Contributions to

Contrib. Mineral. Petrol. 58, 63-81 (1976)

Mineralogy and
Petrology
9 by Springer-Verlag 1976

Geochemistry of Eocene Calc-Alkaline Volcanic Rocks

from the Kastamonu Area, Northern Turkey

Angelo Peccerillo* and S.R. Taylor

Research School of Earth Science, Australian National University, A.C.T., Canberra, Australia

Abstract. Analytical data for Sr, Rb, Cs, Ba, Pb, rare earth elements, Y,
Th, U, Zr, Hi', Sn, Nb, Mo, Ni, Co, V, Cr, Sc, Cu and major elements
are reported for eocene volcanic rocks cropping out in the Kastamonu area,
Pontic chain of Northern Turkey. SIO2% versus K 2 0 % relationship shows
that the analyzed samples belong to two major groups: the basaltic andesitic
and the andesitic ones. High-K basaltic andesites and low-K andesites occur
too. Although emplaced on continental type basement (the North Anatolian
Crystalline Swell), the Pontic eocene volcanics show elemental abundances
closely comparable with typical island arc calc-alkaline suites, e.g. low SiO2 %
range, low to moderate K 2 0 % and large cations (Cs, Rb, Sr, Ba, Pb)
contents and REE patterns with fractionated light and almost fiat heavy
REE patterns. Z REE and highly charged cations (Th, U, Hf, Sn, Zr) are
slightly higher than typical calc-alkaline values. Ferromagnesian elements
show variable values. W i t h i n the basaltic andesite group the increase of
K % , large cations, Z R E E , La/Yb ratio and high valency cations and the
decrease of ferromagnesian element abundances with increasing SIO2% con-
tent indicate that the rock types making up this group developed by crystal-
liquid fractionation of olivine and clinopyroxene from a basic parent magma.
Trace element concentration suggest that the andesite group was not derived
by crystal-liquid fractionation processes from the basaltic andesites, but could
represent a distinct group of rocks derived from a different parent magma.

Introduction

The tectonic evolution of the Mediterranean area has been recently reviewed
by several authors [1, 2]. It has been pointed out that many of the tectonic
and magmatic features have been caused by a complex series of underthrusting
* On leavefrom: Istituto di Mineralogia, Petrografia e Geochimicadell'Universit/t,Via Lamarmo-
ra 4, Firenze, Italy (present address)
64 A. Peccerillo and S.R. Taylor

and collision of minor plates occurring between the two large cratons of Africa
and Europe. Disagreement still exists concerning the movements of these minor
plates and on the directions of subduction of ancient oceanic areas. One way
to approach these problems is the study of igneous belts typically associated
with converging plate boundaries.
On the northern margin of the Turkish plate, an Upper Cretaceous and
Eocene volcanic belt occurs. We have undertaken a study on major and trace
element of both Cretaceous and Eocene volcanics cropping out in the Kastamonu
area of northern Turkey.
In this paper data and discussion will deal with petrology and geochemistry
of Eocene volcanics. The data on the Upper Cretaceous rocks will be reported
on separately.

Geological Setting

The general geological and tectonic features of the Pontic chain have been
reported by several authors [3-5]. Here only a brief summary is given. The
Pontic chain which rims the southern border of the Black Sea is the central
portion of an extensive belt running from western Bulgaria through Turkey
to the Caucasus [5]. The lowest exposed rocks in the Pontids form an extensively
folded metamorphic basement composed of gneisses, schists, phyllites and am-
phibolites believed to be Paleozoic in age. On this basement lie the Mesozoic
formations, which consist of Triassic limestones, Jurassic shales, sandstones,
quartzites and limestones in some place associated with diabases and spilites,
and neritic carbonatic sediments. The most streaking features of the Pontic
chain are the volcano-sedimentary complexes of Upper Cretaceous and Eocene
age. The Upper Cretaceous volcanic activity took place mainly in the central-
eastern part of the Pontic belt. It consists dominantly of andesitic and basaltic
lavas, tufts, agglomerates often intercalated with limestones, marls and
sandstones. Volcanism was both subaerial and submarine as evidenced by the
occasional occurrence of pillow lava structures. The Eocene volcanic activity
took place along a belt parallel to the Upper Cretaceous volcanic chain, but
slightly displaced southward. It consists of andesitic lavas, tufts and agglomerates
often interbedded with neritic calcareous sediments and marly and arenaceous
flysch. From the end of the Eocene to the Miocene extensive acidic and inter-
mediate plutonic activity occurred with intrusions along the southern border of
the chain.
The problem of the relative plate movements in the eastern Mediterranean
area during the late Mesozoic and early Cenozoic is still under debate. According
to Dewey et al. [1] the tectogenetic processes and magmatic features of the
Pontic chain were caused by the southward subduction of the Tethys I oceanic
area under the Turkish plate. According to this view, the Black Sea is considered
as a remanent of the Tethys I oceanic area. This view has been recently ques-
tioned by Adamia [6]. Boccaletti et al. [2] suggest the occurrence in the Upper
Cretaceous-Paleocene of two subduction zones with northward polarity. The
Izmir-Ankara and Tauro-Lycian ophiolitic belts are thought to represent the
Geochemistry of Eocene Calc-Alkaline Volcanic Rocks 65

Fig. 1. Geological sketch map of the Kastamonu area. cr metamorphic crystalline basement; mof
mesozoic ophiolites ; krfcretaceous flysch ; ev eocene volcanics; ef eocene flysch ; eol eocene-oligocene
formations (from the Geological Map of T u r k e y - S h e e t of Sinop, 1/250,000)

remnants of the two underthrust oceanic areas. Similar hypothesis has been
more recently put forward by Ataman et al. [7].

