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Lithos 324–325 (2019) 439–453

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Lithos

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Exhumation of the high-pressure northwestern Cyclades, Aegean:
New P-T constraints, and geodynamic evolution
Ioannis Baziotis a,⁎, Alexander Proyer b, Evripides Mposkos c, Brian Windley F. d, Ioanna Boukouvala a
a
Department of Natural Resources Management and Agricultural Engineering, Agricultural Univ. of Athens, Iera Odos 75, 11855 Athens, Greece
b
Department of Earth and Environmental Sciences, Botswana International University of Science and Technology (BIUST), PB 14 Palapye, Botswana
c
School of Mining and Metallurgical Engineering, National Technical University of Athens, 9 Heroon Politechniou St., Zografou, Athens GR-15780, Greece
d
Department of Geology, The University of Leicester, Leicester LE1 7RH, United Kingdom

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

Article history: The Cycladic Blueschist Unit in the southern Aegean of Greece comprises Lower and Upper Tectonic Units (LTU,
Received 10 June 2018 UTU), both of which were affected by high-pressure, low-temperature metamorphism. However, in the Penteli
Accepted 21 November 2018 area the LTU contains predominant greenschists with only traces of blueschist facies minerals (glaucophane-
Available online 26 November 2018
and phengite-bearing). In contrast, the UTU contains well-preserved blueschists (glaucophane- and lawsonite-
bearing). Our new integrated thermodynamic data indicate that prograde metamorphism was different in
Keywords:
Exhumation of blueschists
the two units, which were juxtaposed relatively late, at P b 0.6 GPa. New P-T data from the LTU show that
Subduction zone peak P (~1.3–1.2 GPa) was reached at ~300 °C, followed by exhumation, first with a significant temperature
Aegean domain increase to ~480 °C at pressures of ~0.7–0.8 GPa, and subsequent drastic cooling. For the UTU, the maximum
Cycladic Blueschist Unit P was at ~0.9 GPa at a T of ~310–330 °C, followed by gentle cooling during exhumation.
Thermodynamic modeling © 2018 Elsevier B.V. All rights reserved.
Multi-equilibrium method

1. Introduction constrain both the prograde and retrograde P-T evolution of the little-
known blueschist-bearing Penteli area in western ACCB (Fig. 1 B).
The Attic-Cycladic Crystalline Belt (ACCB) is one of the most in-
tensely studied young high-pressure low-temperature metamorphic 2. Geological setting
belts in the world (Jolivet and Patriat, 1999; Ring et al., 2010). It is situ-
ated on the northern side of the north-dipping Hellenic subduction zone The rocks in the Penteli area are sub-divided into Lower and Upper
(show the ACCB on Fig. 1A) and formed as a result of major extensional Tectonic Units (LTU, UTU). The LTU contains four main lithologies:
collapse of the Alpine orogenic belt in the Aegean that resulted from the schists, marbles (with lenses of mafic-ultramafic rocks), quartzo-
collision between the Eurasian plate and Gondwana-derived fragments feldspathic orthogneisses and migmatites (Fig. 1B). The UTU is com-
in the Cenozoic (Altherr et al., 1982; Jolivet and Brun, 2010). The ACCB posed of marbles intercalated with variety of schists and lenses of
underwent high-pressure/low temperature (HP/LT) blueschist to mafic greenstones intercalated between the schists. Residual Neogene
eclogite facies metamorphism in the Eocene (ca. 50–40 Ma), and a sediments occur west of the Penteli area, and east of Parnitha rocks
Barrovian-type greenschist-amphibolite facies overprint in the Oligo- (Krohe et al., 2010; Mposkos et al., 2007). Both the LTU and UTU in
cene/Miocene (ca. 25–20 Ma; Okrusch and Bröcker, 1990; Wijbrans Penteli underwent penetrative deformation during their tectono-
et al., 1990; Tomaschek et al., 2003; Putlitz et al., 2005; Lagos et al., metamorphic evolution, and their overall structure is characterized by
2007; Bröcker et al., 2013; Dragovic et al., 2015; Lister and Forster, large-scale nappes and thrust-imbricated repetition of original litho-
2016; Laurent et al., 2017). In the northwestern extension of the stratigraphy (see Fig. 1; map and cross sections from Lozios, 1994).
ACCB, only the Lavrion area in eastern Attica (Fig. 1A) has been investi- This study focuses on poorly known high-pressure rocks in both the
gated in terms of petrology, geochemistry, ore mineralogy and LTU and UTU of the Penteli area (Fig. 1; Lozios, 1994). The LTU contains
geodynamic evolution (Baziotis et al., 2009; Jolivet et al., 2003; Liati only scarce glaucophane as relict inclusions in albite and/or garnet,
et al., 2013; Scheffer et al., 2016, 2017). In this study, we report new whereas the UTU contains well preserved high-pressure rocks, charac-
conventional geothermobarometric and multi-equilibria data that terized by abundant glaucophane in the matrix with albite, but without
epidote (Evans, 1990). The aim of this study is to constrain discrete
stages along the prograde and retrograde metamorphic evolution of
⁎ Corresponding author. the LTU and UTU. Local domain equilibria between phengite and chlo-
E-mail address: ibaziotis@aua.gr (I. Baziotis). rite, which are predominant in phyllosilicate schists, were used to

https://doi.org/10.1016/j.lithos.2018.11.027
0024-4937/© 2018 Elsevier B.V. All rights reserved.
440 I. Baziotis et al. / Lithos 324–325 (2019) 439–453

Fig. 1. (a) Simplified geological map of Penteli area. The numbers correspond to the estimated temperatures based on graphite thermometry. (b) Inset shows the location of Penteli, as part
of the NW extension of the HP Cyclades belt. (c,d) Geological cross-sections showing the large-scale structure and lithological relations in LTU (adapted from Lozios, 1994).
I. Baziotis et al. / Lithos 324–325 (2019) 439–453 441

