Lithos 394–395 (2021) 106184

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Lithos

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Two contrasting P-T paths for metamorphic sole amphibolites of the

Dinaride Ophiolite Zone (Krivaja-Konjuh ultramafic massif, Central
Bosnia and Herzegovina) and their geodynamic implications
Dražen Balen a,⁎, Hans-Joachim Massonne b
a
Department of Geology, Faculty of Science, University of Zagreb, Horvatovac 95, 10000 Zagreb, Croatia
b
Institut für Mineralogie und Kristallchemie (closed), Universität Stuttgart, Azenbergstraβe 18, 70174 Stuttgart, Germany

a r t i c l e i n f o a b s t r a c t

Article history: The Inner Dinarides, a part of the Alpine-Dinaride mountain chain in south-eastern Europe, are known for ex-
Received 25 October 2020 tended ophiolite-derived ultramafic massifs. The sampled rocks from the metamorphic sole of such a massif,
Received in revised form 9 April 2021 the Jurassic Krivaja-Konjuh ultramafic massif in central Bosnia and Herzegovina, are mainly garnet amphibolites,
Accepted 17 April 2021
with large grains of pyrope-almandine garnet commonly surrounded by kelyphite coronae, and pargasite am-
Available online 24 April 2021
phibolites. The bulk-rock geochemistry points to mantle peridotite as the protolith for pargasite amphibolite
Keywords:
and N-MORB for garnet amphibolite. Pressure-temperature (P-T) pseudosections were constructed in the
P-T path MnNCKFMASHTO system and contoured by isopleths for the modal and chemical composition of minerals. On
Metamorphic sole this basis, a counterclockwise P-T path with maximum P-T conditions of 1.2 GPa and 960 °C was deduced for
Ophiolite pargasite amphibolite as a bottom part of an overriding plate. This part was cooled by subducting oceanic
Amphibolite crust. In addition, the Jurassic intra-oceanic subduction enabled infiltration of hydrous fluid necessary to form
Kelyphite the pargasite amphibolites. A clockwise P-T path with maximum pressure conditions at ca. 2.1 GPa (ca. 65–70
Dinarides km depth) and temperatures of 810 °C was reconstructed for garnet amphibolite from an upper part of the
subducting plate which was exhumed in a subduction channel and came in contact with the pargasite amphib-
olite. Thus, these amphibolites formed before they were involved in a metamorphic sole at the interface between
continental crust and obducting ophiolite.
© 2021 Elsevier B.V. All rights reserved.

1. Introduction pressure-temperature (P-T) paths give us keys for a deduction of

A metamorphic sole originates in direct contact between the over-
riding plate of obducting oceanic crust and the underlying plate which
is usually of continental nature. According to a summary by Agard
et al. (2018) such a sole consists of pieces of crust that are stripped
from young slabs and underplated beneath the (nascent) mantle
wedge shortly after subduction initiation. Although subordinate by vol-
ume, the sole rocks are widespread, with comparable characteristics
worldwide, and consist of various rock types. In addition, these rocks
experienced extreme metamorphic conditions and bear wealth of infor-
mation that are important for studies concerning the evolution of sub-
duction zones and orogenic processes in general (e.g. Dilek and
Flower, 2003; Dimo-Lahitte et al., 2001; Guilmette et al., 2009, 2018;
Leat and Larter, 2003; Robertson, 2002, 2004, 2012; Robertson et al.,
2009; Stern, 2010; Wakabayashi and Dilek, 2003). Details of the meta-
morphic evolution of sole rocks through reconstructions of their
⁎ Corresponding author.
E-mail addresses: drbalen@geol.pmf.unizg.hr (D. Balen),
h-j.massonne@imi.uni-stuttgart.de (H.-J. Massonne).
these processes and corresponding tectonic scenarios.
The Inner Dinarides, a part of the Alpine-Dinaride folded, thrust and
imbricated mountain chain in southeastern Europe, comprise ophiolite-
related ultramafic massifs and diverse metamorphic rocks known in the
literature, regarding the western part of this mountain chain, as
Dinaride Ophiolite Zone (DOZ; e.g. Pamić et al., 2002) or Central
Dinaridic Ophiolite Belt (e.g. Lugović et al., 1991). The relics of a partially
dismembered ophiolite of the DOZ, which originated along the contact
of the European plate and the Adria microplate, were related to the evo-
lution and closure of the Neo-Tethys ocean. This closure involved an
intra-oceanic NE-dipping subduction zone (e.g. Karamata, 2006; Pamić
et al., 2002) believed to be responsible for the formation of metamor-
phic sole rocks. During the subduction process the protoliths of meta-
morphic sole rocks (i.e. basic and ultrabasic rocks) came in contact
with the hot upper mantle resulting in the formation of high- to low-
grade metamorphic rocks of the eclogite-, granulite-, amphibolite-,
and greenschist-facies (e.g. Pamić et al., 2002). If this is true, the P-T evo-
lution of these rocks was governed by ocean-floor dynamics, geometry
of the (intra-oceanic) subduction zone and characteristics of a hot
sub-oceanic mantle wedge (e.g. Agard et al., 2018).

https://doi.org/10.1016/j.lithos.2021.106184
0024-4937/© 2021 Elsevier B.V. All rights reserved.
D. Balen and H.-J. Massonne Lithos 394–395 (2021) 106184

In the Krivaja-Konjuh ultramafic massif (KKUM, central Bosnia and
Herzegovina), the target of our research, metamorphic sole rocks
occur under a NE-dipping peridotite (spinel lherzolite) thrust sheet
(Pamić et al., 1977; Fig. 1). The metamorphic sole rocks comprise a nar-
row and irregularly outcropping band, composed exclusively of am-
phibolites, that was already subject of research of several groups of
authors focusing on petrography and extraction of (peak) P-T data as
a database for deducing tectonic scenarios (Balen et al., 2004; Operta
et al., 2003; Pamić et al., 2002; Šegvić et al., 2019, 2020). However,
due to the lack of well-constrained P-T paths as common consequence
of the limits of conventional geothermobarometry for such a metamor-
phic environment, the detailed understanding of corresponding meta-
morphic processes, including changes at the microdomain scale, was
generally restricted.
Here, we present P-T paths that are, as far as we know, a first
quantitative approach, using phase equilibrium modeling through the
construction of pseudosections, for the metamorphic sole of the
KKUM and other ophiolite complexes in the Dinarides. This modeling
is not restricted to simplified and generalized chemical systems but
achieved for a complex chemical system in which these sole rocks
were formed. In comparison with the previously derived P-T data, the
P-T paths obtained in our study are related to specific chemical compo-
sitions of minerals in the rocks studied. Observed microtextures and
these compositions in the fixed and complex chemical system are the
base for quantifying a number of critical P-T points along these paths
that reveal the nature of the investigated rocks and relate them to pro-
cesses of the final closure of a part of the Neo-Tethys. In our view, the
methodological approach, leading to two contrasting P-T paths

Fig. 1. A Geological sketch-maps of the Dinarides and North Hellenides showing the position of ophiolite complexes (Pamić et al., 1977, 2002). 1 = Carpathians, 2 = Serbo-Macedonian
Massif, 3 = Pelagonides and Korab, 4 = Mesozoic-Paleogene carbonate platform including Ionian zone, 5 = allochthonous Paleozoic-Triassic complexes, 6 = Mesozoic clastic sediments of
the passive continental margin, 7 = Dinaride ophiolite zone and Mirdita zone, 8 = ultramafic massifs, 9 = Vardar zone, 10 = Neogene-Quaternary sedimentary rocks, 11 = transversal
faults. The shown ultramafic massifs are B = Borje, Ba = Banija, Bu = Bulquise, Č = Čavka, D = Đakovica, DB = Dren Boula (Guevgueli), G = Goleš, I = Ibar, K = Kopaonik, KK = Krivaja-
Konjuh, Ko = Kozara, Lj = Ljubić, M = Maljen, MT = Mirdita-Tropoje, O = Ozren, OS = Ozren Sjenica, PG = Puke-Gomsique, R = Raduša, S = Skatavica, Sh = Shebeniqut, V = Vardar,
Z = Zlatibor. B Simplified geological map of the Krivaja-Konjuh ultramafic massif (Pamić et al., 1977).