Sampling

All the samples of the present study were collected in the Kastamonu area. Samples T69-158
and T69-159 come from Havza and Corum outcrops lying south-east of Kastamonu. The Kastamonu
series lies on the Paleozoic crystalline basement and the contact is believed to be faulted. In
this area the interbedded relationship between volcanics and Eocene flysch is clear. Andesitic
lavas, tufts, agglomerates and breccias occur. The samples have been collected along the entire
outcrop which runs approximately E-W from Kastamonu to Arac. The description of the samples
is given in appendix. Figure 1 is a sketch geological map of the Kastamonu area, taken from
the geological map of Turkey Sinop sheet (1/250,000).

Classification

Rocks found in island arc or subduction zone environments present many problems in classification.
Chemical rather than petrological or mineralogical parameters have come to be preferred on account
of the difficulty in resolving the mineralogy of the commonly encountered fine grained groundmass
66 A. Peccerillo and S.R. Taylor

banak/?e

Hi, h-l( dacl?~o

o
shoshom?e

~bsarok/?e t @ h - i f andes/?e

rh~o*?e
dac/te

/ .to I\
an~tes/te 9 l 9

"1
basalt/c ff 9 eo
9~ I ~,ndeslte
basaH ~. 9

I Zo~/a~( I hasa/t/c /ow-/(andesi?e

I thole:lie [ andes/?e_
52 56 63 70

Fig. 2. Relationship between Si02 and K 2 0 content. Lines on the K 2 0 divisions mark the boundaries
between: arc tholeiite series (I), calc-alkaline series (II), high-K calc-alkaline series (III) and shosho-
nite series (IV)

in these rocks. The most significant variations among the major elements are usually in the abun-
dances of SiO2 and K20. The minor, but significant variation in potassium are frequently not
readily apparent to petrographic examination. For such reasons, we have adopted a classification
modified from that of Taylor [8]. This is based on the variation of SiO2 and K 2 0 and a diagrammatic
representation is given in Figure 2. It should be emphasised that this represents an attempt to
divide a continuum and that the boundaries are not rigid. The slope on the K 2 0 divisions attempts
to match the observed trends in natural rocks.
The large number of elements studied here calls for subdivision and the scheme adopted
is that of Taylor [9] which separates the major elements, large cations, rare earth elements, large
high-valency cations and ferromagnesian elements.

Analytical Methods

The major elements were determined by electron microprobe on glass beads prepared by fusion
of pure rock powder [10]. Accuracy and precision of the method are variable for the different
oxides ([I0], Table 1). NazO and KEO data obtained on some of our samples by classical flame
photometric methods compare well with the microprobe results, which seems to exclude appreciable
loss of alkalies during glass preparation. Rb, Sr, Zr and Y were analyzed by X-ray fluorescence
spectroscopy on pressed rock powder pellets. Calibration was made against natural rock standards.
Precision expressed as relative deviation is + 5 % for the range of values found in our samples.
Cr, V, Sc, Ni, Co and Cu were determined by emission spectrography using the method of Ahrens
and Taylor [11]. Precision expressed as relative deviation is + 5%, but reaches values of 10-20%
at low ppm levels. Cs, Pb, Ba, REE, Y, Th, U, Hf, Sn, Nb and Mo were determined by spark
source mass spectrography using the method of Taylor [12]. Tm and Lu abundances are calculated.
The precision expressed as relative deviation is _+5%.
Geochemistry of Eocene Calc-Alkaline Volcanic Rocks 67

d d d ~ M g d d

d,

.,'N

&
~D

P~
&

&
<

0 ~'-' r
~ < ~ Z ~ ~ ~ ~ ;~ ~"
68 A. Peccerillo and S.R. Taylor

Results

Major Elements

Data are given in Table 1, with some additional X R F values for Rb, Sr, Zr
and Y. SIO2% ranges from values of about 52% to 63.5%. This agrees with
Ketin's [3] statement that the Eocene volcanic belt of the Pontic chain consists
essentially of andesites while the basic and acidic members of the calc-alkaline
series are present only in minor amounts. An important feature of the major
element chemistry of the samples is given by the S i O 2 - K z O relationship shown
in Figure 2. It is possible to divide the Kastamonu volcanics into four groups.
The first group with relatively low SiO2 and K 2 0 contents pl0t in the zone
between basaltic andesites and andesites. They are referred to here as basaltic
andesites. This group shows a very good positive correlation between K 2 0
and SiOz. The average 8 i 0 2 % and K 2 0 % is 56.02 and 0.83 respectively. A
second group plots in the field of low-K andesites while a third group falls
in the upper part of the andesitic field close to the dacite limit. These are
referred to as andesites. The average SiOz% and K 2 0 % is 61.6 and 1.6 respec-
tively. Samples T69-158 and T69-159 show a high K 2 0 content at a low S i O 2
content and plot in the field of high-K basaltic andesites.
In the modern island arcs, the calc-alkaline volcanics show an increase of
K 2 0 at a same SiO 2 content away from the oceanic trenches [13]. This increase
shows a close correlation with increasing depth of earthquake foci (Benioff zone)
under the volcanic arc. Using the K-h diagram of Ninkovich and Hays [14], the
basaltic andesite data plot very close to the curve of 120 km depth to the Benioff
zone. The andesite data plot between the curves of 120-150 kin. Since these
samples are geographically contiguous this difference could be explained by
a shift in the position of the subduction zone. Such interpretation assumes