constrain the P–T evolution (Parra et al., 2002a; Trotet, 2000; Trotet Table 1
et al., 2001a, 2001b; Vidal and Parra, 2000). Additionally, Raman Raman spectrum parameters and temperatures obtained using the equation given in the
main text for the LTU and UTU of Penteli.
micro-spectroscopy of carbonaceous material (RSCM) is applied to con-
strain the peak temperature of metamorphism (Beyssac et al., 2002a, Sample G position G FWHMa D1 FWHM D2 FWHM R1 R2 T( ͦC)
2002b; Rahl et al., 2005). The P-T information is used to constrain the Μ7-1 1583.3 29.65 37.58 21.55 1.45 0.57 426
style of exhumation (cf. Baziotis et al., 2017). Finally, we correlate and Μ7-3 1583.3 32.02 38.14 21.81 1.48 0.57 431
evaluate the metamorphic evolution of the Penteli area with that of Μ7-4 1580.3 30.58 40.32 28.78 1.48 0.58 414
Μ7-5 1580.1 33.57 38.35 22.80 1.28 0.53 452
the remaining ACCB, to improve understanding of the tectonic develop-
Μ7-6 1580.5 29.27 39.50 26.95 1.44 0.58 413
ment of this Cenozoic Aegean orogenic belt. Μ7-7 1581.5 30.72 39.17 21.71 1.28 0.56 422
Μ7-8 1581.2 30.89 38.35 22.86 1.40 0.57 421
3. Analytical methods Μ7-9 1581.6 28.26 38.52 23.85 1.03 0.51 433
Μ7-10 1580.3 38.10 39.34 22.55 1.30 0.50 484
All collected samples were fresh and unaltered. Mineral analyses 11-03-04-2 1578.6 30.43 38.10 30.18 1.17 0.50 469
11-03-04-3 1581.5 25.97 42.34 18.17 0.95 0.47 468
were performed with a JEOL JSM-6310 scanning electron microprobe
11-03-04-4 1583.2 31.98 38.10 21.85 1.37 0.51 481
at the Institute of Earth Sciences, Karl-Franzens University, Graz, 11-03-04-9 1581.2 19.60 41.70 15.79 0.86 0.43 495
Austria. Analytical conditions for spot analyses were 15 kV accelerating 11-03-05-1 1580.1 17.70 41.08 15.50 0.47 0.37 475
voltage, 5 nA beam current, a data acquisition time of 100 s and a beam 11-03-05-2 1580.9 18.40 42.51 11.90 0.52 0.38 477
11-03-05-3 1580.4 21.71 43.87 14.98 0.65 0.41 474
diameter of 2 μm, or wherever was possible increased the beam diame-
11-03-05-4 1581.0 25.00 42.10 18.90 0.82 0.54 370
ter up to 4–8 μm. Chemical standards used were quartz (Si), titanite (Ca, 11-03-05-5 1581.7 19.58 41.64 15.80 0.87 0.51 411
Ti), corundum (Al), rhodonite (Mn), garnet (Mg, Fe), adularia (K) and 11-03-05-6 1579.6 17.65 41.10 15.43 0.43 0.47 359
jadeite (Na). All samples were measured with an energy dispersive sys- 11-03-05-7 1580.9 19.00 41.77 23.10 0.41 0.46 364
tem (EDS) except for Na that was measured with a wavelength disper- 11-03-05-9 1581.2 18.40 42.50 11.90 0.53 0.39 469
11-03-05-10 1581.4 18.66 42.58 17.66 0.57 0.40 467
sive system (WDS). Representative mineral compositions are given in
11-03-06-1 1581.2 18.44 43.43 17.70 0.41 0.36 471
Tables S1–S14. 11-03-06-2 1580.1 19.23 41.80 23.13 0.42 0.41 420
Carbonaceous material (CM) was analyzed by Raman spectros- 11-03-06-5 1581.0 20.89 40.02 24.57 0.29 0.38 418
copy (Beyssac et al., 2002a) and maximum temperatures reached 11-03-06-7 1581.0 18.43 42.56 11.90 0.5 0.47 376
11-03-06-8 1580.8 18.33 42.57 11.89 0.52 0.39 466
by the samples were computed using the temperature equation of
78-1 1581.6 25.90 42.22 18.17 1.07 0.57 380
Baziotis et al. (2006). Seventy samples of graphite-rich phyllites, 78-2 1581.5 25.92 42.34 18.01 1.06 0.56 389
schists and slates were collected from selected LTU and UTU outcrops 78-3 1581.0 19.72 41.77 15.93 0.87 0.50 422
in the Penteli area but RSCM analyses were performed on ten (six 78-4 1580.8 30.50 40.40 28.70 1.26 0.51 469
from LTU and four from UTU) representative samples (Table 1). We 78-6 1578.1 27.23 39.57 23.17 0.87 0.44 486
78-8 1580.2 21.17 42.08 19.91 1.06 0.49 464
used a Renishaw confocal RM1000B Raman microprobe at the
MCS-2 1580.5 35.64 38.66 27.87 1.11 0.47 493
Department of Geosciences, National Technical University, Athens. MCS-4 1580.1 30.55 40.30 28.71 1.26 0.50 480
Raman spectra were excited at room temperature using the MCS-5 1580.7 21.22 42.28 19.99 1.08 0.46 499
632.817 nm line of the He\\Ne laser. The spot at the surface of the MCS-9 1580.0 30.66 40.43 28.71 1.25 0.51 468
MCS-10 1583.1 31.90 38.02 21.78 1.36 0.50 491
sample was about 5 μm using a 100× objective with laser power
020801-a 1590.8 48.65 41.85 20.39 2.82 0.68 278
b 5 mW. To avoid matrix effects, we focused under the surface of 020801-b 1590.5 43.40 42.80 24.58 2.57 0.68 303
the CM with an acquisition time of 100 s. The software Grams32 pro- 020801-c 1589.7 41.02 41.11 27.09 2.82 0.68 279
vided by Renishaw was used for deconvolution of the Raman spectra 020801-d 1589.4 34.27 39.72 26.07 2.52 0.69 301
to the constituted bands and determination of full width at half max- 020802-a 1586.8 33.73 37.22 20.18 2.58 0.66 321
020802-b 1592.1 47.86 43.57 21.01 2.53 0.66 324
imum (FWHM), peak height, peak area and peak position by fitting to
020802-c 1588.1 40.28 40.69 27.35 2.64 0.65 324
mixed Gaussian-Lorentzian curves. We focused on a first-order 020802-d 1587.4 35.16 35.89 17.50 2.61 0.67 309
1000–1800 cm−1 region. RSCM results are listed in Table 1. 020803-a 1585.3 37.25 34.63 17.75 2.54 0.65 343
020803-b 1587.4 41.70 34.71 16.10 2.10 0.58 330
4. Field occurrence and petrography 020803-c 1586.5 20.07 42.85 18.27 1.10 0.61 340
020803-d 1587.3 19.29 44.58 18.61 1.00 0.60 337
020804-a 1588.2 21.29 38.08 15.75 1.79 0.74 264
4.1. LTU 020804-b 1587.3 40.20 39.49 23.84 2.92 0.69 251
020804-c 1589.9 42.88 42.22 24.37 2.85 0.69 262
4.1.1. Migmatites 020804-d 1590.6 45.74 40.92 21.05 2.92 0.69 252
Migmatites occur as tectonic slices and lenses ranging from a a
FWHM: full width at half maximum.
hundred meters to more than one kilometer in length, intercalated
within calc-schists or between calc-schists and marbles. These Microcline occurs as coarse-grained porphyroclasts, commonly with
migmatites formed after partial melting of para-gneisses and were
Carlsbad twinning (Fig. S2c), that contain inclusions of plagioclase with
then re-metamorphosed under lower-grade conditions. More details corroded edges or it is predominant in the fine-grained matrix. In fine-
about these migmatites are given in the supplementary information
grained domains, quartz grains are completely recrystallized with
(Fig. S1). the development of flattened quartz ribbons (ultramylonite; Fig. S2c).
Albite occurs as anhedral grains in the matrix and as subhedral inclu-
4.1.2. Orthogneisses
sions in cloudy cores of microcline porphyroclasts (Fig. S2d). Phengite
Orthogneisses occurring as tectonic slices within the calcitic schists
forms fine-grained flakes enclosed in microcline, or medium-grained
or between calcitic schists and marbles consist of leucocratic phengite
clasts with characteristic mica-fish shapes (Fig. S2a) and stair-
gneisses (often with K-feldspar augen) and dark amphibole-epidote-
stepping trails, or local isolated grains lying parallel or oblique to the
albite gneisses.
foliation. Biotite, where present, is intergrown with muscovite parallel
1. Phengite gneisses: Mineral assemblages consist of microcline- to the foliation; it is often replaced by chlorite.
quartz-phengite±albite±biotite; zircon, apatite and opaques are In ultramylonite domains fine-grained K-feldspar dominates,
accessories. Penetrative deformation has led to mylonites and phengite occurs as relics with corroded edges, and albite is almost
ultramylonites (Fig. S2a, b). absent (Fig. S2b).
442 I. Baziotis et al. / Lithos 324–325 (2019) 439–453

2. Amphibole-epidote-albite-orthogneisses (metadiorite) have the calcite ± opaque. Sodic amphibole mostly occurs as subhedral to
mineral assemblage albite + green amphibole + epidote/ euhedral elongate crystal in the matrix, although it also forms inclusions
clinozoisite + quartz + biotite + phengite + chlorite ± calcite; in albite and calcite (Fig. 3e–h). Chlorite is either a major phase of the
they are coarse-grained, and have different assemblages from the matrix or is a replacement after biotite or amphibole (Fig. 3g,h).
metabasites Phengite flakes are aligned parallel to the main rock foliation, or rarely
form inclusions in albite (Fig. 3h).
Albite occurs as medium to coarse-grained porphyroblasts contain-
ing inclusions of phengite, epidote and green amphibole. Epidote 5. Mineral chemistry
forms coarse-grained crystals or medium-grained aggregates. Biotite
and phengite are in textural equilibrium lying parallel to the rock folia- 5.1. LTU
tion, as does chlorite. In most cases, biotites occur with green amphi-
boles in anastomosing networks around albite porphyroblasts and/or 5.1.1. Schists
have characteristic C′-type shear band cleavages. Prismatic green
amphibole crystals are oriented parallel to the foliation or occur as ori- 5.1.1.1. Phengite. The K-rich white micas are mainly phengites with Si
ented inclusions in albite. ranging from 3.126 to 3.526 a.p.f.u.. The celadonite component ranges
from 5.9 to 36.2%, pyrophyllite from 7.1 to 34.9% and paragonite is up
4.1.3. Schists to 15% (Fig. 4, S4). Core-rim profiles in zoned phengites exhibit the fol-
The schists of LTU are divisible into: calcite-chlorite-garnet, lowing variations (from core to rim): decrease of Si (3.445 to 3.175 a.p.f.
chloritoid-phengite, chlorite-phengite, paragonite-chlorite-phengite u.), increase of AlIV (0.539 to 0.815 a.p.f.u.), increase of AlVI (1.643 to
and paragonite-chloritoid-phengite schists. These schistose assem- 1.915 a.p.f.u.), decrease of Fe2+ (0.203 to 0.059 a.p.f.u.) and decrease
blages are pervasively foliated. of Mg (0.223 to 0.112 a.p.f.u.).