2
D. Balen and H.-J. Massonne
(clockwise and counterclockwise) in our study, has a high potential and
should be more generally applied not only to quantify the Late Jurassic
part of the geodynamic evolution of the Dinarides but also to reveal
the metamorphic sole evolution of various ophiolites worldwide (see,
e.g., Plunder et al., 2016).
2. Geological setting
2.1. General aspects
The Dinarides are a mountain chain that extends through southeast-
ern Europe and originated from Alpine-cycle orogenic processes. This
chain can be broadly subdivided into two folded and thrust parts:
(1) External Dinarides that are mainly related to the evolution of a car-
bonate platform, and (2) Inner Dinarides that contain a partially dis-
membered ophiolite which was obducted in the course of the collision
of the European plate and the Adria microplate (Pamić et al., 1998,
2002). The generalized models for the geodynamic and petrogenetic
evolution of the ophiolite of the Central and NW Dinarides involve
mid-ocean ridge spreading in the now closed Neo-Tethys ocean branch
in the early Mesozoic, Late Jurassic convergence, and NE-dipping sub-
duction that preceded the final obduction of the ophiolite onto the
Adria continental margin (Pamić et al., 1998, 2002).
Partially dismembered ophiolite crops out as numerous, several
hundreds of km2 extended massifs that follow the Dinaridic stretching
as elongated zone from Croatia (Zagreb area) in the northwest to
Albania in the southeast (Fig. 1). The ophiolite massifs are composed
of ultrabasic and basic rocks accompanied by metamorphic sole rocks
(e.g. Borojević Šoštarić et al., 2014; Chiari et al., 2011; Karamata, 1968;
Lanphere et al., 1975; Milovanović et al., 2004; Operta et al., 2003;
Srećković-Batoćanin et al., 2012; Šegvić et al., 2019, 2020).
Available geochronological data for the mid-ocean ridge spreading
point to its extension until Late Jurassic (ca. Oxfordian) times as can
be deduced from Sm-Nd ages at 157.9 ± 7.6 Ma for olivine-bearing
gabbros with N-MORB signatures of the Southern Kozara massif
(Ustaszewski et al., 2009). This age is compatible within analytical un-
certainties with Sm–Nd isochron ages for a metamorphic sole rock of
the KKUM (162 ± 14–160 ± 7 Ma; Šegvić et al., 2020). Thus, the tran-
sition from mid-ocean ridge spreading to Late Jurassic convergence
and intra-oceanic subduction with formation of metamorphic sole
rocks must have occurred very rapidly around 155–160 Ma. A conse-
quence of this limited period of time is that the inferred existence of
an upper plate island arc in the aforementioned models must be called
in question.
2.2. Krivaja-Konjuh ultramafic massif (KKUM)
The KKUM (Fig. 1) is one of the best-preserved and largest ophiolite
complexes in southeast Europe (ca. 500 km2 in area) that occurs as a
NE-dipping about 2 km thick thrust sheet that was thrust onto the Juras-
sic ophiolite mélange. This sheet is underlaid in its southeastern part by
metamorphic sole rocks (up to 1200 m thick; Pamić et al., 1977) gradu-
ally decreasing in metamorphic degree toward southwest. The KKUM is
mainly composed of serpentinized peridotite (spinel lherzolite). The fo-
liation in the metamorphic sole rocks is parallel to the foliation of the
spinel lherzolite indicating that both rock types were deformed to-
gether. In the early views, the final emplacement of the sole rocks of
the KKUM terminated in Early Cretaceous times, indicated by (1) am-
phibolite fragments in the adjacent sediments of the Tithonian-
Berriasian Pogar Formation overlying the ophiolite mélange and
(2) overlying contemporaneous (Jurassic-Cretaceous) carbonate sedi-
ments at Magulica Mt. located ca. 5 km north-northeast from the am-
phibolite sampling localities at the village of Vijaka (Hrvatović, 2006;
Pamić et al., 1977, 1978). However, the finding of radiolarian assem-
blages assigned to the latest Bajocian-Early Bathonian (Šegvić et al.,
2014) in the chert-rich shaly to silty matrix within the ophiolitic
3
Lithos 394–395 (2021) 106184
mélange set the formation of the Dinaridic metamorphic sole rocks be-
fore the end of the Jurassic.
The KKUM metamorphic sole is mainly composed of amphibolites
(monomineralic amphibole schists and diopside-, garnet-, garnet-
diopside- and corundum-bearing amphibolites; Pamić et al., 1977;
Fig. 1). The classic outcrops known for more than a century (Barić,
1969; Kišpatić, 1897; Pamić and Kapeler, 1970) can be found in
the vicinity of Vijaka following tributary creeks to the Krivaja
river. The age of metamorphic sole amphibolites, obtained by K-Ar
dating of amphibole fractions from corundum-bearing amphibolites,
is 170 ± 11 Ma and 157 ± 4 Ma; amphibole from the associated
garnet-amphibolites gave ages of 174 ± 14 Ma and 168 ± 8 Ma
(Lanphere et al., 1975).
2.3. Previous data on geothermobarometry
First geothermobarometric calculations for corundum-bearing am-
phibolite were performed by Operta et al. (2003) and for other types
of KKUM amphibolites by Balen et al. (2004). Both author groups used
calibrations of various authors (Dale et al., 2000; Gerya et al., 1997;
Holland and Blundy, 1994; Plyusnina, 1982) for the assemblage amphi-
bole + plagioclase (reaction edenite + albite = richterite + anorthite
in quartz-free rocks, Al and Si contents in amphibole) and other assem-
blages including garnet and clinopyroxene. However, due to the lack of
quartz, the application of this conventional geothermobarometry was
limited especially for obtaining pressures. In spite of these obstacles,
Balen et al. (2004) reported P-T conditions of 1.07–1.18 GPa and
745–800 °C derived for garnet amphibolite with kelyphite around gar-
net rims whereas other types of amphibolites yielded 670–730 °C (com-
mon amphibolite), 630 °C at 0.67–0.73 GPa (garnet amphibolite
without kelyphite), and 830 °C (clinopyroxene-garnet amphibolite).
Geothermobarometric estimations on corundum-bearing amphibolites
gave P-T conditions of 0.6–1.0 GPa and 620–830 °C for amphibole and
plagioclase inclusions in corundum porphyroblast and 0.45–0.8 GPa
for the main metamorphic assemblage (Operta et al., 2003). These
early estimates are thought to reflect metamorphic conditions at
preserved stages along the P-T evolution and are compatible with
results obtained later by Šegvić et al. (2019) using a similar geothermo-
barometric approach. These authors obtained peak P-T conditions cal-
culated from different mineral pairs in the range between 850 and
1100 °C at 1.1 to 1.3 GPa. Šegvić et al. (2020) estimated peak P-T condi-
tions of ~1 GPa and ~ 800 °C for garnet-clinopyroxene amphibolite.
3. Analytical methods and procedures
3.1. Samples
In total somewhat more than one hundred amphibolite samples
were collected during field campaigns in 2016–2018. The structure of
these samples is mainly parallel to the main foliation in the field
(Pamić et al., 1977, 1978). Based on macroscopic field inspections, opti-
cal investigations and reconnaissance results obtained with the electron
microprobe (EMP), 19 samples were selected for whole-rock geochem-
ical analyses. Although all amphibolites are commonly dark greyish-
green to light green in hand specimens and exhibit partly a granoblastic,
porphyroblastic or nematoblastic texture with variable grain size and
comprise similar major minerals such as amphibole, plagioclase, and
pyroxenes, the whole-rock geochemistry reported below in section
“Whole-rock compositions and protolith nature” resulted in two different
geochemical groups (for data see Supplementary Table 1). One group,
comprising 6 samples, resembles mantle peridotites as protoliths
whereas the other more heterogeneous group (13 samples) points to
basic rocks of the oceanic crust as protoliths. A representative of each
group (Fig. 2) was selected (PA = pargasite amphibolite representing
the mantle peridotite group and GA = garnet amphibolite the oceanic
crust group) for detailed analyses. Samples PA (GPS coordinates:
D. Balen and H.-J. Massonne
N44.1972°, E18.4295°) and GA (N44.2037°, E18.4323°) were taken
around Vijaka (Fig. 1).
3.2. Optical microscopy
Optical investigations were performed on standard thin sections of
about 100 samples. A ZEISS Axiolab polarized-light microscope with
25×, 100× and 200× magnifications, CANON EOS 500D camera, and
software packages EOS Utility and AxioVision 4.8.2. was used.
3.3. Whole-rock analyses
Fist-sized samples of metamorphic-sole rocks (19 samples, ca.
2–2.5 kg in weight each) were crushed in a jaw crusher and powdered
in an agate mill. The obtained powders were air-dried and sieved
through a 0.125 mm stainless-steel screen. The sample preparation in-
cluded the splitting of 0.2 g rock powder for chemical analyses. After
fusion of the rock powder with LiBO2-Li2B4O7 and subsequent diges-
tion in diluted nitric acid at Bureau Veritas Commodities Canada Ltd.
(Vancouver, for details see commodities.bureauveritas.com) the ob-
tained solutions were analyzed for major and trace elements, includ-
ing rare earth elements (REE), using inductively coupled plasma
(ICP) mass spectrometry (MS) and ICP optical emission spectrometry
(OES). The analytical accuracy was controlled using internal geological
reference materials (STD DS10, STD OREAS45EA, STD SO-19). Loss on
ignition (LOI) was determined by weight difference before and after
4 h ignition at 1000 °C.
3.4. Electron-microprobe analyses of minerals
Chemical analyses and back-scattered electron (BSE) imagery of
minerals in the metamorphic sole rocks were performed with a
CAMECA SX100 EMP at the Institut für Mineralogie und Kristallchemie,
Universität Stuttgart, Germany. Operating conditions for quantitative
analysis included an acceleration voltage of 15 kV, a beam current of
15 nA, and a beam diameter of about 3 μm. Standards used comprise
natural minerals and pure oxides (albite, periclase, corundum, wollas-
tonite, orthoclase, rutile, rhodonite, fayalite, barite, Fe2O3, Cr2O3). The
PAP correction procedure provided by CAMECA was utilized. For visual-
ization of reaction textures and zoning patterns of minerals, simulta-
neous mapping of the concentrations of five different elements was
undertaken. Operational conditions were 50 nA, 15 kV, 60 ms per step
and step width 3 μm.
Fig. 2. Amphibolites from the metamorphic sole in central Bosnia. A pargasite amphibolite with corundum and sapphirine, B garnet amphibolite. Both samples were collected at outcrops
near the village of Vijaka. Amp – amphibole, Crn – corundum, Grt – garnet, Pl – plagioclase.
4
Lithos 394–395 (2021) 106184
3.5. Calculation method for obtaining P-T pseudosections
The PERPLE_X (version 6.8.9, updated February 2020) computer-
program package (Connolly, 2005; Connolly and Petrini, 2002) was
used to calculate P-T pseudosections. Numerous reconnaissance calcu-
lations were performed in order to reconstruct the evolution of the
metamorphic history comparing calculated and observed assemblages
of minerals and their chemical compositions. Finally, detailed
pseudosections were worked out for the selected pargasite amphibolite
(PA) and garnet amphibolite (GA) within the P-T range of 0.2–1.8 or
0.2–2.6 GPa and 500–1100 °C in the system MnNCKFMASHTO. The
chemical compositions of these rocks, obtained by ICP-OES (see
above), had to be slightly modified (Table 1) to fit this system. There-
fore, (1) the CaO content was reduced according to the bulk-rock phos-
phorus content, assuming that P was bound exclusively to (ideally
composed) apatite, (2) 10% of the Fe (e.g., Massonne et al., 2007) was
assumed to be trivalent during metamorphism, and (3) the bulk was
normalized to 100%.
The pseudosection calculations were performed with the thermody-
namic dataset hp62ver.dat of Holland and Powell (2011) and the fol-
lowing solid-solution models: cAmph(G) for clinoamphibole (Green
et al., 2016), Omph(GHP) for Na-bearing clinopyroxene (Green et al.,
2007), feldspar for plagioclase (Fuhrman and Lindsley, 1988), Ilm
(WPH) for ilmenite (White et al., 2000, 2014), Sp(WPC) for spinel
(White et al., 2002), Sa(WP) for sapphirine (Wheller and Powell,
2014), Gt(W) for garnet, Bi(W) for biotite, Opx(W) for orthopyroxene,
Mica(W) for white mica, Chl(W) for chlorite (White et al., 2014) and
Ep(HP11) for clinozoisite-epidote (Holland and Powell, 2011). The
model melt(G) was used for tonalitic melt. H2O was considered as satu-
rated phase. Slight modifications in the files perplex_option.dat for ini-
tial resolution and solution_model.dat for cAmph(G) and Ilm(WPH)
parameters were applied following software inputs/recommendations
in order to stabilize the calculation process.
Using the sub-programs werami and pstable from PERPLE_X, the P-T
diagrams were contoured by isopleths for modal amounts and chemical
parameters. The obtained graphical results were taken as raw data. The
final pseudosections and contoured P-T diagrams were redrawn by
smoothing curves as demonstrated by Connolly (2005).
4. Results
4.1. Petrological investigations on representatives of the two sample groups
The petrology of the two selected rocks (PA and GA) is subsequently
described in detail.
D. Balen and H.-J. Massonne Lithos 394–395 (2021) 106184