Table 2. Trace element data. All values in p p m (wt.) except where indicated at wt%

Basaltic Andesites Low K

Andesite

T69-21 T69-22 T69-25 T69-24 T69-36 T69-27

Cs 0.49 0.45 0.36 1.30 0.68 0.45

Rb 9 17 13 20 19 12
K% 0.55 0.65 0.64 0.77 0.87 0.62
Ba 88 103 122 140 192 150
Eu 0.87 0.85 0.80 0.86 0.98 0.93
Pb 3.4 2.94 2.18 3.7 3.06 3.3
Sr 307 313 386 392 375 344
Ca% 6.95 7.28 5.86 5.23 5.22 5.38
Na% 2.19 2.40 2.85 2.88 3.03 2.71
K/Rb 611 382 492 385 458 517
x 10 3 K/Cs 11.2 14.4 17.8 5.9 12.8 13.8
Rb/Cs 18.4 37.7 36.1 15.4 27.9 26.6
Geochemistry of Eocene Calc-Alkaline Volcanic Rocks 69

t h a t the m a g m a g e n e r a t i o n , a n d the source o f the K - h r e l a t i o n s h i p o f D i c k i n s o n

a n d H a t h e r t o n [13] is f u n d a m e n t a l l y r e l a t e d to the s u b d u c t i o n zone, r a t h e r
t h a n to the m a n t l e a b o v e this zone. T h e h i g h - K b a s a l t i c andesites c o m e f r o m
C o r u m a n d H a v z a zone which lie s o u t h - e a s t o f K a s t a m o n u . F r o m a n a l o g y
with the p o l a r i t y r e l a t i o n s h i p s o f the K z O % in the m o d e r n island arcs, the
h i g h - K r o c k s o f C o r u m a n d H a v z a c o u l d p r o v i d e evidence for a s o u t h - e a s t
d i p p i n g o f the paleoseismic zone, as p r o p o s e d b y D e w e y et al. [1]. It is o b v i o u s
t h a t a m o r e w i d e s p r e a d s a m p l i n g over all the P o n t i c v o l c a n i c belt is necessary
in o r d e r to c o n f i r m this d e d u c t i o n .

Large Cations

T r a c e e l e m e n t d a t a are r e p o r t e d in T a b l e 2.
T h e a b u n d a n c e s o f large c a t i o n s (Cs, R b , Pb, Ba, Sr a n d Eu) are typical
o f island arc calc-alkaline rocks. R b , Pb, Ba a n d Eu show all a very g o o d
c o r r e l a t i o n with K % .

REE + Y

T h e 2; R E E is v a r i a b l e a n d shows a general t e n d e n c y to increase with increasing

SiO2 a n d K 2 0 c o n t e n t s for the a n a l y z e d samples. L a / Y b versus SiO2 is shown
in F i g u r e 3 a n d L a / Y b versus K is s h o w n in F i g u r e 4. T h e f o u r different g r o u p s
p l o t in different areas. T h e b a s a l t i c andesites s h o w the lowest L a / Y b values
a n d a g o o d positive c o r r e l a t i o n o f L a / Y b versus K % a n d SIO2%. T h e andesites
show the highest R E E a b s o l u t e a b u n d a n c e as well as L a / Y b values which
increase t h r o u g h the g r o u p with increasing SIO2% content. I n F i g u r e 5 the

Andesites High K basaltic

andesites

T69-93 T69-20 T69-19 T69-91 T69/108 T69/40a T69-158 T69-159

0.51 1.09 1.73 1.00 0.33 0.59 2.06 1.60

43 39 44 53 11 38 48 68
1.30 1.49 1.55 1.71 0.89 1.53 1.60 2.23
179 220 216 256 258 330 583 670
1.14 1.06 1.06 1.41 0.75 0.99 1.0 1.14
4.78 4.44 6.57 4.84 4.19 6.95 22 12.5
414 454 408 359 376 405 779 583
5.41 4.82 4.97 4.10 4.36 4.12 6.29 6.88
3.02 3.I5 3.21 3.18 2.90 2.84 2.69 2.15
302 382 352 323 809 403 333 328
25.5 13.7 9.0 17.1 27.0 25.9 7.8 13.9
84.3 35.8 25.4 53 33.3 64.4 23.3 42.5
70 A. Peccerillo and S.R. Taylor

Table 2 (continued)