4.1.3.1. Calcitic schists. Calcite-rich schists and marbles are the predomi- 5.1.1.2. Chlorite. The XMg [XMg = Mg/(Mg + Fe)] is in the range of 0.41–
nant lithologies in the Penteli LTU. Mineral assemblages contain calcite 0.70, and the Si content of 2.51–2.84 a.p.f.u.. Most chlorites plot between
+ quartz + chlorite + phengite + albite + garnet ± zircon ± apatite ± the amesite and clinochlore/daphnite fields (Fig. 5). Furthermore,
titanite ± opaques. the sudoite-clinochlore-daphnite diagram clearly shows that
the tschermakitic substitution is more extensive than FeMg−1. The
4.1.3.2. Paragonite-chlorite-phengite and paragonite-chloritoid-phengite clinochlore component ranges from 34 to 62% and the daphnite from
schists. Aligned chlorite, phengite and chloritoid mark the main foliation 26 to 52%.
and S\\C structures suggesting stable coexistence. Additionally, many
chloritoid porphyroblasts contain chlorite + phengite inclusions. 5.1.1.3. Chloritoid. Chloritoid is rich in iron with XFe [Fe2+/(Mn + Mg
Paragonite occurs either in the matrix with phengite and chloritoid or + Fe2+)] in the range of 0.77–0.95 and XMn [XMn = Mn/(Mn + Mg
phengite and chlorite or as inclusions in chloritoid. + Fe2+)] up to 0.13 (Fig. 5f). Two different zonations are shown in
Table S8.
4.1.4. Metabasites
The metabasites occur as massive, green, coherent lenses interca- 5.1.1.4. Paragonite. The paragonite composition is relatively homoge-
lated with schists and marbles. They are crosscut by numerous second- neous. The Si content is in the range 2.928–3.097 a.p.f.u. and XNa [XNa
ary veins composed of calcite and stilpnomelane. A large metabasite = Na/(Na + K)] of 0.878–0.980. The Fe\\Mg substitution is limited,
lens surrounded by calcite-rich schist is shown in Fig. S1 f. The predom- with Mg up to 0.043 a.p.f.u. and Fe+2 in the range of 0.010–0.044 a.p.f.u.
inant mineral assemblage is calcic amphibole + chlorite + albite + ep-
idote + phengite + titanite ± garnet ± stilpnomelane ± quartz ± 5.1.1.5. Garnet. The garnet generally displays a zonation from core to rim
biotite ± apatite ± opaque (Fig. 2). Blue sodic amphibole occurs as in- with Mn decrease, while Fe, and Ca either increase or decrease. We have
clusions in garnet, albite and epidote (Fig. 2f–h). Epidote is one of the measured three garnet profiles from a schist (sample 97P6). The results
predominant phases in the metabasites. It occurs either as large are summarized in Fig. S6.
subidiomorphic to idiomorphic porphyroblasts, as grain aggregates, or
as inclusions in albite or garnet. Garnets are subhedral to anhedral, 5.1.2. Orthogneisses
and variably replaced by chlorite and epidote. Pumpellyite occurs only Representative compositions of phengite and biotite from two sam-
as inclusions in garnet and varies slightly in composition. Stilpnomelane ples of orthogneisses are given in Tables S6, S10. The Si values of
occurs as randomly oriented aggregates either oblique or parallel to the phengite range from 6.9–7.26 a.p.f.u. Higher Si values are observed in
main foliation of the rock and matrix. phengites from sample PE4 that contains biotite as additional phase.
There is also a slight tendency for Mg/(Mg + Fe) to increase with in-
4.2. UTU creasing Si. The amount of Mg + Fe2+ in phengite exceeds Si-6 from
0.003 to 0.568 a.p.f.u. This indicates that an appreciable amount of
4.2.1. Schists iron is in a trivalent state substituting for AlVI. Phengite shows composi-
The most common mineral assemblage is: sodic-amphibole + tional zoning with increasing Fe and decreasing Al from core to rim
phengite + chlorite + epidote + calcite ± albite ± lawsonite ± biotite indicating increasing substitution of Fe3+ for Al towards the rim. Biotite
± titanite ± stilpnomelane ± quartz ± apatite ± opaque (Fig. 3). has a Mg/(Mg + Fe) ratio ranging from 0.46 to 0.50. The AlIV and Ti
Phengites together with large laths of sodic amphibole are oriented par- values vary from 2.04 to 2.06 and from 0.32 to 0.36 a.p.f.u respectively.
allel to the main rock foliation (Fig. 3a,b). Epidote occurs as The An-content in albite is in the range 0–2%.
subidiomorphic to idiomorphic inclusions and porphyroblasts. Small bi-
otite flakes coexist with secondary chlorite (Fig. 3b). Lawsonite, ob- 5.1.3. Metabasites
served only in calc-schists, is included in epidote and albite (Fig. 3c).
5.1.3.1. Phengite. The Si content ranges from 3.166 to 3.553 a.p.f.u., the
4.2.2. Metabasites celadonite component from 32.6 to 62.2%, the paragonite from 2.7 to
The overall mineral assemblage is: sodic-amphibole + chlorite + 11.0% and the pyrophyllite component is up to ~14.0% (Fig. 4,S4b).
phengite + albite ± biotite ± titanite ± stilpnomelane ± quartz ± Part of iron is in a trivalent state substituting Al as indicated by the Si
I. Baziotis et al. / Lithos 324–325 (2019) 439–453 443

Fig. 2. (a,b) Optical microscope and (c-f) scanning electron microscope images of the LTU schists. (a,b) Optical microscope and (c-f) scanning electron microscope images of the LTU
metabasites. The main and oblique foliation is given as straight dashed white and black lines, respectively.

vs. Altot and (Fe2++Mg) vs AlVI relations. Furthermore, the core-rim 5.1.3.2. Chlorite. The XMg [XMg = Mg/(Mg + Fe)] is in the range of 0.34–
analyses of zoned phengites show (from core to rim) a decrease of 0.40 and Si of 2.78–3.10 a.p.f.u., being richer in the daphnite component
Si from 3.72 to 3.166 a.p.f.u., an increase of AlIV from 0.603 to 0.723 compared to chlorite in the schists (Fig. 5).
and of AlVI from 1.592 to 1.646 a.p.f.u., an increase of Fe2+ from 0.162
to 0.201 and a decrease of Mg from 0.302 to 0.256 a.p.f.u.. Such a chem- 5.1.3.3. Biotite. Biotites are poor in titanium (Ti = 0.035–0.089 a.p.f.u.),
ical zonation is connected with increases of the muscovite and while Si ranges from 5.713 to 5.968 a.p.f.u., AlIV and AlVI from 2.032 to
ferromuscovite components. 2287 and 0.530 to 0.961 a.p.f.u., respectively. The XFe is in the range
0.46–0.55.
444 I. Baziotis et al. / Lithos 324–325 (2019) 439–453

Fig. 3. (a,b) Optical microscope and (c-f) scanning electron microscope images of the LTU schists. (a,b) Optical microscope and (c-f) scanning electron microscope images of the LTU
metabasites.