Table 1
Whole-rock major (wt%) and trace (ppm) element contents obtained with ICP-MS and ICP-OES including characteristic element ratios for pargasite (PA) and garnet (GA) amphibolite.
These samples, modified to fit the MnNCKFMASHTO system, were selected for pseudosection modeling as representatives of two different amphibolite groups. Mg# = Mg-number =
100*MgO/(MgO + FeO) [mol%], Eu* = 2 EuN/(Sm + Gd)N: europium anomaly. O2 refers to the estimated amount (10 % of total iron) of trivalent iron in the rock.

Sample PA GA MnNCKFMASHTO PA GA PA GA PA GA PA GA

wt% wt% ppm ppm ppm

SiO2 39.65 44.94 SiO2 41.792 46.299 Ba 27 3 Pb 1.1 0.8 La 0.2 2

TiO2 0.06 1.40 TiO2 0.063 1.442 Co 75.7 48.9 Rb 2 <0.1 Ce 0.6 7.6
Al2O3 21.91 14.26 Al2O3 23.093 14.691 Cu 13.6 66.3 Sc 6 50 Pr 0.04 1.36
Fe2O3 5.80 13.75 FeO 5.503 12.750 Ga 13.8 15.3 Sr 33.3 76 Nd 0.3 8.4
Cr2O3 0.10 0.03 O2 0.061 0.142 Hf 0.1 1.8 V 40 389 Sm 0.13 3
MnO 0.06 0.23 MnO 0.063 0.237 Nb 0.5 1.9 Zn 34 35 Eu 0.06 1.05
MgO 16.82 9.92 MgO 17.729 10.220 Ni 324.7 38.3 Zr 2.5 56.4 Gd 0.23 4.34
CaO 9.72 11.83 CaO 10.231 12.066 Y 2.5 34.6 Tb 0.05 0.78
Na2O 1.25 2.05 Na2O 1.318 2.112 Dy 0.36 5.57
K2O 0.14 0.04 K2O 0.148 0.041 (La/Yb)N 0.65 0.40 Ho 0.1 1.22
P2O5 <0.01 0.09 (La/Sm)N 0.96 0.42 Er 0.25 3.7
LOI 4.10 1.20 (Gd/Yb)N 0.88 1.02 Tm 0.03 0.55
Sum 99.61 99.74 Sum 100.000 100.000 Eu* 1.06 0.89 Yb 0.21 3.44
Mg# 85 59 ΣREE (ppm) 2.59 43.55 Lu 0.03 0.54

Sample PA (Fig. 3) mainly contains medium- to coarse-grained
amphibole (diameter 2–5 mm; up to 70–80 vol%) and plagioclase
(10–15 vol%) with subordinate amounts (1–5 vol%) of relic
clinopyroxene (1–2 mm) and spinel (0.5 mm) enveloped by sap-
phirine and blasts of corundum (ca. 1.5 mm in thin sections, locally
reaching cm size; Fig. 2A). Kyanite, chlorite, clinozoisite and white
mica occur as accessory phases around corundum. Amphibole
grains in PA as well as in most samples with similar mineral
mode share a moderately to strongly shape-preferred orientation
that produced a noticeable lineation in the field and an obvious
schistosity. Plagioclase grains up to 1 mm in size equally define a
moderate shape-preferred orientation. They occur either as single
grains, dispersed among amphibole grains, or in small bands elon-
gated in the lineation direction.
Sample GA (Fig. 4) shows a fine-grained (0.3–0.5 mm) granoblastic
texture with a massive structure. The major minerals are garnet as large
grains (up to 2 cm, usually 1–2 mm in size, modal content is ~25 vol%
without kelyphite corona), smaller (below 1 mm) clinopyroxene (~10
vol%), plagioclase (~10 vol%), and amphibole (~55 vol%). Orthopyroxene
occurs as minor phase (~1–2 vol%). Opaque minerals (ilmenite with sec-
ondary titanite, magnetite, spinel and scarce pyrite and chalcopyrite)
predominate among the accessories over clinozoisite, apatite and zir-
con. Megascopically, reddish garnet is isometric, rounded and fre-
quently cracked. Plagioclase also occurs enclosed in garnet. Such
inclusions are round (Fig. 4B) indicating plagioclase consumption dur-
ing garnet growth. Garnet is commonly surrounded by kelyphite rims
consisting of various proportions of greenish amphibole needles, plagio-
clase and opaque mineral(s). Complete transformation to a symplectite

Fig. 3. A: Plane-polarized transmitted-light photomicrograph of typical microtextures of the pargasite amphibolite (PA). B-D: Similar objects as shown in 3A under crossed nicols.
Amp – amphibole, Cpx – clinopyroxene, Crn – corundum; Pl – plagioclase, Spl – spinel, Spr – sapphirine.