Basaltic andesites Low K

andesites

T69-21 T69-22 T69-25 T69-24 T69-36 T69-27

Ba/Rb 9.7 6.1 9.4 7.0 10.1 12.5

Rb/Sr 0.03 0.05 0.03 0.05 0.05 0.03
Sr/Eu 353 368 482 456 382 370
La 9.7 10.33 9.88 12.04 15.13 11.0
Ce 20.7 24.60 23.69 26.5 36.16 24.9
Pr 2.5 2.4 2.36 2.98 3.84 2.74
Nd 11.1 11.2 10.26 12.05 14.45 11.26
Sm 2.5 2.39 2.27 2.27 2.78 2.49
Eu 0.87 0.85 0.80 0.86 0.98 0.94
Gd 2.59 2.71 2.38 2.35 2.79 2.52
Tb 0.50 0.45 0.40 0.40 0.45 0.42
Dy 2.99 2.90 2.44 2.54 2.83 2.71
Ho 0.67 0.67 0.56 0.55 0.62 0.59
Er 2.04 1.93 1.65 1.65 1.84 1.55
Tm 0.32 0.31 0.26 0.28 0.30 0.25
Yb 1.94 1.89 1.59 1.70 1.82 1.49
Lu 0.30 0.29 0.25 0.45 0.28 0.23
S REE 58.72 62.92 57.46 66.62 82.38 61.62
Y 20 21 18 17 21 15
SREE§ 78.72 83.92 75.46 83.62 103.38 76.62
La/Yb 5.0 5.46 6.21 7.08 8.31 7.38
Gd/Eu 2.98 3.19 2.97 2.73 2.84 2.68
Eu/Eu* 1.07 1.04 1.10 1.17 1.10 1.18
Eu* 0.81 0.82 0.73 0.73 0.89 0.80
Th 1.82 2.11 1.65 2.71 2.75 2.26
U 0.50 0.57 0.62 0.93 0.80 0.74
Zr 97 110 118 129 136 110
Hf 2.52 2.42 2.55 3.06 2.60 2.97
Sn 0.97 0.84 0.95 0.89 1.02 0.78
Nb 10 8 11 13 17 10
Ti% 0.58 0.59 0.44 0.38 0.34 0.49
Mo . . . . 1.32 0.90
Th/U 3.62 3.70 2.66 2.92 3.4 3.07
x 10 -3 K / U 11.0 11.4 10.3 8.3 10.9 8.37
Zr/Hf 38.5 45.4 46.3 42.2 52.3 37.0
Zr/Nb 9.7 13.7 10.7 9.9 8.0 11.0
Cr 210 250 58 13 12 55
V 135 170 110 76 82 88
Sc 28 30 18 10 11 17
Ni 90 95 27 9 6 24
Co 27 27 20 16 16 13
Cu 52 62 35 16 22 35
Fe% 6.02 5.79 4.82 4.89 4.29 3.87
Mg% 4.89 2.33 2.32 2.00 1.67 1.41
Al% 9.28 9.92 10.64 10.52 10.83 10.71
Si% 24.42 25.57 26.30 26.99 27.22 27.89
V/Ni 1.50 1.79 4.07 8.44 13.66 3.66
Cr/V 1.55 1.47 0.53 0.17 0.15 0.63
Ni/Co 3.33 3.52 1.35 0.56 0.37 1.85
Fe/Ni 669 609 1785 5433 7150 1612
Geochemistry of Eocene Calc-Alkaline Volcanic Rocks 71

Andesites High K basaltic

andesites

T69-93 T69-20 T69-19 T69-91 T69/108 T69/40a T69-158 T69-159

4.2 5.6 4.9 4.8 23.4 8.7 12.1 9.8

0.10 0.09 0.11 0.15 0.03 0.09 0.06 0.12
363 428 385 255 501 409 779 5l 1
20.70 23.5 21.0 24.9 19.00 21.79 14.1 15.3
44.9 47.2 41.8 53.7 34.8 41.65 29.1 32.6
4.68 5.73 4.14 5.7 3.52 4.31 3.56 4.02
20.14 22.3 17.03 22.45 12.65 16.81 15.2 18.08
4.31 3.8 3.65 4.38 2.16 2.86 3.27 3.49
1.14 1.05 1.06 1.41 0.75 0.99 1.00 1.14
4.28 3.48 3.49 4.29 2.05 2.99 3.19 3.53
0.79 0.60 0.59 0.67 0.32 0.48 0.53 0.52
4.96 3.78 3.79 4.05 1.99 3.09 3.01 2.92
1.16 0.9 0.84 0.77 0.44 0.64 0.68 0.58
3.54 2.52 2.46 2.11 1.25 1.84 1.93 1.75
0.58 0.25 0.40 0.36 0.21 0.30 0.29 0.28
3.54 2.64 2.43 2.14 1.26 t.83 1.77 1.63
0.55 0.24 0.38 0.34 0.19 0.28 0.27 0.26
112.65 118.0 100.9 125.0 78.9 97.68 77.9 83.48
46 27 25 18 15 21 19 22
158.65 145.0 125.9 143.0 93.9 118.68 96.9 105.48
5.85 8.90 8.64 11.6 15.08 11.9 7.97 9.38
3.75 3.31 3.29 3.04 2.73 3.02 3.19 3.09
0.83 0.90 0.93 1.02 1.12 1.07 0.98 1.02
1.37 1.16 1.14 1.38 0.67 0.93 1.02 1.12
3.18 4.32 4.56 5.57 3.07 4.82 4.59 5.30
1.06 1.01 1.35 2.01 0.66 0.92 1.66 1.31
226 219 223 210 146 159 87 111
4.23 4.76 5.53 6.20 3.04 3.83 2.49 2.30
1.14 1.66 1.78 1.68 0.74 0.97 1.14 1.14
18 23 24 24 18 20 4.5 7
0.49 0.41 0.39 0.39 0.36 0.35 0.55 0.55
1.21 - 1.59 2.22 0.57 1.28 - 1.27
3.00 4.31 3.36 2.75 4.63 5.25 2.78 4.05
12.3 14.8 11.5 8.5 13.5 16.6 9.6 17.0
53.4 46.0 40.3 33.9 48.0 41.5 34.9 48.7
12.6 9.5 9.3 8.7 8.1 7.9 19.3 16.0
15 10 10 8 35 26 35 220
125 110 105 84 74 84 250 190
13 10 10 8 10 10 32 31
5 6 -- - 11 8 20 45
8 10 8 4 9 10 38 29
7 16 i3 5 20 11 80 66
3.56 4.41 3.33 3.12 3.57 2.97 7.59 5.67
0.82 0.95 0.75 0.55 1.27 1.02 2.53 3.31
10.77 9.96 10.13 10.24 9.72 9.96 9.79 8.42
27.88 28.29 28.73 29.21 29.55 29.73 24.40 25.78
25.0 18.33 -- -- 6.73 10.5 1.75 4.22
0.12 0.09 0.10 0.10 0.47 0.31 0.14 1.16
0.62 0.6 -- -- 1.22 0.80 0.53 1.55
7120 7356 -- - 3245 3712 3795 1260
72 A. Peccerillo and S,R. Taylor