5.1.3.4. Ca-amphibole. The Ca-amphibole composition ranges from actin- Fe-/Mg-hornblende in the rim. However, actinolite also forms rims
olite to ferro-hornblende (see amphibole classification IMA, Leake et al., around pargasitic or actinolitic hornblende. In these zoned crystals
1997, 2004, Mogessie et al., 2004; Fig. 6). The NaB is up to 0.586 a.p.f.u., five types of zones have been identified (from core to rim).
the AlVI varies from 0.013 to 1.175 and AlIV from 0.090 to 1.602 a.p.f.u.,
the XMg changes from 0.406 to 0.799 and the XFe is up to 0.968. Some
analyses plot in the Ca-Na-amphibole field, and in particular in the 5.1.3.5. Na-amphibole. The Na-amphibole occurs as inclusions in garnet,
ferro-winchite and winchite fields. Their NaB is up to 1.291 a.p.f.u., the epidote, albite, and as residual crystals in Mg-hornblende. Their compo-
XMg ranges from 0.405 to 0.577 and the XFe is up to 0.338. The most sition ranges from Fe-glaucophane to glaucophane (Fig. 6, S5), with NaB
common zonation in the Ca-amphibole is from actinolite in the core to in the range of 1.411–1.898 a.p.f.u, XMg of 0.363–0.610 and XFe is up to
I. Baziotis et al. / Lithos 324–325 (2019) 439–453 445

5.2. UTU

5.2.1. Schists

5.2.1.1. Na-amphibole. The Na-amphibole ranges from Mg-riebeckite to
glaucophane (Fig. 6). The NaB is in the range of 1.398–1.980 a.p.f.u.,
XMg = Mg/(Mg + Fe+2) of 0.503–0.767 and XFe = Fe+3/(Fe+3 + Al)
is up to 0.801.

5.2.1.2. Phengite. Phengite has a Si content in the range 3.157–3.581 a.p.f.
u., celadonite 8.5–52.9%, pyrophyllite up to 21% and paragonite up to 7%
(Fig. 4,S4). Part of the iron is ferric, because many analyses plot below
the tschermakitic line in the Si vs. Altot and above the same line in the
(Fe+2 + Mg) vs. AlVI diagram. Finally, many analyses satisfy the crite-
rion of Mg + Fetot N Si-6, due to the presence of ferric iron substituting
Al in octahedral sites.

5.2.1.3. Chlorite. The X Mg [XMg = Mg/(Mg + Fe)] is in the range
0.69–0.73 and the Si content ranges from 3.01 to 3.49 a.p.f.u.
Chlorite is rich in the clinochlore (53–69%) and daphnite compo-
nents, and poor in amesite, due to limited tschermakitic substitution
[AlIVAlVISi−1(Mg,Fe)−1](Fig. 5).

5.2.1.4. Epidote-Clinozoisite. Epidote displays a chemical zonation with
an increase of Fe3+ and a decrease of Al from core to rim. Using the
pistacite component [XFe3+ = 100·Fe3+/(Fe3++Al)] there are two
groups; in the first XFe is up to 7.02%, while in the second it ranges
from 25.80 to 33.15%.

5.2.1.5. Lawsonite. Lawsonite is nearly pure in composition, with Al in
the range of 1.89–1.92 a.p.f.u. and Fe3+ from 0.04 to 0.07 a.p.f.u.

5.2.1.6. Stilpnomelane. Stilpnomelane has a homogeneous compo-
sition. The Al 2O 3 content ranges from 5.32 to 5.64 wt%, FeO
Fig. 4. Ternary plots for Ms-Cel-Prl showing the tschermakitic and pyrophyllitic
substitutions of LTU (a) and UTU (b) micas from Penteli. Mineral abbreviations:
from 19.32 to 19.83 wt% and MgO from 12.66 to 12.98 wt%. Only
Ms.: muscovite, Cel: celadonite, and Prl: pyrophyllite. the K 2O content is highly variable from 0.55 to 2.36 wt%. The X Fe
[XFe = Fe2+/(Fe2++Mg)] is relatively constant (0.46–0.47).

0.255. The Na-amphibole displays four different zones in AlVI and AlIV 5.2.2. Metabasites
(from core to rim) shown in Table S12.
5.2.2.1. Na-amphibole. The composition of Na-amphibole ranges
5.1.3.6. Epidote-clinozoisite. Epidote-clinozoisite porphyroblasts are from crossite to glaucophane (Fig. 6). The NaB is in the range of 1.851–
compositionally homogeneous. However, some grains show a slight zo- 2.000 a.p.f.u, the XMg (Mg/Mg + Fe) of 0.605–0.760 and the XFe3+
nation with an increase of Fe3+ and a decrease of Al from core to rim. (Fe3+/Fe3++AlVI) is up to 0.400. We have observed four different
However, we have observed the opposite zonation, too. The pistacite types of zones based on variations of AlVI, AlIV, NaB and (Na + K)A, as
component [100·Fe+3/(Fe+3 + Al)] varies considerably between sam- shown in Table S1.
ples in a range of 3.06–22.09%.
5.2.2.2. Phengite. The K-rich white mica in metabasite from the UTU cor-
5.1.3.7. Pumpellyite. Pumpellyite has Al2O3 content ranging from 23.83 to respond to phengite. The Si content is in the range 3.154–3.745 a.p.f.u.
25.87 wt%, FeO* from 3.13 to 5.58 wt% and MgO from 2.07 to 3.32 wt%. The paragonite component is up to 13% with Na up to 0.133 a.p.f.u.
MnO is highly variable from 0.01 to 2.41 wt%, and Al↔Fe3+ substitution The celadonite component ranges from 9.2 to 59.9%, while the pyro-
is limited. In contrast, more extensive Fe↔Mg substitution is indicated phyllite component indicates vacancies in dodecahedral occupancy
by a strong negative correlation of Fe* and Mg. with SiIV excess in the range of 10.1–24.0% (Fig. 4,S4). Furthermore,
part of the iron is in ferric form; this is indicated in plots of phengites
5.1.3.8. Garnet. Garnets are zoned with an increase of almandine and a in the space Si vs. Altot and (Fe2++Mg) vs. AlVI, where most grains
decrease of spessartine from core to rim. The Mg content is low, up to plot towards higher Fe2++Mg from the ideal 1:1 due to the presence
0.056 a.p.f.u. We have measured two garnet core-rim profiles from the of Fe3+. Also, the phengites have Mg + Fetot N Si-6 due to Fe+3↔Al sub-
metabasite sample PE1 (Fig. 7). In the first, grossular and spessartine de- stitution in octahedral occupancy.
crease, while almandine increases from the core to the rim; in the sec-
ond, grossular and almandine increases from the core to the rim. 5.2.2.3. Chlorite. Chlorite is relatively Al-poor with limited tschermakitic
substitution [AlIVAlVISi−1(Mg,Fe)−1] (Fig. 5). The XMg is in the range
5.1.3.9. Stilpnomelane. Stilpnomelane is generally homogeneous in com- 0.53–0.77 and Si of 2.70–3.07 a.p.f.u. In one metabasite sample, we ob-
position. The Al2O3 content is in the range of 6.09–6.50 wt%, FeO of served an association of Cr-rich and Fe-rich chlorites. The Cr-rich chlo-
26.1–26.8 wt%, MgO of 6.21–7.20 wt% and K2O of 0.81–1.13 wt%. The rites have XMg in the range 0.73–0.97 and Si 2.77–3.15 a.p.f.u. The Cr
XFe [Fe2+/(Fe2++Mg)] is relatively high, ranging from 0.67 to 0.70. content is variable from 0.35 to −1.74 wt%.
446 I. Baziotis et al. / Lithos 324–325 (2019) 439–453

Fig. 5. Ternary plots for (a, c) Ame-Clin/Daph-Sud and (b, d) Sud-Clin-Daph showing the tschermakitic, di-tri-octahedral and iron-magnesium substitutions of LTU (a, b) and UTU (c,
d) chlorites from Penteli. In (e) Si vs. XMg plot showing different chemistry for LTU and UTU chlorites. (f) Ternary Mg-Fe-Mn plot for chloritoid. on the Mineral abbreviations: Ame:
amesite, Clin: clinochlore, Daph: daphnite, Sud: sudoite and Ctd: chloritoid.