5
D. Balen and H.-J. Massonne Lithos 394–395 (2021) 106184

Fig. 4. A-B: Plane-polarized transmitted-light photomicrographs of typical microtextures in garnet amphibolite (GA). C-D: similar to A-B but under crossed nicols. Amp – amphibole, Cpx –
clinopyroxene, Grt – garnet, Pl – plagioclase.

is not uncommon (Fig. 4C). Clinopyroxene is colorless to pale green.
Commonly it is fresh. In some thin sections of rocks similar to GA,
clinopyroxene shows undulatory extinction. Plagioclase grains occur ei-
ther in polycrystalline lenses or as single grains dispersed among am-
phibole grains.
4.2. Whole-rock compositions and protolith nature
The whole dataset of 19 chemical whole-rock analyses is given in the
Supplementary Table 1. Additionally, chemical compositions of the rep-
resentative samples (PA and GA) together with necessary adjustments
for pseudosection modeling are highlighted in this table. Chemical
data are fairly similar for most of the main components (SiO2, Al2O3,
CaO, alkalies) including trace elements. Based on the SiO2 content,
these compositions are basic (GA contains 46.30 wt% SiO2 after normal-
ization) or ultrabasic (PA with SiO2 = 39.65 wt%) with moderate differ-
ences in contents of Al2O3, Fe2O3 (for total Fe) and MgO.
The whole-rock composition of PA is characterized by high quanti-
ties of Al2O3, MgO and CaO (21.9, 16.8 and 9.7 wt%, respectively) with
a high Mg/Fe ratio (Table 1, Figs. 5A, B). Normalization of trace elements
to primitive mantle (McDonough and Sun, 1995) results in negative
anomalies of Th, Nb, La, Pr and Ti, and positive ones for Ba, U, Ta, Pb,
Sr, Eu and Y (Fig. 5C). Such a pattern resembles those for mantle perido-
tite that was altered during subduction. The REE diagram normalized to
primitive mantle (Fig. 5D) after McDonough and Sun (1995) shows
lower concentrations of REE compared to the primitive mantle with a
slight increase of the normalized values toward the heavy REE (although
not reaching primitive mantle values). Characteristic parameters of REE
such as (La/Yb)N = 0.65, (La/Sm)N = 0.96, and (Gd/Yb)N = 0.88 without
a clear Eu anomaly (Eu* = 2 EuN/(Sm + Gd)N = 1.06) are similar to
those in peridotite. Thus, the minor and trace element data suggest
that the ultrabasic protolith of sample PA was originally a mantle
peridotite.
The observed mineral assemblage in sample GA suggests that the
protolith of this sample was a basic igneous rock. This is confirmed by
the whole-rock composition (Table 1) that shows relatively high
contents of Al2O3, Fe2O3, MgO and CaO (14.3, 13.8, 9.9 and 11.8 wt%, re-
spectively) and relatively low SiO2 contents (44.9 wt%). According to
the TAS diagram of LeBas et al. (1986), the igneous protolith had a
subalkaline nature (Na2O = 2.05, K2O = 0.04 wt%) (Fig. 5A), whereas
the AFM ternary diagram after Irvine and Baragar (1971) (not shown
here) demonstrates that the protolith of GA belongs to the tholeiitic se-
ries. In the Ti-V diagram (Shervais, 1982) presented in Fig. 5B, the com-
position of GA plots in the field of N-MORB close to the field of island-arc
tholeiites. However, considering the TiO2 content (1.4 wt%) only, GA
could also be an island-arc basalt, typically showing TiO2 contents
below 1.5 wt% (see Jakes and Gill, 1970; Perfit et al., 1980). Normaliza-
tion of the trace elements to primitive mantle after McDonough and Sun
(1995) yielded negative anomalies of Nb, Ta, Sr, and Ti in the corre-
sponding spider diagram (Fig. 5C) which demonstrate depletion in
large-ion lithophile elements and rise of normalized concentrations to-
ward elements with increasing compatibility. Such a pattern clearly re-
sembles those of N-MORBs. In the diagram of REE normalized to
primitive mantle after McDonough and Sun (1995), sample GA shows
~5–10 times higher concentrations of REE than the primitive mantle stan-
dard (Fig. 5D), whereas a slight negative Eu anomaly (Eu* = 0.89) points
to plagioclase fractionation in the crystallizing magma. The diagram of
normalized REE shows a decrease toward light REE ((La/Sm)N = 0.42),
whereas heavy REE ((Gd/Yb)N = 1.02) are characterized by a flat pattern.
Both characteristics are typical of N-MORBs.
4.3. Mineral chemistry
Amphibole is the main constituent in the matrix of amphibolite sam-
ples PA (Table 2, Fig. 6) and GA (Table 3, Fig. 7). Grains of amphibole
characterized with intense greenish pleochroism in sample PA show
significant contents of calculated trivalent Fe (0.4–0.5 Fe3+ per formula
unit = p.f.u.). Contents of Si (6.16–6.26 p.f.u.), Ti (0.01 p.f.u.), Ca
(1.71–1.76 p.f.u.), Na (0.45–0.54 p.f.u.) and K (0.04 p.f.u.) are fairly uni-
form. The composition of such an amphibole is that of a pargasite (Leake

6
D. Balen and H.-J. Massonne Lithos 394–395 (2021) 106184

Fig. 5. Classification and discrimination diagrams showing major and trace element contents in the 19 analyzed samples (circles in A-B) and the two representative amphibolite samples
(C-D) from the KKUM metamorphic sole in central Bosnia and Herzegovina (PA = pargasite amphibolite, GA = garnet amphibolite): A TAS diagram (Le Bas et al., 1986), B Ti-V diagram
(Shervais, 1982), C primitive mantle-normalized element diagram, D patterns of REE after normalization to primitive mantle using values by McDonough and Sun (1995). Bold lines refer
to element contents in samples PA and GA. Shaded areas in C and D represent element concentration spans for PA (dark gray) and GA (light gray) groups (see text).

et al., 1997) and, to a limited extent, Mg-hornblende. The composition
of matrix amphibole in GA corresponds to Ti-pargasite. This amphibole
shows XMg = Mg/(Mg + Fe2++Mn2+) = 0.67–0.70. Contents of Si
(6.10–6.17 p.f.u.), Ti (0.31–0.35 p.f.u.), Ca (1.73–1.78 p.f.u.), Na
(0.84–0.88 p.f.u.) and K (0.03 p.f.u.) scatter moderately. In comparison
to this matrix amphibole, amphibole from the kelyphite is characterized
by lower XMg (0.6) and higher silica content (6.4 p.f.u.). Contents of Ti =
0.13 p.f.u., Ca = 1.9 p.f.u., Na = 0.81 p.f.u. and K = 0.02 p.f.u. are typical
of this amphibole (Table 3). Amphibole (pargasite) enclosed in garnet is
characterized by XMg = 0.74, Si = 6.08 p.f.u., Ti = 0.22 p.f.u. Ca = 1.71 p.
f.u. Na = 0.84 p.f.u. and K = 0.03 p.f.u.
Garnet occurs only in rocks represented by sample GA. In the whole
collection of samples which are metamorphosed rocks with N-MORB
signature, generally two types of garnet exist: (1) Garnet porphy-
roblasts, that are up to 2 cm in diameter, commonly round with little
or no resorption, and only slightly chemically zoned, contain abundant
inclusions of randomly distributed minerals. (2) Garnet grains, that
are only up to 2–3 mm in diameter, commonly resorbed along their
edges with partial replacement by kelyphite, and clear chemical zoning,
contain inclusions of plagioclase, amphibole, as well as minor rutile, il-
menite and titanite. The zonation pattern of the latter garnet type in
sample GA is characterized by a general decrease of Xgrs [Ca/(Ca +
Mg + Fe2+ + Mn)] from core to rim (0.25 to 0.16), whereas Xalm
[Fe/(Ca + Mg + Fe + Mn)] and Xprp [Mg/(Ca + Mg + Fe + Mn)] in-
crease from core to rim (0.43 to 0.49 and 0.30 to 0.35, respectively)
(Table 3, Fig. 7G, H). Contents of spessartine component are low and rel-
atively constant (up to 2 mol%).
Plagioclase of sample PA is almost compositionally uniform,
anorthite-rich (93–98 mol% An) and commonly altered to thom-
sonite. The GA plagioclase shows a greater chemical variability de-
pending on the textural position. Plagioclase inclusions in garnet
are either lath-shaped or rounded with 44 mol% An. Matrix plagio-
clase is characterized by a slightly variable anorthite content of
48–51 mol%. Plagioclase in the kelyphite contains higher anorthite
contents: 71–86 mol% around garnet and 57 mol% in symplectite
around pyroxene.
Clinopyroxene is widespread in the matrix of sample GA and in
textural equilibrium with matrix minerals, whereas orthopyroxene is
only a constituent of symplectites around clinopyroxene. Matrix
clinopyroxene is closest in composition to diopside with high alumina
content (Xdiopside = 0.49, Al2O3 = 4.9 wt%). Orthopyroxene is hyper-
sthene (Xenstatite = 0.58, Xferrosilite = 0.34).

7
D. Balen and H.-J. Massonne Lithos 394–395 (2021) 106184

Table 2
Electron microprobe analyses (in wt%) of selected minerals from pargasite amphibolite (PA). Formulae of minerals are calculated on the basis of 23 O and 13 cations (excluding Ca, Na and
K) for amphibole, 8 O for plagioclase, 20 O for sapphirine, 4 O and 3 cations for spinel, Si = 1.000 p.f.u. for titanite, 28 O for chlorite, and 21 O for mica. Fe3+-Fe2+ (amphibole, spinel), H2O⁎
and OH⁎ were calculated by stoichiometry. XMg = Mg/(Mg + Fe2++Mn2+).