, i . l , , . . l . , , . l . ,

10

o 9
o 9
o
o

I I I I . . . . I . . 9 . i . 9
50 55 60 65
sio 2 %
Fig. 3. La/Yb ratio versus Si02/o content for the analyzed samples. Basaltic andesite (o), andesite
(e), low-K andesite (A), high-K basaltic andesite (-k)

' I ' I ' I

10
00
O
O r
O
O
O

.o

9 I I I , I

1.o K ~ 2.0 ~0
Fig. 4. La/Yb ratio versus K 2 0 % content. Symbols as in Figure 3

R E E patterns normalized to chondritic a b u n d a n c e s are shown. All the analyzed

samples have typical fractionated light R E E and almost " f l a t " heavy R E E
pattern and no u n f r a c t i o n a t e d patterns similar to island arc tholeiites [15] or
m i d - o c e a n ridge basalts are f o u n d in these rocks. The andesites have similar
patterns for light R E E but differ in heavy R E E (exp. T69-93) whereas basaltic
 Geochemistry of Eocene Calc-Alkaline Volcanic Rocks 73

100 I00
II I l l l l l l l l , , , , , , ~ 1 , , I , ,

| so 50

o r reg-lse "~'-- 2
10

Andeslte Hlgh-K basaltic andeslte 5

I l l ~ I l l l l l l l l A I I I I I t I I I I I I I C
LaCaPrd SmEuGdTbDyHoErTmyb L a C e Pr N d SrnEuGdTbDyHo Er Trn Y b
100 100
I I I I I I ! I I I I I I I I I I I I I I I I [ I I
7"69 36
5O 50
*'-~.
e"%o~%0%o
o
10 10
E
o. $
5

E Basaltic ancleslt e LOW- K andealte

CL
CL

I I I I I I i t i I I I I B I I I I I I I a I I I i I D
L a C o Pr Nd S m E u G d Tb D y H e Er T m Y b LO C e Pr N d Srn EuGd TbDy HoEr TmYb
Fig. 5A-D. Chondrite normalized REE patterns for the analyzed samples: A Andesite range (evi-
denced is T69-93); B Basaltic andesite range (evidenced is T69-36); C High-K basaltic andesite;
D Low-K andesite

9 d ! . . . . I " " " !

O& 0 9

200

E O
t~ qP 9 9

o o o
o 0
tO0
9 9 I t 9 9 9 ! | I I
55 60 65
slo
Fig. 6. Diagram showing the positive correlation between Zr and SIO2% content. Symbols as
in Figure 3

andesites show differences in light R E E (exp. T69-36). T h e two h i g h - K basaltic

andesites have similar p a t t e r n s with T69-159 m o r e enriched in absolute a b u n -
dance a n d with m o r e f r a c t i o n a t e d p a t t e r n in respect to T69-158.
74 A. Peccerilloand S.R. Taylor

Europium Anomalies

Many of the samples show an Eu anomaly which is not common in calc-alkaline

rocks. Three basaltic andesites have significant positive Eu anomalies (Eu/Eu*
> 1.10) together with the low-Si andesite. In the andesites, the more basic samples
have significant negative Eu anomaly (Eu/Eu*< 0.9). In this group the Eu/Eu*
values increase with the increasing SiOz content. Since plagioclase is the only
mineral which is believed to produce significant Eu anomalies in the rocks
[16, 17] it can be inferred that separation and accumulation of plagioclase
has been important in the genesis of several members of the Kastamonu series.

High Valency Cations

Th and U averages are slightly higher than the values given by Jakeg and
White [18] for average calc-alkaline rocks. Th/U is quite variable and does
not show any regular behaviour through the series. Both Zr and Hf show
a positive correlation with SiO2 but there are many exceptions (Fig. 6). The
absolute abundance of these two elements is greater than typical calc-alkaline
values.
The Nb abundance is very high (16 ppm average) compared to average
andesitic values (4.3 ppm [8]). In summary, all the high valency cations show
higher abundances than typical calc-alkaline series at any SIO2% content. They
show also a general increase through the series passing from the basic to the
acidic members.