6. Zoning, reactions and p-t changes of zoning were observed in chloritoid: 1) an increase of XMg towards
the rim and 2) an increase of XFe towards the rim. The former can be as-
The observed compositional variations and zoning of some minerals sociated with growth during prograde metamorphism, and the latter
played a key role in the responsible metamorphic reactions, which can with decompression and cooling during retrograde metamorphism.
be interpreted in the context of the inferred ambient P-T conditions, Garnet records a decrease of the spessartine and an increase in the gros-
and the related geodynamic environment. sular components from core to rim, which can indicate formation dur-
ing a pressure increase. The low pyrope content (0.1–2%) suggests
formation at a relatively low temperature.
6.1. LTU

6.1.1. Schists 6.1.2. Metabasites
Mineral assemblages of the schists change systematically with bulk The Ca-amphibole of the metabasites records the prograde path as
composition: garnet, as the mineral with the lowest XMg coexists with indicated by the formation of actinolite around pargasitic amphibole,
the most Fe-rich chlorite, followed by the assemblages: pg-ctd, ctd-chl i.e. a decrease of AlVI from 1.175 to 0.058 a.p.f.u. and of AlIV from 1.602
and pg-chl towards more magnesian bulk compositions. The Al-poor to 0.120 a.p.f.u. Further progress along the prograde path is recorded
schists are represented by the assemblage chl-KF (cf. Proyer, 2003). by actinolite inclusions in albite and hornblende formation around ac-
Furthermore, the decrease in the celadonite and an increase in the mus- tinolite, i.e. an increase in NaB and of AlVI from 0.225 to 0.407 a.p.f.u.
covite components from core to rim in white mica indicates either de- and AlIV from 0.150 to 0.259 a.p.f.u. indicates an increase of temperature.
compression or temperature increase at constant pressure. Two types The replacement of hornblende by actinolite (AlIV from ~0.58 to 0.41 a.p.
I. Baziotis et al. / Lithos 324–325 (2019) 439–453 447

Fig. 6. Amphibole chemistry from LTU (a,b) and UTU (c,d) of Penteli. A compositional profile is also shown for AlIV vs. AlVI (e) and (Na + K)A vs. NaB (f) for amphibole from LTU.

f.u. and AlVI from ~0.43 to 0.25 a.p.f.u.) indicates decompression with a
synchronous decrease of temperature.
The Na-amphibole in metabasites has a zonation profile that also re-
cords part of the prograde and retrograde paths. In particular,
glaucophane growth around actinolite (AlVI increases from ~0.6 to
1.6–1.8 a.p.f.u. with contemporaneous increase of NaB from ~0.2 to
~1.4 a.p.f.u. and a decrease of AlIV from ~0.7 to ~0.2 a.p.f.u.) indicates
an increase of temperature and pressure. A temperature decrease and
slight pressure increase is also suggested by the replacement of Fe-
hornblende by actinolitic hornblende (AlIV from ~0.84 to 0.67 a.p.f.u.
and AlVI from ~0,57 to 0,45 a.p.f.u.), and the presence of glaucophane
in the rims. The subsequent replacement of glaucophane by actinolitic
hornblende (AlIV ~0.55 a.p.f.u. and NaB ~0.25 a.p.f.u.) was likely due to
a temperature increase during decompression. Other grains show a
gradual change from glaucophane to actinolite, e.g. by an AlVI decrease
from ~1.5–1.7 a.p.f.u. (core) to ~0.4–0.6 a.p.f.u. (rim), also due to a tem-
Fig. 7. Garnet rim-rim profiles for a metabasite (sample PE1) from the LTU of Penteli. perature increase.
448 I. Baziotis et al. / Lithos 324–325 (2019) 439–453

6.2. UTU the subduction path. Conversely, the matrix minerals that define
the main foliation of the rock formed at P of 0.5–0.87 GPa and T of
6.2.1. Schists 420–480 °C, suggesting heating during exhumation.
In a complex Na-amphibole profile, the glaucophane component in-
creases from the core (AlVI ~1.3 a.p.f.u.) to an intermediate zone (AlVI 7.1.2. Graphite thermometry
~1.4 a.p.f.u.) and is then replaced by riebeckitic amphibole towards We have applied the RSCM method following the approach of Rahl
the rim (AlVI ~0.4 a.p.f.u.). et al. (2005). The T, R1 and R2 parameters of the calibrated samples
Other amphiboles show mainly a decrease of AlVI from ~1.3 (core) to are best fitted using a second order non-linear polynomial function of
~0.3 a.p.f.u. (rim) with contemporaneous increase of AlIV from ~0.2 the form:
(core) to ~0.3 a.p.f.u. (rim) and a drop in NaB from ~1.97 (core) to 1.57
a.p.f.u. (rim); this zonation is interpreted as due to a pressure decrease
T ðin °CÞ ¼ 737:3 þ 320:9  R1–1067  R2–80:638  R12
at rather constant temperature. The NaB may be low, since many Na-
amphibole rims plot in the Mg-riebeckite field (Fig. 6), suggesting
bulk composition control. The R1 (D1/G)H ranges between 3.22 and 0.12 and the R2 [D1/(D1
+ D2 + G)A] between 0.73 and 0.10; both ratios decrease with temper-
6.2.2. Metabasites ature. The R1 decreases continuously up to T 600 °C, whereas the R2
Na-amphibole in metabasites shows mainly an increase in the increases above ~350 °C.
glaucophane component towards the rim, indicating a pressure in- The RSCM from the schists of the LTU indicates two groups of tem-
crease. In particular, AlVI increases from ~1.2 (core) to ~1.6 a.p.f.u. perature. In the first, the ratios R1 and R2 are in the range of 0.85–1.37
(rim) with a contemporaneous decrease of AlIV (from~ 0.08 as far and 0.29–0.6, respectively, while in the second group the values are
down as 0.01 a.p.f.u.). 0.29–0.87 and 0.29–0.59. The estimated temperatures are 360–433°C
and 452–499 °C, respectively (Table 1). The lower T group concerns
the calcitic schists, whereas the higher the paragonite−/chloritoid-
7. P-T results bearing schists.