Amphibole Plagioclase Sapphirine Spinel Titanite Chlorite Mica

PA-21 PA-13 PA-19 PA-11 PA-2 PA-8 PA-3 PA-7 PA-1 PA-27 PA-27a

inclusion inclusion envelope

SiO2 45.41 44.92 43.26 44.52 13.14 0.00 0.00 0.00 29.84 28.74 45.73
TiO2 0.10 0.06 0.00 0.01 0.00 0.00 0.03 0.00 39.19 0.01 0.00
Al2O3 17.06 18.01 36.73 35.54 64.37 66.92 26.51 57.25 1.07 22.64 38.25
Cr2O3 0.00 0.00 0.00 0.00 0.00 42.79 10.84 0.03 0.00 0.00
Fe2O⁎3 4.93 3.96 0.12 0.63 0.73 0.79 0.52
FeO 0.00 0.00 3.66 11.87 22.85 15.52 5.04 0.21
MnO 0.02 0.06 0.00 0.00 0.03 0.06 0.33 0.16 0.04 0.00 0.00
MgO 16.80 17.16 0.00 0.02 19.05 19.90 9.03 16.90 0.00 30.78 0.07
CaO 11.92 11.63 18.84 18.10 0.04 0.03 0.01 0.00 27.74 0.42
Na2O 1.68 2.02 0.22 0.79 0.04 0.04 0.58
K2O 0.20 0.24 0.00 0.01 0.00 0.00 10.18
BaO 0.00 0.01 0.00 0.00 0.00 0.03
H2O* 2.18 2.19 12.65 4.55
Total 100.30 100.26 99.17 99.00 100.33 99.40 102.28 101.46 98.46 99.86 100.04
3+
Si 6.257 6.160 Si 2.012 2.070 Si 1.531 Fe 0.012 0.017 0.015 Si 1.000 Si 5.451 6.026
Aliv 1.743 1.840 Al 2.014 1.947 Al 8.841 Fe2+ 0.250 0.582 0.339 Al 0.042 Al_T 2.549 1.974
Sum T 8.000 8.000 Fe3+ 0.004 Ti 0.000 Mn 0.001 0.009 0.004 Cr 0.001 sum4 8.000 8.000
Ti 0.010 0.007 Mn3+ 0.000 Fe 0.356 Mg 0.748 0.410 0.658 Ti 0.988 Al_O 2.512 3.966
Alvi 1.027 1.071 Cr 0.000 Mn 0.003 sum4 1.011 1.001 1.000 Fe3+ 0.013 Ti 0.001 0.000
Cr 0.000 0.000 Ti 0.000 Mg 3.309 Mn3+ 0.001 Fe2+ 0.800 0.023
Fe3+ 0.511 0.409 sum1 4.030 4.017 Ca 0.005 Ti 0.000 0.001 0.000 sum1 1.045 Mg 8.703 0.014
Fe2+ 0.000 0.000 Ba 0.000 Na 0.009 Al 1.988 0.951 1.761 Ca 0.996 sum6 12.017 4.004
Mn2+ 0.002 0.007 Ca 0.939 0.902 Cr 0.000 1.030 0.224 Na 0.002 Ca 0.060
Mg 3.450 3.508 Na 0.020 0.072 sum6 1.988 1.999 2.000 sum2 0.998 Ba 0.002
Sum O 5.000 5.000 K 0.000 0.001 Na 0.147
Ca 1.760 1.708 sum2 0.959 0.974 K 1.712
Na 0.449 0.538 sum8 1.920
K 0.036 0.042
Ba 0.000 0.001 An 0.979 0.926 XSi 0.726
Sum Y 2.245 2.289 Ab 0.021 0.073 XMg 0.916
XMg 0.999 0.998 Or 0.000 0.001 XFe 0.084

Chlorite and mica occur in the matrix (chlorite, Fig. 6A, G; Table 2) or
around corundum grains (only mica) in sample PA (Figs. 6H; Table 2).
XMg of chlorite is 0.92. Silicon p.f.u. in mica is 6.03 (on the basis of 21
O). Accessory minerals are spinel with sapphirine rims (Fig. 6A–B;
Table 2), various Ti-phases found in different textural positions (rutile,
ilmenite, titanite; Figs. 6E–F, 7A, B, D; Table 2), corundum and kyanite
(Fig. 6C, G, H; Table 2).
4.4. Pressure-temperature (P-T) modeling
The calculated P-T pseudosections for PA and GA (Figs. 8 and 9)
show that different dry phases coexist with hydrous ones. Further-
more, the calculated pseudosections resemble each other and gener-
ally those calculated for metamorphosed basic to ultrabasic rocks
(e.g. Lo Po et al., 2018; Massonne, 2016; Scodina et al., 2019). The
dry phases in the different assemblages are: (1) plagioclase that ap-
pears within the whole temperature range and pressures below 0.9
GPa, (2) sapphirine which occurs only in the pseudosection for PA
and occupies small assemblage fields in the range 1.15–1.4 GPa and
920–980 °C, (3) corundum which is stable in several P-T fields with
various assemblages above 0.7 GPa and at 680–1000 °C, (4) spinel
which shows an important and typical reaction with sapphirine for
the PA composition, (5) kyanite in PA which occupies assemblage
fields at P above 0.8 GPa and 610–720 °C, (6) orthopyroxene and
clinopyroxene occurring up to 1050 °C at low- to medium-pressure
and together with garnet in GA, and (8) pyrope-rich garnet at P-T
conditions above 0.6 GPa and 700 °C. A maximum pressure for ilmen-
ite in sample GA at 1.5 GPa at 900 °C as well as the P-T fields for other
Ti-phases (rutile, titanite) give orientation for the direction of P-T
paths to be reconstructed. Hydrous phases with minor contents
(≤ 10 vol%) in the modelled rocks are chlorite and mica. The chlorite
content slightly decreases with rising temperature. Amphibole is a
major hydrous phase and stable over a wide range of temperatures
up to pressures of 2 GPa. Calculated and experimentally obtained
maximum temperatures on pargasitic amphibole (Holloway and
Ford, 1975; Jenkins, 1983) are in good agreement with our calcula-
tions. The calculated P-T conditions of the solidus curve are above
1000 °C for sample PA and 750 °C for sample GA at medium pressures.
The P-T pseudosections were contoured with isopleths for garnet
molar fractions (Xprp, Xalm, Xgrs), anorthite component in plagioclase,
Si (p.f.u.) in amphibole and mineral modal contents. Intersections, or at
least a proximity, of corresponding isopleths result in P-T conditions on
the metamorphic path. The derivation of these conditions is strongly
based on the compositional and modal characteristics of garnet. The
compositional trend of garnet in sample GA results in P-T conditions
of 2.0–2.1 GPa and 810 °C for the formation of the garnet core. Consid-
ering Xprp, Xalm, and Xgrs of the inner core, the P-T path starts at 2.0
GPa and 700 °C. The amount of spessartine component in garnet is too
small (<2 mol%) to be a reliable indicator for specific P-T conditions.
The garnet “rim” composition (or garnet outer mantle composition,
since the outermost part of garnet was replaced by kelyphite) corre-
sponds to P-T values of 0.6 GPa and 850 °C. Since the studied rocks
reached conditions of the amphibolite-eclogite facies (see, e.g., Fig. 8
in Scodina et al., 2019, for ranges), the occurrence of plagioclase is ex-
cluded from assemblages on the early P-T path (those above 0.9 GPa).
Intersection of isopleths for the Si content in amphibole and XCa in pla-
gioclase led to conditions (0.75–80 GPa and 880 °C) of a later stage in
the evolution of GA.

8
D. Balen and H.-J. Massonne Lithos 394–395 (2021) 106184

Fig. 6. A-H BSE images of microtextures in the pargasite amphibolite sample PA. Amp – amphibole, Chl – chlorite, Cpx – clinopyroxene, Crn – corundum, Ilm – ilmenite, Ky – kyanite, Ms –
muscovite, Pl – plagioclase, Spl – spinel, Spn – titanite (sphene), Spr – sapphirine, Rt – rutile, Zrn – zircon.