Ferromagnesian Elements

In the basaltic andesites the ferromagnesian element abundances decrease with

increasing SiOz content. In Figure 7 the Ni and Cr versus SiO/ relationship
is shown. In the andesites the ferromagnesian elements are less abundant and
only Vanadium shows a decrease with increasing SiO2, while the other elements
are more variable. The samples T69-40a and T69-108 with high SiO2 values
are more enriched in ferromagnesian elements (except V) than the other more
basic members of the group.

Comparison with Other Island Arcs

Jakeg and White [19, 20] proposed that differences between calc-alkaline rocks
from island arcs and from continental margins have genetical significance. The
main differences between the two series are that SiO2 range, KzO/Na/O ratio
and K20, Rb, Ba, Sr, Th, U and Zr abundances are all thought to be higher
in the continental margin calc-alkaline suite. Since the Pontic Eocene volcanic
chain lies on a continental type basement it is of interest to compare the Kasta-
monu volcanics with typical island arc and continental margin calc-alkaline
suites.
Geochemistry of Eocene Calc-Alkaline Volcanic Rocks 75

' ' " I . . . . I . . . . I ' '

o %

!00

o 9

I:
0
0
!0

, ~ , i t t I I ! t t t s I t ,
55 60 65
siO 2 %

! I I I , , , w I , , I , I I I
100 @
0

o &

10
0

i , , j , , , , I ,L,L , i , ,
55 60 65
SiO 2
Fig. 7. Cr/SiO2 (A) and Ni/SiO2 (B) relationship for the analyzed samples. Symbols as in Figure 3
76 A. Peccerilloand S.R. Taylor

The basaltic andesites have Rb, Ba and Sr averages close to the values
of the basic members of the island arc calc-alkaline series given by Jakeg and
White ([18], Table 2b). The andesites have K20, Rb and Sr abundances and
K/Rb ratios similar to typical island arc andesites, while U and Th show slightly
higher values. On these grounds, the Kastamonu rocks, although emplaced
on a continental basement, have many features more closely comparable with
typical island arc calc-alkaline rocks than with continental margin andesites.
The basaltic andesites have low XREE (ranging from 58 ppm to 82 ppm)
while andesites show slightly higher values than typical circumpacific andesites
which have generally ZREE values below 100 ppm [21, 22]. Y is variable but
close to andesitic values. All the high valency cations, as already pointed out,
have high abundances compared to average andesitic values [9, 18] at any
SiO2 content. The ferromagnesian elements are typically low in abundance
in the andesites with low Ni/Co and high V/Ni ratios. For the basaltic andesite
group, their abundance is high and decreases with increasing SiO2 content.
In this group Ni/Co ratio decreases from 3.3 to 0.37 and V/Ni ratio increases
from 1.5 to 10.8 with increasing SiO2 content and both reach typical calc-alkaline
values (Ni/Co < 1 and V/Ni > 10 [21]) only in the most acidic samples. These
characters, together with the low K20% of the basaltic andesites could suggest
some similarities with island arc tholeiites [15]. However this possibility is ruled
out by their fractionated REE pattern as well as by their high abundance
in many of the other trace elements, especially the high valency cations. These
elemental abundances reinforce the view that there is a continuum of elemental
concentrations, with much fine scale variability. Many of these variations are
consistent with different degrees of partial melting, with some distinct differences
in the trace element contents of the source material.

Discussion

On the basis of both major and trace element abundances the calc-alkaline
volcanic rocks of Kastamonu region have been divided in four groups. The
first group, the basaltic andesites, is characterized by low I;REE, Rb, Ba,
Pb and high concentration of ferromagnesian elements, and a relatively fraction-
ated REE pattern. Rb, Ba, Pb, ZREE, La/Yb ratio and the high valency cations
increase in abundance from the most basic to the acidic members. Conversely,
the ferromagnesian elements decrease from high values of the samples T69-21
and T69-22 to low values typical of island arc andesites. All these characters
suggest the occurrence of crystal-liquid fractionation within the group. Probable
phases which have separated are olivine and clinopyroxenes. Both minerals
have had a major role in producing the most acidic samples from the more
primitive ones. The fractionation of olivine can account for the behaviour of
Ni and Co which are readily accomodated in the olivine lattice. However,
clinopyroxene separation is also necessary in order to explain the decreasing
amounts of trivalent ferromagnesian elements (e.g. V, Sc). Clinopyroxene fractio-
nation also accounts for the increasing La/Yb ratio [16]. This process, however,
can not explain some of the features of some samples of the group (e.g. same
Geochemistryof Eocene Calc-AlkalineVolcanic Rocks 77