7.1. LTU 7.1.3. Chlorite-chloritoid thermometry
This empirical thermometer is based on Fe\\Mg exchange between
7.1.1. Thermobarometric calculations based on the multi-equilibrium chlorite and chloritoid (Vidal et al., 1999). Three different groups
method (MEM) of temperature have been estimated: 306–364 °C, 359–487 °C and
Peak and retrograde P-T conditions were calculated from the compo- 510–621°C (Table 4). These groups are texturally divided into two cate-
sitions of mineral phases that are close or in contact, and considered to gories; the first group (lower T) related to the chlorite-chloritoid pairs
have been stably coexisting in the schists and metabasites. We used that lie oblique to the main foliation, while the second and third groups
pairs of chlorite-phengite, chlorite-chloritoid, triplets of chlorite- (mid- and high-T) are defined by the minerals that formed in the main
phengite-paragonite, and of chlorite-phengite-chloritoid as equilibrium foliation of the rock (Fig. 2). The range of 306–487 °C is in accordance
assemblages. To derive peak metamorphic conditions, we used core com- with the T values estimated using the independent methods of MEM
positions, and for retrogression rim compositions. Because of the exis- and graphite thermometers (Fig. S7). The lower temperatures are con-
tence of complex amphibole zonal patterns, indicating a complex P-T sistent with those estimated from the chlorite-chloritoid pairs that
history, these conditions should be regarded as tentative, but they still equilibrated near the peak of metamorphism. The extremely high T
provide robust snapshots of the ambient pressures and temperatures re- are ascribed to disequilibrium.
corded by the rocks during their tectono-metamorphic evolution. The
thermodynamic dataset and solid-solution properties are from the 7.1.4. Phengite barometry
TWEEQU Ver. 2.02 (Berman, 1991; updated database of Berman, 1988). The phengite geobarometers were applied to the mineral assemblage
The P-T conditions were calculated using a multi-equilibrium method phengite + biotite + K-feldspar + quartz (Massonne and Szpurka,
based on the assumption of local equilibrium between the chosen, adja- 1997: MS97; Parra et al., 2002a: P02) (Table 5). In the first barometer
cent, non-reactive minerals (Parra et al., 2002a, 2002b; Rimmelé et al., (MS97), experimental work was undertaken in the systems K2O-MgO-
2005; Vidal and Parra, 2000). The method and reactions are the same as Al2O3-SiO2 (KMAS) and K2O-FeO-Al2O3-SiO2 (KFAS) with H2O in excess,
in Willner et al. (2004) and Willner (2005). The solid-solution models and the authors applied the results to the KFAS+H2O system in the T
are referenced in Table 2 and the results are given in Table 3. range 150–550 °C and P up to 2.8 GPa. In the second geobarometer by
The pairs and triplets that are oblique to the main foliation of the Parra et al. (2002a), the thermodynamic data and solid solution proper-
schists indicate conditions of P 0.97–1.12 GPa and T 326–370 °C. One ties were calibrated for the systems KMASH (H: H2O), KFASH, KFMASH,
group of minerals from the metabasitic assemblage oblique to the KNASH (N: Na2O) for the T range 150–750 °C and P 0.05–3.0 GPa. The
main foliation give higher pressures (1.3–1.4 GPa) and lower tempera- inferred conditions for each geobarometer overlap the respective T and
tures (250–300 °C) indicating conditions that were close to the end of P range of the Penteli rocks, thus we were able to apply each of these
temperature-dependent geobarometers.
Table 2
The phengites from the Penteli schists suggest two groups of pres-
Sources of solid solutions and thermodynamic data used to estimate the multi-equilibrium
conditions. sure, based on the maximum Si content for the T values of 400 °C and
450 °C, which represent the average estimations from the RSCM. The
Solid solution Thermodynamic data
first P group ranges from 0.64 to 0.90 GPa (MS97) and 0.74–1.05 GPa
Amphibole Dale et al. (2000), Wei and Powell Holland and Powell (1998) (P02), while the second P group ranges from 0.36 to 0.53 GPa (MS97)
(2003), White et al. (2003)
and 0.48 to 0.67 GPa (P02). The phengites from the orthogneisses indi-
K-white mica Parra et al. (2002a, 2002b) Berman (1988, 1991)
Chlorite Holland et al. (1998), Vidal et al. Berman (1988, 1991), cate also two pressure groups; the first P group ranges from 0.66 to
(1992, 2001, 2005) Holland et al., 1998 0.82 GPa (MS97) and 0.76 to 0.93 GPa (P02), while the second P group in-
Chloritoid Vidal et al. (1999, 2001) Berman (1988, 1991) dicates 0.93–1.10 GPa (MS97) and 0.97–1.15 GPa (P02). The phengites
Epidote Holland and Powell (1998) Holland and Powell (1998) from the metabasites indicate a pressure range of 0.67–0.99 GPa
Plagioclase Newton et al. (1980) Berman (1988, 1991),
(MS97) and 0.92–1.05 GPa (P02). All pressures should be regarded as
Holland et al., 1998
minimal, because biotite was absent from the observed assemblage.
I. Baziotis et al. / Lithos 324–325 (2019) 439–453 449

Table 3
Average estimated invariant points from the LTU and UTU of Penteli.

Sample Rock type P (GPa) T ( ͦC) Chl Ctd Phg Pg Amph Ep/Czo Pl/Ab

LTU
11-03-04-1 Schist 0.98 326 + +
11-03-04-2 Schist 0.65 480 + + + +
11-03-04-3 Schist 0.97 370 + + +
11-03-05-1 Schist 0.56 470 + + + +
11-03-05-2 Schist 0.54 416 + + + +
11-03-05-3 Schist 1.12 352 + + +
11-03-05-4 Schist 0.97 410 + + +
11-03-05-5 Schist 0.96 435 + + +
11-03-06-1 Schist 0.85 446 + + +
11-03-06-2 Schist 0.87 468 + + +
11-03-06-3 Schist 0.81 481 + + +
11-03-06-4 Schist 0.73 478 + + +
11-03-06-5 Schist 0.72 468 + + +
PenA-1 Metabasite* 1.05 393 + + + + +
PenA-2 Metabasite* 0.89 391 + + + + +
PenA-2 Metabasite* 1.18 327 + + + + +
PenB-1 Metabasite* 1.05 350 + + + + +
PenB-2 Metabasite* 1.36 243 + + + + +

UTU
020801 Schist⁎ 0.81 298 + + + + +
020801 Schist⁎ 0.82 301 + + + + +
020801 Schist⁎ 0.90 307 + + + + +
020801 Schist⁎ 0.74 286 + + + + +
020801 Schist⁎ 0.70 279 + + + + +
020802 Schist⁎ 0.51 265 + + + +
020802 Schist⁎ 0.52 269 + + + +
020802 Schist⁎ 0.58 274 + + + +
020802 Schist⁎ 0.69 278 + + + +
020802 Schist⁎ 0.61 282 + + + + +
040816 Metabasite⁎ 0.78 298 + + + +
040816 Metabasite⁎ 0.82 307 + + + +
040816 Metabasite⁎ 0.87 311 + + + +
040816 Metabasite⁎ 0.51 287 + + + +
040816 Metabasite⁎ 0.49 276 + + + +
040816 Metabasite⁎ 0.52 277 + + + +

*: Estimated invariant point based on reactions 1–4:
6czo + 7qtz + 11gln + 10Fe-cel → 22ab + 3 Mg-cel + 2dph + 7 ms + 6tr (1).
6czo + 7qtz + 11gln + 7 Mg-cel → 22ab + 2clin + 7 ms + 6tr (2).
dph + 5 Mg-cel → 5Fe-cel + clin (3).
30czo + 35qtz + 55gln + 35Fe-cel → 110ab + 7dph + 3clin + 35 ms + 30tr (4).

7.2. UTU estimated to be 0.7–0.9 GPa at a T of 279–307 °C, whereas the retro-
grade P-T conditions were calculated to be 0.5–0.7 GPa and 260–278
7.2.1. The MEM method °C. In the metabasites, the MEM was applied to the equilibrium between
The MEM method was applied to the schists to study the equilibrium amphibole, chlorite and phengite, but only the retrograde conditions
between amphibole, epidote, chlorite, and phengite. The peak P was were recorded at P 0.49–0.82 GPa and 276–311 °C. The variation in P-
T conditions indicates coeval re-equilibration at peak conditions, while
retrogression took place at different times.
Table 4
Temperatures obtained from chlorite-chloritoid pairs from schists of LTU of Penteli. 7.2.2. Graphite thermometry
The study of RSCM from the carbon-bearing schists near Marathona
Sample lnKd T( ͦC)
Lake indicates that the rocks were metamorphosed at a low grade. The
110,304-1 2.36 320
ratios R1 and R2 are in the range of 2.10–2.92 and 0.58–0.71, respec-
110,304-2 2.44 306
110,304-3 2.13 364 tively (Table 1). The corresponding temperature estimates are in the
110,305-1 1.45 543 range of 252–343 °C. There is considerable compositional variation
110,305-2 1.22 629 even within one sample, with up to 50 °C variation in calculated
110,305-3 1.44 548 temperature.
110,305-4 1.72 461
110,305-5 1.85 428
110,305-6 1.72 461 8. Discussion
110,305-7 1.85 428
110,305-8 1.68 474 8.1. Metamorphic evolution
110,305-9 1.87 422
110,305-10 2.16 359
110,306-1 1.77 449 8.1.1. LTU
110,306-2 1.85 427 The mineral assemblages and mineral chemistry of the
110,306-3 1.74 456 orthogneisses of the LTU at Penteli indicate that HP/LT metamorphism
110,306-4 1.73 459 was followed by a greenschist facies overprint. The minimum pressure
110,306-5 1.73 459
of ~1.0 GPa (at 300 °C) was constrained using the Si-in-phengite
450 I. Baziotis et al. / Lithos 324–325 (2019) 439–453

Table 5
Estimated pressures based on Si-in phengite after application of geobarometers of
Massonne and Szpurka (1997) and Parra et al. (2002a) for the schists, metabasites and
gneisses from the LTU of Penteli.