9
 D. Balen and H.-J. Massonne

Table 3
Electron microprobe analyses (in wt%) of selected minerals from garnet amphibolite (GA). Formulae of minerals are calculated on the basis of 23 O and 13 cations (excluding Ca, Na and K) for amphibole, 8 O for plagioclase, Al + Cr + Fe3+ = 4
and Fe2++Mn + Mg + Ca + Na = 6 for garnet, 6 O and 4 cations for pyroxenes, 3 O and 2 cations for ilmenite, Si = 1.000 p.f.u. for titanite, 4 O and 3 cations for spinel. Fe3+-Fe2+ for most minerals, H2O⁎ and OH⁎ were calculated by stoichiometry.
XMg = Mg/(Mg + Fe2++Mn2+).
Amphibole Garnet Plagioclase Clinopyroxene Orthopyroxene Ilmenite Titanite Spinel

GA-7 GA-5c GA-26 GA-42 GA-71 GA-80 GA-31 GA-100 GA-101 GA-7a GA-57 GA-50 GA-11 GA-3 GA-8 GA-29 GA-36

matrix matrix inclusion kelyphite core rim inclusion matrix matrix pyroxene garnet symplectite
symplectite

SiO2 42.11 41.44 41.49 43.69 SiO2 40.04 39.74 SiO2 57.07 56.34 55.99 54.10 50.23 46.66 SiO2 50.72 SiO2 52.31 TiO2 52.12 SiO2 30.69 SiO2 1.96
TiO2 2.78 3.15 1.96 1.20 TiO2 0.17 0.08 TiO2 0.01 0.01 0.01 0.02 0.01 0.00 TiO2 0.56 TiO2 0.07 Al2O3 0.00 TiO2 39.07 TiO2 5.68
Al2O3 12.68 12.92 13.56 21.82 Al2O3 22.28 22.26 Al2O3 27.86 28.14 28.19 30.06 32.57 34.62 Al2O3 4.86 Al2O3 2.04 V2O3 0.00 Al2O3 1.03 Al2O3 2.64
Cr2O3 0.17 0.12 0.17 0.00 Cr2O3 0.03 0.03 Cr2O3 0.00 0.00 0.00 0.00 0.00 0.00 Fe2O3⁎ 0.34 Fe2O3⁎ 1.15 Cr2O3 0.00 Cr2O3 0.01 Cr2O3 1.37
Fe2O3⁎ 3.76 4.38 6.99 0.00 Fe2O3⁎ 1.04 1.06 Fe2O3⁎ 0.30 0.09 0.22 0.30 0.38 0.48 FeO 9.89 FeO 22.45 FeO 41.79 Fe2O3⁎ 1.55 V2O3 0.00
FeO 9.36 10.09 7.21 8.59 FeO 20.80 22.92 Mn2O3 0.03 0.00 0.03 0.00 0.00 0.00 MnO 0.18 MnO 0.73 Fe2O3⁎ 4.69 Mn2O3 0.05 FeO 36.38
MnO 0.17 0.13 0.25 0.11 MnO 0.76 0.84 MgO 0.02 0.01 0.01 0.00 0.00 0.00 MgO 12.55 MgO 21.77 MnO 0.68 MgO 0.02 Fe2O3⁎ 47.87
MgO 12.50 11.62 12.18 7.28 MgO 8.31 9.50 CaO 8.83 9.99 10.62 11.71 14.14 16.87 CaO 20.15 CaO 0.49 MgO 2.46 CaO 26.39 MnO 0.27
CaO 11.32 10.93 10.88 12.03 CaO 9.49 6.11 Na2O 6.09 6.02 5.52 4.83 3.16 1.52 Na2O 0.62 Na2O 0.00 NiO 0.00 Na2O 0.00 MgO 0.32
Na2O 2.94 3.09 2.94 2.85 Na2O 0.00 0.00 K2 O 0.05 0.03 0.03 0.02 0.00 0.01 K2O 0.00 NiO 0.00
K2 O 0.17 0.16 0.16 0.11 BaO 0.00 0.00 0.00 0.00 0.00 0.00 ZnO 0.00
BaO 0.00 0.00 0.00 0.05 CaO 1.36

10
H2O* 2.05 2.04 2.05 2.04
Total 100.00 100.06 99.84 99.78 Total 102.92 102.55 Total 100.25 100.63 100.62 101.04 100.48 100.16 Total 99.87 Total 101.02 Total 101.75 Total 98.82 Total 97.86

Si 6.171 6.101 6.078 6.421 Si 5.919 5.875 Si 2.548 2.516 2.504 2.419 2.274 2.138 Si 1.895 Si 1.937 Ti 0.957 Si 1.000 Fe2+ 1.155
Aliv 1.829 1.899 1.922 1.579 Ti 0.019 0.009 Al 1.466 1.481 1.486 1.584 1.738 1.869 Al_T 0.105 Al_T 0.063 Al 0.000 Al 0.040 Mn 0.009
Sum T 8.000 8.000 8.000 8.000 sum4 5.938 5.884 Fe3+ 0.010 0.003 0.007 0.010 0.013 0.016 sum4 2.000 sum4 2.000 V 0.000 Cr 0.000 Mg 0.018
Mn3+ 0.001 0.000 0.001 0.000 0.000 0.000 Al_O 0.109 Al_O 0.027 Cr 0.000 Ti 0.957 Ni 0.000
Ti 0.306 0.349 0.215 0.133 Al 3.881 3.878 Cr 0.000 0.000 0.000 0.000 0.000 0.000 Ti 0.016 Ti 0.002 Fe3 0.086 Fe3+ 0.038 Zn 0.000
Alvi 0.361 0.342 0.420 2.201 Cr 0.004 0.004 Ti 0.000 0.000 0.000 0.001 0.000 0.000 Fe3+ 0.009 Fe3+ 0.032 sum6 1.043 Mn3+ 0.001 sum4 1.182
Cr 0.019 0.014 0.020 0.000 Fe3+ 0.116 0.118 sum1 4.026 4.002 4.000 4.013 4.025 4.024 Fe2+ 0.309 Fe2+ 0.695 Fe2+ 0.853 sum 1.037 Si 0.075
Fe3+ 0.414 0.485 0.770 0.000 sum6 4.000 4.000 Ba 0.000 0.000 0.000 0.000 0.000 0.000 Mn 0.006 Mn 0.023 Mn 0.014 Ca 0.921 Ti 0.162
Fe2+ 1.147 1.242 0.883 1.056 Ca 0.422 0.478 0.509 0.561 0.686 0.828 Mg 0.699 Mg 1.202 Mg 0.090 Na 0.000 Al 0.118
Mn 0.021 0.017 0.031 0.014 Fe2+ 2.571 2.833 Na 0.527 0.521 0.479 0.418 0.278 0.135 Ca 0.807 Ca 0.019 Ni 0.000 sum2 0.921 Cr 0.041
Mg 2.731 2.551 2.660 1.596 Mg 1.832 2.094 K 0.003 0.002 0.002 0.001 0.000 0.000 Na 0.045 sum6 2.000 sum8 0.957 Fe3+ 1.367
Sum O 5.000 5.000 5.000 5.000 Ca 1.502 0.967 sum2 0.952 1.001 0.989 0.980 0.964 0.963 sum6 2.000 V 0.000
Mn 0.095 0.105 Ca 0.055
Ca 1.777 1.725 1.708 1.895 Na 0.000 0.000 components components components sum6 1.818
Na 0.836 0.881 0.836 0.814 sum8 6.000 6.000 An 0.443 0.478 0.514 0.572 0.712 0.859 Diopside 0.494 Enstatite 0.584
K 0.031 0.030 0.029 0.021 Ab 0.554 0.521 0.484 0.427 0.288 0.140 Hedenbergite 0.218 Ferrosilite 0.338
Ba 0.000 0.000 0.000 0.003 components Or 0.003 0.002 0.002 0.001 0.000 0.001 Jadeite 0.020 Al 0.013
Enstatite
Sum Y 2.644 2.636 2.573 2.733 grossular 0.250 0.161 Opx 0.148 Cpx 0.019
pyrope 0.305 0.349 Tschermakite 0.089 Na Cpx 0.000
almandine 0.428 0.472 Rest 0.031 Rest 0.046
XMg 0.700 0.670 0.744 0.599 spessartine 0.016 0.018
Lithos 394–395 (2021) 106184
D. Balen and H.-J. Massonne Lithos 394–395 (2021) 106184

Fig. 7. A-D: BSE images of microtextures in the garnet amphibolite sample GA. E-F: BSE images showing enlarged details of the symplectite corona around garnet (E) and clinopyroxene (F).
G-H: Distribution maps for Ca and Mg in garnet (large grain in the center), surrounding symplectite, and clino- and ortho-pyroxene in the matrix obtained with a CAMECA SX100 EMP
(sample GA). Amp – amphibole, Cpx – clinopyroxene, Grt – garnet, Ilm – ilmenite, Opx – orthopyroxene, Pl – plagioclase, Spn – titanite (sphene), Rt – rutile.