2;REE in T69-21 and T69-25). Furthermore, T69-25, T69-24 and T69-36 have
a significant positive Eu anomaly ( E u / E u > 1.1). Since plagioclase is the only
common rock mineral which is known to produce this effect, it is inferred
that some of the plagioclase phenocrysts did not crystallize in equilibrium with
the surrounding matrix but are of accumulative origin. Sample T69-22 does
not fit in this general frame owing to its notably higher ferromagnesian element
abundance in respect to the most primitive rock (T69-21) and higher FeO/MgO
ratio in respect to some of the more acidic members of its group.
An alternative is that the parent magma had the composition of T69-25
and the two more basic members of the group are derived from this magma
by accumulation of olivine and clinopyroxene. However, the olivine crystals
of the samples T69-21 and T69-22 do not show any reaction rim and this
process can not explain, for example, the higher FeO/MgO ratio, Rb, ! ; R E E
and Th abundances of T69-22 and the similar 2;REE in T69-21 in respect
to T69-25.
The andesites show higher abundance of K, large cations, REE and high
valency cations but are depleted in ferromagnesian elements in respect to the
basaltic andesites. The most basic members of the group show significant nega-
tive Eu anomalies (Eu/Eu*<0.9). La/Yb ratio shows a general tendency to
increase with increasing S i O 2 content but this pattern is not well defined. There
is some overlap between the La/Yb values between the most acidic basaltic
andesites and the basic members of the andesite group (Fig. 3). The ferromagne-
sian elements are relatively more abundant in the most SiO2-rich samples of
the series (i.e. T69-108 and T69-40a) which have also the highest La/Yb ratios.
Could this group or at least some members be derived from the basaltic
andesitic magma by processes of crystal liquid fractionation or represents a
distinct group of rocks derived from a different parent magma? Samples T69-108
and T69-40a can not be derived by crystal-liquid fractionation from the basaltic
andesites, because they have a higher abundance of many ferromagnesian ele-
ments compared to the more acidic samples of the basaltic andesitic group
(see Fig. 7). The most basic members of the andesite group could be derived
from the basaltic andesites by continuing separation of olivine and clinopyrox-
ene. Separation of plagioclase is also necessary in order to explain the negative
Eu anomalies of these samples in respect to the positive Eu anomalies of the
basaltic andesitic group. However this process is not able to explain some
important features of the basic members of the andesites. It does not explain
(for example) the relatively high V abundance compared to the acidic samples
of the andesite group. In addition the La/Yb ratio of these samples is lower
or similar to the values of the acidic members of the basaltic andesite group.
If we assume that a process of crystal fractionation of pyroxene has to occur
in order to derive these andesites from the basaltic andesitic group we would
expect an increase in La/Yb ratio. This does not occur. It can therefore be
inferred that trace element behaviour do not suggest a simple crystal-liquid
fractionation relation between basaltic andesitic and andesitic groups. Instead
basaltic andesites and andesites could represent two different group of rocks
derived from distinct parent magmas.
Plagioclase and clinopyroxene separation and accumulation can have played
78 A. Peccerillo and S.R. Taylor

some role within the andesite group as evidenced by the decrease of some
ferromagnesian elements, the increasing Eu negative anomaly and La/Yb ratio.
However, all these patterns are poorly defined. Samples T69-108 and T69-40a
represent still another problem. Although they are the most acidic andesitic
rocks with highly fractionated REE patterns, they have relatively large concen-
trations of ferromagnesian elements, and relatively low amount of high valency
cations, some K-type elements and S REE. Many of these characteristics apply
also to the low-K andesite T69-27. This sample and T69-108 both have a signifi-
cant positive Eu anomaly. On the SiO2/Cr and SiO2/Ni diagrams (Fig. 7a,
b) T67-27, T69-108 and T69-40a plot on the same line as T69-22. If we assume
that T69-22 is not part of the basaltic andesitic group but represents a different
magma, one could suggest that all these four samples belong to a same series
which has suffered crystal-liquid fractionation with some accumulation of plagio-
clase in the samples T69-27 and T69-108. This can explain some features of
these rocks but the La/Yb ratio of T69-40a does not fit into this pattern.
In summary, geochemical data do not suggest in the Kastamonu series
a derivation of all the rocks from one parent magma by simple crystal-liquid
fractionation and accumulation. Instead it is necessary to infer the exsistence
of several different parent magmas in order to account for the overall features
of the Kastamonu volcanic series.
The high-K basaltic andesites come from different areas, and thus cannot
be directly related to the Kastamonu rocks. The detailed trace and major element
evidence do not suggest derivation from the basaltic andesites by fractional
crystallization. The interpretation adopted here is that they are a separate K-rich
magma. Since their area of outcrop lies south-east of Kastamonu, the Dickinson-
Hatherton K-h relationship [13] indicates that the Benioff zone could have
been deeper in that direction. It has to be pointed out that two samples are
not sufficient to draw any conclusion on this point and that a more widespread
petrological study over all the Pontic volcanic chain is necessary in order to
test this hypothesis.

Acknowledgements. The present study was carried out when one of the authors (A.P.) was visiting
fellow at the Research School of Earth Science, Australian National University, Canberra, sponsored
by a N.A.T.O. fellowship.
Both the authors wish to thank Prof. F.P. Sassi, University of Padua, for kindly providing
the samples studied in this work and P. Muir, W.B. Nance and Dr. D. Whitford for help during
the analytical work and discussion on the analytical result.
Financial support was partially provided by the National Council of Research of Italy (research
project n. 74.00045.05 Florence).