Sample Rock type Massonne and Szpurka Parra et al.
(1997) (2002a)

T in °C 350 400 450 400 450

11-03-04-1 Schist 5.3 6.5 7.7 7.4 9.2
11-03-04-2 Schist 1.1 2 3 2 3
11-03-04-6 Schist 2.3 3.3 4.5 3.5 5.1
11-03-04-8 Schist 5.9 7.1 8.6 8.3 10.1
11-03-04-9 Schist 4 5 6.2 6 7.7
11-03-04-10 Schist 6.2 7.4 9 8.8 10.5
11-03-04-12 Schist 5.4 6.4 7.6 7.3 9.1
11-03-04-1 Schist 3.7 4.9 5.5 5.5 6.9
11-03-04-15 Schist 2.5 3.5 4.7 4 5.5
11-03-04-17 Schist 3 4.1 5.3 5.1 6.7
11-03-04-21 Schist 3.1 4.2 5.4 5.2 6.8
11-03-05-8 Schist 1.5 2.5 3.7 3 4.5
11-03-05-9 Schist 1.1 2 3 1.9 2.9
11-03-05-26 Schist 2.6 3.6 4.8 4.8 6.5
11-03-06-3 Schist 1.2 2.2 3.4 2.1 3.1
11-03-06-7 Schist 1.5 2.5 3.7 3 4.5
11-03-06-12 Schist 1.1 2 3 1.9 2.9
11-03-06-14 Schist 5.4 6.7 8.1 7.6 9.4
78-1 Schist 5.4 6.4 7.6 7.6 8.7
78-4 Schist 2.7 3.7 4.9 5 6.6
78-7 Schist 1.4 2.4 3.6 2.1 3.1
MCS-6 Schist 2.7 3.7 4.9 5 6.6
MCS-39 Schist 2.5 3.5 4.7 4.7 6.4
MCS-40 Schist 3 4.1 5.3 5.1 6.7
MCS-42 Schist 1.2 2.2 3.4 2.6 4.1
Amp48 Metabasite 5.4 6.6 7.8 7.5 9.3
Amp84 Metabasite 3.8 5 5.6 5.6 7
Amp85 Metabasite 1.5 2.5 3.7 3 4.5
Amp90 Metabasite 6.7 8.2 9.9 9.2 10.5
Amp99-rim Metabasite 1.1 2 3 1.9 2.9
Amp100-core Metabasite 4.1 5.1 6.3 6.1 7.8
Amp103 Metabasite 5.3 6.3 7.5 7.4 9.2
97P9-1-rim Gneiss 4.4 5.8 7.1 6.6 8.4
97P9-2 Gneiss 5.2 6.6 8.2 7.6 9.3
97P9-4-core Gneiss 4.6 5.8 7.3 6.7 8.5
97P9-5-core Gneiss 5 6.4 8 7.5 9.2 Fig. 8. P-T paths for the LTU and UTU of Penteli based on our thermodynamic data. P-T
97P9-6 Gneiss 5.1 6.5 8.1 7.5 9.2 constraints for the LTU and UTU of Penteli based on local scale equilibria. Peak, and
97P9-7 Gneiss 4.6 5.8 7.3 6.7 8.5 retrograde P–T conditions were calculated with the TWEEQU Ver. 2.02 (Berman, 1991;
97P9-8-rim Gneiss 4.5 5.9 7.2 6.7 8.5 updated database of Berman, 1988) from the compositions of mineral phases that are in
PE5-7 Gneiss 7.4 9.1 10.8 9.4 11.2 close contact and considered to be stably coexisting. The average error for T is ~50 °C
PE5-8 Gneiss 7.5 9.2 10.9 9.5 11.3 and ~2 kbar for P. For more details see “Thermobarometric calculations based on the
PE5-9 Gneiss 5.9 7.4 9.1 8.2 10 multi-equilibrium (MEM) method”. The solid-solution models used are listed in Table 2.
PE5-10 Gneiss 6 7.5 9.2 8.3 10.1 The three rectangles correspond to the T ranges estimated from the RSCM method. Also,
PE5-11 Gneiss 6 7.5 9.2 8.3 10.1 P-T paths or Lavrion metabasites (Baziotis et al., 2009), Sifnos eclogites from
PE5-12 Gneiss 6 7.5 9.2 8.3 10.1 Schmädicke and Will (2003), Evia blueschists (Katzir et al., 2000) and Syros from
PE5-13 Gneiss 7.5 9.2 10.9 9.5 11.3 Laurent et al. (2018). Dotted boundaries are from Evans (1990). Abbreviations are as
PE5-14 Gneiss 7.6 9.3 11 9.6 11.4 follows: PA: pumpellyite-actinolite facies, GS: greenschist facies, A: amphibolite facies,
PE5-15 Gneiss 7.3 9 10.7 9.3 11.1 E: eclogite facies, EBS: epidote-blueschist facies, LBS: lawsonite-blueschists facies AEA:
PE5-16 Gneiss 6.6 8.2 9.9 7.6 9.3 albite-epidote-amphibolite facies.
PE5-17 Gneiss 7.6 9.3 11 9.7 11.5
PE5-18 Gneiss 5.4 7 8.4 7.8 9.5
PE5-19 Gneiss 5.2 6.6 8.2 7.6 9.3 and the presence of zoned calcic-amphiboles in the matrix of the
PE5-20 Gneiss 6 7.5 9.2 8.3 10.1
metabasic rocks. Additional constraints of the exhumation path are sug-
gested by the multi-equilibria between chlorite-phengite, chlorite-
phengite-chloritoid and chlorite-chloritoid in metapelite, and by
geobarometer. The temperature of 300 °C was obtained from the MEM graphite thermometry (based on RSCM) at ~0.6 GPa and 452–499 °C
results of phengites that were oriented oblique to the main foliation of (Fig. 8). The LTU rocks were decompressed and continuously heated
the rock. Τhe observed high Si-values in phengite are also common in during their exhumation from a depth of ~45 km up to ~18–20 km.
other high-pressure terranes, and in particular in rocks of the The decompression history is also “decoded” using the different group
blueschists facies (Bröcker et al., 2004; Carswell et al., 2000; Schmid of temperatures obtained using RSCM and P-T using MEM for calcitic
et al., 2000). Additional constraints suggested by the multi-equilibria vs. Pg-Ctd schists. In the latter case, the higher RSCM T, have been ob-
between chlorite-phengite, chlorite-phengite-chloritoid and chlorite- tained from the areas where the “meta-migmatites” occurred
chloritoid from the metapelites indicate a peak high-pressure of ~1.2– (Fig. 1B). Due to that, we may associate such higher T, with the case of
1.3 GPa at a T of 300 °C. Furthermore, the inclusions of glaucophane, re-heating the former migmatitic rocks, and possible kept a population
pumpellyite, clinozoisite, and actinolite in garnet from the metabasites of graphite former at higher T. Another scenario, which is related more
indicate that the HP event occurred within the glaucophane + with the tectonic evolution of the studied area, is associated with
pumpellyite stability field. Decompression was associated with a signif- the nappe formation during exhumation. The rocks being exhumed fol-
icant increase in temperature indicated by the absence of pumpellyite lowing similar geotherms, however, may preserve their original
I. Baziotis et al. / Lithos 324–325 (2019) 439–453 451