11
D. Balen and H.-J. Massonne
Fig. 8. P-T pseudosection calculated in the MnNCKFMASHTO system for the (modified) composition of pargasite amphibolite sample PA with PERPLE_X. The greytones of the P-T fields
refer to the variance (the darker the higher) of the corresponding mineral assemblage. Small fields are omitted for clarity. Abbreviations after Whitney and Evans (2010).
5. Discussion
5.1. Protoliths and their geotectonic environments
The minor and trace element data (Table 1, Fig. 5, Supplementary
Table 1) point to the origin of the basic and ultrabasic protoliths
that later became part of an ophiolite complex as it was postulated
in numerous earlier papers (e.g. Pamić et al., 2002; Šegvić et al.,
2019; Trubelja et al., 1995 and references therein). The high quantities
of Al2O3 and MgO with high Mg-number (Mg# = 85 for PA in con-
trast with Mg# = 59 for GA) and the low abundances of SiO2, TiO2
and Fe2O3 clearly point to an ultrabasic rock (peridotite) as protolith
of sample PA. The compatible trace elements Ni, Co, and V show rela-
tively high contents of 325 ppm, 76 ppm, and 40 ppm, respectively,
whereas incompatible elements (Zr, Y, Ba) are low (3 ppm, 3 ppm,
and 27 ppm, respectively) and similar to those in ultrabasic rocks
from Alpine ophiolites (Beccaluva et al., 1980; Furnes et al., 2020).
According to geochemical characteristics, the protolith of sample PA,
as a representative of the extended group of pargasite amphibolites,
12
Lithos 394–395 (2021) 106184
probably formed in a deeper level as mantle peridotite. Trace element
patterns normalized to primitive mantle (Figs. 5C, D) show the char-
acteristic element distribution of upper mantle peridotite with a neg-
ative Ti anomaly pointing to the influence of fluids. Fluids in an
environment characterized by subduction of oceanic crust beneath
an oceanic plate could come from a dehydrating subducting slab and
previously serpentinized mantle. Therefore, a plausible position for
the protolith of PA is the lower part of the upper plate in such an en-
vironment and, thus, the possible base of an ophiolite sequence. Dur-
ing metamorphism of this usually dry base H2O-bearing minerals
(pargasitic amphibole and others) formed, which require significant
amounts of H2O for their genesis.
Sample GA shows a typical MORB signature (see the concentrations
of Ti, Zr and Y). The REE show a relatively low abundance for the light
REE with (La/Sm)N = 0.42, a slight negative Eu anomaly (Eu* = 0.89)
and a flat curve for the heavy REE. The sum of REE equals 44 ppm
which is significantly higher than for sample PA (3 ppm). The trace-
element normalized pattern (Figs. 5C, D) is characterized by a steep
slope from Rb to Sr and relatively smooth pattern from Zr to Lu. A
D. Balen and H.-J. Massonne
Fig. 9. P-T pseudosection calculated in the MnNCKFMASHTO system for the (modified) composition of garnet amphibolite sample GA with PERPLE_X. The greytones of the P-T fields refer
to the variance (the darker the higher) of the corresponding mineral assemblage. Small fields are omitted for clarity. Abbreviations after Whitney and Evans (2010).
slightly negative Sr anomaly could be ascribed to an alteration process
prior to metamorphism. Based on the major and trace elements, the
gabbroic/basaltic protolith of sample GA formed as N-MORB and origi-
nated in the upper part of an oceanic plate.
The geochemical data for both selected rocks PA (+ 5 other samples
of the nineteen ones analyzed, Supplementary Table 1) and GA (+ 12
other samples) differ in Mg# and sum of REE. Furthermore, normalized
patterns (Figs. 5C, D) are neither coherent nor sub-parallel. Thus, the
rocks originated from different sources and/or the rocks underwent dif-
ferent petrogenetic processes. Taking into account the geochemical
characteristics of rocks available from the literature (Lugović et al.,
1991; Trubelja et al., 1995; Pamić et al., 2002; Babajić, 2009; Chiari
et al., 2011; Srećković-Batoćanin et al., 2012; Faul et al., 2014; Šegvić
et al., 2019, 2020) and their assignment to original depth positions for
the protoliths, sample PA, which originated from peridotite, should be
ascribed to the lower part of the overriding plate. On the other hand,
sample GA with geochemical characteristics of N-MORB can be related
to the upper part of an oceanic plate that was subducted according to
the derived P-T path.
13
Lithos 394–395 (2021) 106184
5.2. Pressure-temperature paths and metamorphic conditions
5.2.1. Counterclockwise (CCW) P-T path for sample PA
Considering the above discussion of the geochemical data, pargasite
amphibolite, the protolith of which was a peridotite possibly from the
mantle wedge, should have been situated at the bottom part of the over-
riding plate. Primary minerals in a peridotite like olivine, clinopyroxene,
orthopyroxene and chromium spinel, were transformed in contact with
hydrous fluids. An initial starting point of a P-T path (point 1, Fig. 10) is
typically at high-temperature and high- to medium-pressure (~ 0.5–2
GPa) conditions characteristic for spinel-bearing mantle rocks.
Although set arbitrarily, point 1 in the P-T space represents minimal
P-T conditions (ca. 0.9 GPa and 1075 °C) within modelled P-T space
that prevailed before the beginning of metamorphism. Such conditions
fit those expected for the aforementioned mantle wedge. The
earliest metamorphic reaction observed in thin sections is the transfor-
mation of spinel to sapphirine at granulite-facies conditions (point 2; ca.
P = 1.2 GPa, T = 1000 °C; Fig. 6A, B; Awalt and Whitney, 2018).
Sapphirine in our pseudosection occurs in the range of P = 1.2–1.4
D. Balen and H.-J. Massonne
Fig. 10. Contouring of P-T pseudosections for sample PA with isopleths and isomodes for
selected minerals. P-T estimates based on intersecting isopleths are marked with
numbered ellipses/circles. The radii of the ellipses are approximately proportional to the
deviations of the corresponding isopleths from the selected values. Abbreviations after
Whitney and Evans (2010). Arrow shows the CCW P-T path.
GPa and T = 920–1000 °C. Recognizable blasts of corundum (Fig. 6C,
H) characteristic for pargasite amphibolite did not develop in a P-T
field adjacent to the sapphirine field (point 3a) but at conditions of
stable plagioclase at pressures somewhat above 0.8 GPa (740 °C; point
3b) because inclusions of amphibole and plagioclase occur in corundum
blasts. Corundum grew until P-T conditions of point 4 were reached.
Corresponding microtextures were already described by Operta et al.
(2003) and related to pressures between 0.6 and 1.0 GPa at tem-
peratures between 620 and 830 °C. The pseudosection of Fig. 10 con-
strains the coexistence of amphibole and plagioclase inside corundum
to P = 0.9 GPa and T = 680 °C. Large quantities of Al in the system
causing the formation of corundum are one of the chemical peculiarities
of pargasite amphibolite. During metamorphism along a possible near-
isobaric cooling path, kyanite formed as another Al-rich phase at P = 0.8
GPa and T = 660 °C (point 5; Fig. 6G). The main assemblage of pargasite
amphibolite is characterized by amphibole (Si = 6.15 pfu) and plagio-
clase (An93) that equilibrated at P-T conditions of 0.8 GPa and 590 °C
(point 6). Chlorite also occurs along the proposed P-T path (Fig. 6G).
Further retrograde processes led to development of white mica (Si =
3.0 pfu) around corundum (point 7; ca. P = 0.8 GPa, T = 580 °C;
Fig. 6G, H). The P-T path predicts the observed transition from rutile
to titanite (Fig. 6E, F; point 8) at P = 0.8 GPa, T = 500 °C. The sequence
of observed microtextures and calculated mineral stability fields sug-
gests a CCW P-T path with maximal pressure of 1.2 GPa at T = 960 °C.
5.2.2. Clockwise (CW) P-T path for sample GA
The garnet amphibolite originated from a N-MORB representing the
upper part of a down-going oceanic plate (see above). Pressures rose
during subduction of this plate. The maximum value was deduced
from the garnet core composition (Grs25, Prp30, Alm43) and occurrence
of rutile enclosed in garnet (Fig. 7B). The starting point 1 (inner garnet
core) of the metamorphic path in Fig. 11 corresponds to ca. P = 2.0
GPa and T = 700 °C. During prograde conditions garnet grew toward
maximal modal content (calculated 50 vol%) at ca. P = 2.0–2.1 GPa at
T = 810 °C (point 2). This prograde path is compatible with early field
descriptions of garnet amphibolites as eclogite and/or garnetite with
14
Lithos 394–395 (2021) 106184
Fig. 11. Contouring of P-T pseudosections for sample GA with isopleths and isomodes for
selected minerals. P-T estimates based on intersecting isopleths are marked with
numbered ellipses/circles. The radii of the ellipses are approximately proportional to the
deviations of the corresponding isopleths from the selected values. Garnet “rim”
represents rather garnet outer zone domain. The P-T conditions obtained for formation
of the corona microtextures around garnet (kelyphite) and the symplectitic corona
microtextures around clinopyroxene are marked with points 7 and 8, respectively.
Abbreviations after Whitney and Evans (2010). Arrow shows the CW P-T path.
large quantities of garnet in the Vijaka area (Pamić et al., 1973, 1977).
After peak-pressure conditions, garnet was consumed by reactions
and, thus, diminished in size and volume so that only about 25 vol% of
the original 50 vol% remained. However, inclusions in garnet, important
for deducing a P-T path (e.g. Li et al., 2020), can be found inside still large