Appendix

Sample Description

Basaltic andesites

T69-21 Phenocrysts: plagioclase (35%) with oscillatory zoning, augite (15%) olivine (10%). Matrix
(40%): plagioclase, clinopyroxene, magnetite and devitrified glass.
Geochemistry of Eocene Calc-Alkaline Volcanic Rocks 79

T69-33 Granular texture: plagioclase (70%), clinopyroxene (15 %) and magnetite (15%) granules.
T69-22 Phenocrysts: plagioclase (30%), olivine (10%), augite (5%). Matrix (55%): microlites
of plagioclase, olivine, clinopyroxene and magnetite.
T69-118 Phenocrysts : plagioclase (25%) with oscillatory zoning, orthopyroxene (10%), augite (5%),
olivine. Matrix (60%): microlites of plagioclase, orthopyroxene and clinopyroxene. Magne-
tite granules9
T69-25 Phenocrysts: plagioclase (40%) showing oscillatory zoning, brown hornblende (5%), au-
gite, magnetite and olivine. Matrix (50% ca): microlites of plagioclase, clinopyroxene and
magnetite.
T69-117 Phenocrysts: plagioclase (20%) with oscillatory zoning, augite (5%), olivine and magnetite.
Matrix (75%): plagioclase and clinopyroxene microlites and magnetite granules.
T69-28 Phenocrysts: plagioclase (45%), orthopyroxene (5%). Matrix (50%): cryptocrystalline mass
crowded with plagioclase microlites and magnetite granules.
T69-24 Phenocrysts: plagioclase (45%) with oscillatory zoning, augite (5%), orthopyroxene, ma-
gnetite derived from brown hornblende. Matrix (45%): plagioclase and pyroxene microli-
tes and magnetite granules in a cryptocrystalline groundmass.
T68-244 Phenocrysts: plagioclase (35%), orthopyroxene (5%) and magnetite (5%) derived from
transformation of brown hornblende. Matrix (55%): plagioclase, orthopyroxene and ma-
gnetite.
T69-36 Phenocrysts: plagioclase (35%) showing oscillatory zoning, brown hornblende (10%),
magnetite (5%) derived from brown hornblende, orthopyroxene. Matrix (50%): plagio-
clase microlites, orthopyroxene rods and magnetite granules.

Low K Andesites

T69-27 Phenocrysts: plagioclase (35%) with oscillatory zoning, brown hornblende (15%), magne-
tite (5%). Matrix (45%): cryptocrystalline groundmass with plagioclase and brown horn-
blende microlites and magnetite granules. Devitrified glass.
T69-101 Phenocrysts: plagioclase (35%) with oscillatory zoning, brown hornblende (15%), magne-
tite. Matrix (50%): glassy and cryptocrystalline groundmass with plagioclase microlites
and magnetite granules.

Andesites

T69-86 Phenocrysts: plagioclase (20%) with oscillatory zoning, augite (10%), magnetite (5%).
Matrix (65%): plagioclase and clinopyroxene microlites and magnetite granules.
T69-93 Phenocrysts: plagioclase (25%) with oscillatory zoning, angite (5%). Matrix (70%) plagio-
clase microlites and clinopyroxene and magnetite granules. Devitrified glass.
T69-83 Phenoerysts: plagioclase (30%) with oscillatory zoning, brown hornblende (5%), augite
(5%) often substituted with calcite, magnetite. Matrix (50%): plagioclase microlites and
9magnetite granules. Minor amount of clinopyroxene granules.
T69-20 Phenocrysts: plagioclase (30%) with oscillatory zoning, altered pyroxene (10%). Matrix
(60%): cryptocrystalline groundmass with plagioclase microlites and magnetite granules.
Occurrence of chlorite as alteration of mafic minerals.
T68-243 Phenocrysts: plagioclase (40%) with oscillatory zoning, augite (5%), magnetite (5%). Ma-
trix (50%): plagi0clase microlites and magnetite granules in cryptocrystalline groundmass.
T69-19 Phenocrysts: plagioclase (30%) showing oscillatory zoning, brown hornblende (10%)
almost completely transformed to magnetite, altered pyroxene. Matrix (60%) : plagioclase,
magnetite and glass9
T69-88 Phenocrysts: plagioclase (30%) with oscillatory zoning, brown hornblende (15%) almost
completely transformed to magnetite. Matrix (55%) : plagioclase microlites, magnetite gran-
ules and glass.
Phenocrysts: plagioclase (30%), brown hornblende (5%) completely transformed to ma-
gnetite. Matrix (70%): plagioclase microlites, magnetite granules and glass. Occurrence
of chlorite derived from alteration of mafic minerals.
80 A. Peccerillo and S.R. Taylor

T68-242 Phenocrysts: plagioclase (35%) with oscillatory zoning, brown hornblende (15%), magne-
tite. Matrix (50%): plagioclase microlites and magnetite granules.
T69-108 Phenocrysts: plagioclase (35%) showing oscillatory zoning, brown hornblende (10%),
magnetite. Matrix (55%): brown glass with plagioclase microlites and large amount of
magnetite granules.
T69-92 Phenocrysts: plagioclase (25%) with oscillatory zoning, augite (10%) showing a pale green
colour, grown hornblende and magnetite. Matrix (60%): partially devitrified glass with
plagioclase microlites and magnetite granules.
T69-40 a Phenocrysts: plagioclase (35%) with oscillatory zoning, brown hornblende (15%) magne-
tite. Matrix (50%): plagioclase and brown horneblende microlites, magnetite granules
and glass.

High K Basaltic Andesites

T69-158 Phenocrysts: augite (15%), plagioclase (5%). Matrix (80%): microlites of plagioclase and
clinopyroxene. Abundant magnetite granules.
T69-159 Phenocrysts: plagioclase ( 2 5 % ) w i t h oscillatory zoning, augite (15%). Matrix (60%):
plagioclase and minor clinopyroxene microlites. Magnetite granules.

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Received March 11, 1976 / Accepted April 26, 1976