stratigraphy. Thus, such feature represents a mechanical discontinuity, ~30 km (Baziotis et al., 2017). If the UTU was heated at depth, or crossed
which is translated to different parts of the rock pile to reach different a warmer geotherm, actinolite would easily overprint the preexisting
depths within the lithosphere. Therefore, the observed Pg-Ctd assem- blue amphibole.
blage of the schist may record either deeper and/or hotter parts com-
pared to calcitic-bearing one. In order to verify the predominant 8.1.4. Correlation with the ACCB in the context of Aegean evolution
process, still required additional analyses in the field (e.g. deformation) Several models have been proposed to account for the tectono-
and in-the-lab (e.g. pseudosections, EPMA). metamorphic evolution of the Attic-Cycladic Crystalline Belt (Bonneau
and Kienast, 1982; Jolivet et al., 2010; Keiter et al., 2004; Laurent et al.,
8.1.2. UTU 2016; Ring et al., 2010; Roche et al., 2016). Models based on P-T evolu-
The UTU in the Penteli area has a much better preserved record of tion mainly include adiabatic decompression, either associated with
HP/LT metamorphism indicated by the presence of lawsonite and constant temperature and/or with cooling (e.g. Avigad et al., 1992;
glaucophane in metabasite and schist. The occurrence of lawsonite Baziotis et al., 2009; Katzir et al., 2000; Laurent et al., 2018; Matthews
and glaucophane indicates a prograde reaction at the expense of chlo- and Schliestedt, 1984; Schliestedt et al., 1994; Schmädicke and Will,
rite, pumpellyite, and albite at P-T conditions above the boundary 2003; Trotet et al., 2001a). Among these, the more recent advocate
between the pumpellyite-actinolite and lawsonite-blueschist facies rapid uplift of the ACCB, which would enable refrigeration during con-
fields. This represents a univariant reaction and using idealized tinuous exhumation from the blueschist/eclogite-facies of the Apulian
formulae for pumpellyite (Ca2MgAl2Si3O11(OH)2H2O), clinochlore microplate.
(Mg5Al2Si3O10(OH)8) and glaucophane (Na2Mg5Al2Si8O22(OH)2) can The P-T path of metabasic rocks from the Lavrion area is comparable
be defined as: with that of the main ACCB (Baziotis et al., 2009). Notably, the peak P-T
conditions of the Lavrion metabasic rocks are ~0.9 GPa and ~370 °C,
5 pump þ 5 clin þ 12 ab þ 2 qtz ¼ 6 gln þ 10 law þ 14 H2 O followed by a P-T trajectory similar to that of the remaining ACCB,
despite emergence from a shallower crustal level. The low geothermal
The presence of both lawsonite and glaucophane in the rock matrix gradient (10–12 °C/km) of the retrograde overprint is probably related
further suggests that the prograde path crossed the lawsonite- to exhumation in a fore-arc tectonic setting (Schmädicke and Will,
blueschist field following a very cold geotherm during both prograde 2003). Furthermore, in the southern part of Evian Island in the north-
and retrograde metamorphism. Also, the compositional zonation in am- west of the Cyclades, a P-T path inferred from blueschists is character-
phiboles from the UTU is a result of the inferred prograde metamorphic ized by a peak pressure of N1.1 GPa and T of ~400–450 °C followed by
path. This zonation is characterized by an increase of the AlVI and ΝaΒ cooling during decompression at a P b 0.8 GPa and T b 350 °C (Katzir
from the core to rim indicating a prograde increase of pressure. et al., 2000). For metabasalts on Kythnos Island, eclogitic metamor-
The MEM on chlorite-phengite pairs and chlorite-phengite- phism (P~1.6–1.8 GPa and T N 550 °C) was followed by epidote-
glaucophane triplets indicates a maximum P of ~0.7–0.9 GPa and a T blueschist recrystallization (P~0.8–1.0 GPa and T~400–450 °C), and
of ~310 °C. According to the RSCM, the temperatures were in the by later decompression with a slight decrease of temperature to
range 252–343 °C, with an average T of 308 °C. The MEM results indicate greenschist facies conditions (P b 0.7 GPa and T~350–400 °C), as pro-
that UTU was exhumed from a depth of ~30 km, followed by a non- posed by Schliestedt et al. (1994). For Sifnos eclogites, the metamorphic
isothermal trajectory to a pressure of ~0.5 GPa and T of ~260–270 °C history followed a clockwise with cooling during decompression P-T
(Fig. 8). This further demonstrates that during exhumation the UTU path (Fig. 8) with a pressure decrease from 2.2 to 1.2 GPa at 550–440
rocks passed from the lawsonite-glaucophane to the pumpellyite (−ac- °C (Trotet et al., 2001a, 2001b; Groppo et al., 2009; Dragovic et al.,
tinolite) stability field (Fig. 8). The preservation of the peak assemblage 2012). According to Trotet et al. (2001a, 2001b) and Schmädicke and
is attributed to the cold geotherm during retrogression or/and to the ab- Will (2003), the P-T path for Sifnos eclogites is characterized by cooling
sence of water infiltration (Baziotis et al., 2017). Even a minor fluid in- during decompression with peak metamorphic conditions at P~2.0 GPa
gress or internal dehydration would have led to an actinolite-bearing and T~550–600 °C. The P-T path for Syros rocks suggest peak P-T at ~2.2
assemblage in a post-blueschist field, but this is clearly absent from ± 0.2 GPa and T~530 ± 30 °C, and two-stage cooling with decompres-
the UTU rocks (Baziotis et al., 2009). sion delimited by isobaric heating at 1.0–1.2 GPa (Fig. 8). The P-T path of
the LTU rocks of Penteli indicates continuous heating during decom-
8.1.3. The role of amphibole to retrieve the geodynamic history of Penteli pression to a pressure of ~0.7–0.8 GPa followed by emergence from
Amphiboles in the Penteli metabasites of the LTU record distinct the peak temperature of ~480 °C along a cooling trajectory. In contrast,
changes in P-T conditions during their metamorphic evolution. The pro- the P-T conditions recorded for the UTU of the Penteli area were a bit
grade path is depicted by the increase in AlVI and NaB while AlIV de- cooler and less deep, emerging from a peak P~0.9 GPa and T~310–330
creases, which suggests that the formation of glaucophane rims °C. At a pressure of ~0.6 GPa, the two units (LTU, UTU) still record a dif-
around actinolites developed during ongoing subduction. Later replace- ference of ~200 °C in their temperature. However, due to the absence of
ment of glaucophane by actinolitic hornblende points to a temperature relevant age data, it is impossible to establish a precise common time-
increase during decompression. Furthermore, many of the amphibole frame for the two units.
zoning patterns indicate a retrograde pressure decrease and contempo- Several authors proposed that the ACCB was not formed by a single
raneous increase in temperature. In particular, the core-to-rim decrease burial and exhumation event with a single metamorphic peak, but by a
of AlVI indicates the replacement of glaucophane by actinolite or horn- series of high-pressure events followed by extension during which the
blende during a temperature increase. A complex compositional profile HP rocks were (partially) exhumed (Bröcker, 1990; Bröcker et al.,
of Na-bearing calcic amphibole is characterized by Fe-rich hornblende 1993; Bröcker and Enders, 1999; Bröcker and Keasling, 2006; Forster
or actinolitic hornblende in the core, an intermediate zone of Na-rich and Lister, 2005). Recently Laurent et al. (2018) proposed a three-
amphibole, and actinolite or actinolitic hornblende in the rim (Fig. 6). stage exhumation model: An early phase of syn-orogenic exhumation
This amphibole zonation is associated with a pressure-temperature de- within the subduction channel was followed by isobaric heating, and
crease (thick black line shown the retrograde part in Fig. 8). In one am- final cooling during extension and slab retreat. This scenario is similar
phibole profile, patchy glaucophane in the outer retrograde rim may be to that proposed for the Lavrion (Baziotis et al., 2009) area, with the ex-
ascribed to local kinetic phenomena rather than regional P-T increase. ception of the isobaric heating part which has not been observed in
In contrast, the amphiboles in metabasites of the UTU record the Lavrion P-T path. For the case of LTU from Penteli area (this study) it
prograde to peak metamorphic conditions. Glaucophane is the only am- is possible to suggest a similar model. Especially, the post peak T history
phibole in the rock matrix suggesting dry exhumation from a depth of is almost identical with the path proposed for the Syros rocks (see
452 I. Baziotis et al. / Lithos 324–325 (2019) 439–453

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