkaline, calc-alkaline, and peralu-
minous magmas. Jour Petrol 37, 1031–1035
Albuquerque CAR (1973) Geochemistry of biotites from granitic rocks, Northern Portugal. Geochim Acta 37,
1779–1802
Aydin F, Karsli O, Sadiklar M B (1998) Mineralogy, chemistry and petrological significance of biotites in the
Zigana Granitoid (NE-Turkey). Third Inter Turkish Geol Symp, Ankara, Abstracts, 70
Barriere M, Cotten J (1979) Biotites and associated minerals as markers of magmatic fractionation and deuteric
equilibration in granites. Contrib Mineral Petrol 70, 183–192
Bektaş O, Yilmaz C, Taslı K, Akdağ K, Özgür S (1995) Cretaceous rifting of the Eastern Pontide Carbonate
Platform, NE-Turkey: The formation of carbonate breccias and turbitides as evidence of a drowned platform.
Geologia 57, 233–244
Bektaş O, Şen C, Atıcı Y, Köprübaşı N (1999) Migration of the Upper Cretaceous subduction-related volcanism
towards the back-arc basin of the Eastern Pontide Magmatic Arc (NE Turkey). Geol Jour 34, 95–106
Berman RG (1988) Internally-consistent thermodynamic data for minerals in the system Na2O-K2O-CaO-MgO-
FeO-Fe2O3-Al2O3-SiO2-TiO2-H2O-CO2. Jour Petrol 29, 445–522
Best MG, Mercy ELP (1967) Composition and crystallization of mafic minerals in the Guadalupe Igneous
Complex, California. Amer Mineral 52, 436–474
Blundy JD, Holland TJB (1990) Calcic amphibole equilibria and a new amphibole-plagioclase geothermometer.
Contrib Min Petrol 104, 208–224
Buddington AF, Lindsley DH (1964) Iron-titanium oxide minerals and synthetic equivalents. Jour Petrol 5,
310–357
Çoğulu HE (1975) Gümüşhane ve Rize yörelerinde petrolojik ve jeokronolojik araştırmalar. ITU Yayinevi 1034, p
112
Debon F, Le Fort P (1982) A chemical-mineralogical classification of common plutonic rocks and associations.
Trans. R. Soc Edinb Earth Sci 73, 135–149.
Dodge FCW, Smith VC, Mays RE (1969) Biotites from granitic rocks of the Central Sierra Nevada Batholith, Cali-
fornia. Jour Petrol 10, 250–271
Floyd PA, Winchester JA (1975) Magma type and tectonic setting discrimination using immobile elements. Earth
Planet Sci Let 27, 211–218
Gedik A, Ercan T, Korkmaz S, Karataş S (1992) Rize-Findikli-Çamlihemşin arasinda (Doğu Karadeniz) yer alan
magmatik kayaclarin petrolojisi ve Doğu Pontidlerdeki bolgesel yayilimlari. Geol Bull Turkey 35, 15–38
Güven IH (1993) Dogu Pontidler’in 1/250 000 ölcekli komplikasyonu. MTA , Ankara (Unpublished report)
Hey MH (1982) The determination of ferrous and ferric iron in rocks and minerals; and a note on sulphosalicylic
acid as a reagent for Fe and Ti. Miner Magazine 46, 111–118
Huebner JS, Sato M (1970) The oxygen fugacity-temperature relationships of manganese oxide and nickel oxide
buffers. Amer Mineral 55, 934–952
Karsli O, Sadiklar MB (1996) Mineralogy and genesis of Zigana Granitoid (Macka-Trabzon). Beih EJM 8, 133
Karsli O, Sadiklar MB (1997) Granitoyid kayaclarin mineralojik degisiminin belirlenmesinde yeni bir yaklasim:
Zigana Granitoyidi (Macka-Trabzon). Geosound 30, 601–611
Karsli O, Aydin F, Sadiklar MB (2001) Hybridisation of low contrasted coeval magmas: Mineralogical and chem-
ical evidences, Dolek and Saricicek Plutons NE-Turkey. Beih EJM 13/1, 91
182 F. Aydin et al.

Karsli O (2002) Granitoyid kayaclarda magma etkilesimleri icin petrografik, mineralojik ve kimyasal bulgular:
Dolek ve Saricicek plutonlari (Gumushane, KD-Turkiye). Unpublished PhD Thesis, Karadeniz Technical
University, 226 pp
Karsli O, Aydin F, Sadiklar MB (2002) Geothermobarometric Investigation of the Zigana Granitoid, Eastern
Pontides, Turkey. Inter Geol Review 44, 277–286
Ketin I (1966) Turkiyenin tektonik birlikleri. Bulletin of MTA 66, 23–24
Lalonde AE, Bernard P (1993) Composition and color of biotite from granites: two useful properties in the charac-
terization of plutonic suites from the Hepburn interval zone of Wopmay orogen, Northwest Territories. Canadian
Mineral 31, 203–217
Lalonde AE Rancourt DG, Chao GY (1996) Fe-bearing trioctahedral micas from Mont Saint-Hilaire, Quebec,
Canada Miner Magazine 60, 447–460.
Myres J, Eugster HP (1983) The system Fe-Si-O: Oxygen buffer calibrations to 1.500 °K. Contrib Mineral Petrol
82, 75–90
Neiva AMR (1981) Geochemistry of hybrid granitoid rocks and of their biotites from Central Northern Portugal
and their petrogenesis. Lithos 14, 149–163
Pearce JA, Cann JR (1973) Tectonic setting of basic volcanic rocks investigated using trace element analyses.
Earth. Planet Sci Lett 19, 290–300
Pearce JA, Harris NBW, Tindle AG (1984) Trace element discrimination diagrams for the tectonic interpretation of
granitic rocks. Jour Petrol 25, 956–983.
Schmidt MW (1992) Amphibole composition in tonalite as a function of pressure: An experimental calibration of
the Al-in hornblende barometer. Contrib Min Petrol 110, 304–310
Streckeisen A (1976) To each plutonic rock its proper name. Earth Sci Rev 12, 1–13
Speer JA (1984) Micas in igneous rocks. In: Bailey SW (Ed) Micas. Reviews in Mineralogy 13, 299–356
Taylor RW (1964) Phase equilibria in the system FeO-Fe2O3-TiO2 at 1300 °C. Amer Mineral 49, 1016–1030
Yilmaz C, Karsli O (1997) Macka-Zigana yoresinde Ust Kretase surecindeki cokel kayitlari ve bolge jeolojisindeki
onemi. Geosound 30, 331–340
Yilmaz C, Karsli O, Aydin F (1997) Upper Cretaceous intra-arc sedimentation, magmatism, and tectonism in the
south of Trabzon: IAS, 18th Regional Meeting of sedimentology, Heidelberg, Abstracts, 369
Yilmaz C (2002) Gümüşhane-Bayburt Yöresindeki Mesozoyik havzalarinin tektono-sedimantolojik kayitlari ve
kontrol etkenleri. Geological Bulletin of Turkey 45, 141–164
Verhoogen J (1962a), Distribution of titanium between silicates and oxides in igneous rocks. Amer Jour Sci 260,
211–220
Verhoogen J (1962b) Oxidation of iron-titanium oxides in igneous rocks. Jour Geol 70, 168–181
Wones DR, Eugester HP (1965) Stability of biotite: Experiment, theory and application. Amer Mineral 50,
1228–1272
Wones DR (1981) Mafic silicates as indicators of intensive variables in granitic magmas. Mining Geol 31, 191–212