porphyroblasts (Fig. 7A) that seem to have been hardly replaced by
other phases. For example, the aforementioned rounded plagioclase in-
clusions were taken as evidence for the consumption of this phase by
garnet. On the contrary, the replacement of rutile by ilmenite (Fig. 7B)
in garnet took place already along the exhumation path because fluids
could penetrate garnet through cracks. For the expected range of tem-
peratures, the transition of rutile to ilmenite occurred at P ~ 1.5 GPa
(point 3). Furthermore, amphibole (Si = 6.07 pfu), for instance, inside
the garnet domain with Alm47–49 was formed along the CW P-T path
(point 4). The P-T path continues to the plagioclase field which was
reached at P = 0.75–80 GPa and T around 920 °C (point 5) as well as
the aforementioned reaction of rutile to ilmenite. Amphibole (Si =
6.10–6.17 pfu) and plagioclase (An48–51) in the matrix of the rock equil-
ibrated at maximal values of P = 0.75–80 GPa and T = 880 °C (point 6).
The actual garnet rim was replaced by a symplectitic corona (kelyphite)
after infiltration by fluids (Obata et al., 2013; Obata and Ozawa, 2011).
The symplectite consists primarily of amphibole (Si = 6.4 pfu), plagio-
clase (An72) and spinel (magnetite). The obtained P-T conditions for
its formation (point 7) are P = 0.6 GPa and T = 850 °C. Microdomains
of the corona around garnet point to a significant pressure drop from
2.0–2.1 GPa (ca. 70 km) to 0.6 GPa (20 km) equivalent to an exhumation
of 50 km. A similar conclusion concerning near-isothermal decompres-
sion can be drawn from the symplectitic corona around clinopyroxene
(Fig. 7F) that formed at P = 0.55 GPa and T = 820 °C (point 8). These
P-T conditions resulted from the coexistence of orthopyroxene and pla-
gioclase (An57). The ilmenite to titanite transition took place at P =
0.50–0.55 GPa and T = 620 °C (point 9). The sequence of described
microtextures and P-T conditions defines a CW path.
D. Balen and H.-J. Massonne
5.3. General considerations
Reported counterclockwise (CCW) P-T paths are rare (e.g. Li et al.,
2017; Liu and Massonne, 2019; Wakabayashi, 1990; Willner et al.,
2004) and not known yet whether they are typical of metamorphic
sole rocks. However, such examples were recognized and well de-
scribed from the Oman metamorphic sole (e.g. El-Shazly and Coleman,
1990; Hacker, 1991). Except our recent pilot research using older
solid-solution models (Balen and Massonne, 2019) than here, quantita-
tive P-T paths were not modelled nor CCW paths were recognized be-
fore in the Dinarides. Several reconstructions of generalized clockwise
(CW) P-T paths have been proposed recently (e.g. Šegvić et al., 2019,
2020; Srećković-Batoćanin et al., 2012), based on reaction curves that
followed estimation of peak metamorphic conditions by classical
geothermobarometry.
According to geochemical considerations, two rocks chosen in our
research for modeling the metamorphic evolution represent different
parts of mantle and oceanic crustal domains that were trapped at differ-
ent position inside the Jurassic Dinaride subduction zone system. There-
fore they can have a different metamorphic evolution i.e. mutually
distinct P-T paths. A general problem in detailed studies of a few meta-
morphic rocks is their representativeness for a larger area. To check this,
we have optically inspected numerous samples with the polarized-light
microscope. In addition, EMP analyses were also performed on thin sec-
tions of other samples than PA and GA also not as detailed as for the two
selected rocks. These investigations reveal that mineral and
microtextural characteristics may be potentially sufficient to character-
ize two different groups of rocks represented by PA and GA. All other
samples which did not preserve mineral relations in a similar manner
as the selected two samples inevitable record a comparable but incom-
plete part of the above outlined CW or CCW P-T paths.
5.3.1. Geodynamic scenario with implications for the early convergence in
the Dinarides
Distinct P-T paths reaching contrasting peak pressures are a re-
sult of sample positions in differently moving rock volumes. This
could be the case in a deep-seated subduction channel (e.g. Li
et al., 2017) or in an exhumation channel (e.g. Massonne, 2016;
Massonne et al., 2018). The CW path recorded for GA, a metamor-
phosed N-MORB, was set in the upper part of a subducting oceanic
crust, whereas the CCW path for PA is assigned to a metamorphic-
sole rock that originated as peridotite of the hot mantle wedge be-
coming the lower part of the upper (overriding) plate. Both studied
rocks were rapidly exhumed and placed close to each other (at
present time ca. 1.4 km horizontally and 110 m vertically apart)
in the exposed metamorphic-sole zone of the KKUM.
Various authors proposed different scenarios and models for the de-
velopment of the metamorphic sole in the KKUM and other localities re-
lated to ophiolites in the Dinarides. Such scenarios, at least for the
western part of the Dinarides, are based mainly on the composite
model by Pamić et al. (2002). The variation of details in critical times
for the evolution of the Dinarides (Late Jurassic–Early Cretaceous and
Late Cretaceous–Early Paleogene) relies mainly on the suggested exis-
tence of one ocean and its internal evolution (e.g. Gawlick et al., 2020;
Gawlick and Missoni, 2019; Pamić et al., 2002; Schmid et al., 2008,
2020) or two oceanic domains (e.g. Lugović et al., 1991; Robertson
et al., 2013). The case-study models for the petrogenesis of a metamor-
phic sole in different parts of the Dinarides so far were based on “peak”
P-T data without or with dating (e.g. Borojević Šoštarić et al., 2014;
Šegvić et al., 2019, 2020; Srećković-Batoćanin et al., 2012). Šegvić et al.
(2019, 2020) deduced peak P-T conditions of ~800 °C and 1 GPa for
the KKUM metamorphic sole reached at 159 ± 6.8–162 ± 14 Ma. All
these models implied simple CW metamorphic path(s) based on classi-
cal thermobarometry and/or a simplified general petrogenetic grid for
the basaltic system.
15
Lithos 394–395 (2021) 106184
A possible scenario presented here for the genesis of rocks from the
metamorphic sole in the Dinarides is based on pseudosection modeling
and petrogenetic considerations related to intra-oceanic subduction
that occurred inside the Dinaridic segment of the Jurassic Neo-Tethys
ocean. In the case of the pargasite amphibolite, we suggest that the
hot upper mantle wedge overrode the down-going oceanic plate and
came in contact with ascending hydrous fluids. A CCW P-T path
(Fig. 10) would be established when the hot material of the overriding
plate would be scraped off (subduction or tectonic erosion, see von
Huene and Scholl, 1991; Massonne and Li, 2020) and attached to the
cold subducting plate that caused cooling of the hot material.
Such a situation is likely for the collision of an oceanic plate with
another oceanic plate. In this scenario, the subducting oceanic
plate dehydrates to provoke hydration of the overlying material
(e.g. Massonne, 2012; van Keken et al., 2011; Wada et al., 2012).
The CW P-T path with peak-pressure conditions of 2.1 GPa (ca.
70 km depth) was reconstructed for garnet amphibolite originated
from N-MORB (Fig. 11). These conditions were followed by a sig-
nificant pressure decrease to 0.5–0.6 GPa without significant change
of temperature also supported by kelyphite formation around gar-
net. A plausible explanation for the deduced path is the rapid ex-
humation of material from the subducted oceanic crust by at
least 50 km in a subduction channel. The studied rocks from
both plates were further exhumed later on contemporaneously
with the closure of the oceanic domain between the continental
plates Adria and Europe. The part of the Neo-Tethys with KKUM
rocks was closed by the end of the Jurassic (Kimmeridgian?). This
process definitively did not last until Early Cretaceous times (see
Geological Setting). The above geodynamic scenario explains the re-
constructed CW and CCW P-T paths for rocks of the KKUM meta-
morphic sole in Jurassic times.
6. Conclusions
For the first time two-contrasting metamorphic P-T paths were re-
constructed for rocks of the DOZ which present details on the prograde,
peak and especially retrograde metamorphism. These CW (peak P = 2.1
GPa at T = 810 °C) and CCW (peak P = 1.2 GPa at T = 960 °C) paths
demonstrate the involvement of rocks from the metamorphic sole of
an obducting ophiolite in a subduction channel. Such an evolution can
be expected for rocks of other metamorphic soles. The metamorphic
evolution of the studied rocks mainly took place before the metamor-
phic sole developed by the obducting oceanic crust to form the KKUM.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influ-
ence the work reported in this paper.
Acknowledgements
We thank two anonymous reviewers and Lithos editor Marco
Scambelluri for their insightful comments and suggestions. Support by
the Croatian Science Foundation, Hrvatska Zaklada za Znanost (HRZZ)
(IP-2014-09-9541) is acknowledged. The help by Tonči Grgasović and
Davor Kudrnovski (†) during an early stage of field research is greatly
appreciated. The authors are grateful to Petra Schneider for help during
manuscript editing and Thomas Theye for support of our electron
microprobe work.
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.lithos.2021.106184.
D. Balen and H.-J. Massonne
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