3 ANTIPAROS Kervekidis 2015 PDF
3 ANTIPAROS Kervekidis 2015 PDF
3 ANTIPAROS Kervekidis 2015 PDF
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Elias Kevrekidis, Karen St. Seymour, Stylianos Tombros, Degao Zhai, Jiajun Liu,
Dimitrios Zouzias
Abstract. The Agios Georgios argentiferous galena deposit on Antiparos island lies ~12 km from the Miocene Paros pluton and is
hosted by mineralized quartz veins in marbles of the Cycladic Blueschist Unit. Argentiferous galena and clear quartz were depos-
ited in the epithermal stage in veins armoured by higher temperature milky quartz. The Paros pluton is a mesozonal volatile-rich
tourmaline and Li-bearing muscovite leucogranite emplaced at ca. 700 °C and 4 – 5 kbars. Fluid inclusion microthermometry of
vein quartz yielded ore fluid temperatures from 130° to 400 °C, salinities from 4.8 to 15.7 NaCl wt. percent equivalent and pres-
sures of 100 to 135 bars. CO2-effervescence of the ore fluid at the high end of the temperature range is suggested by Raman data
along with CO2 clathrate formation. Closure and boiling and reopening of the mineralized quartz veins occurred between 240° to
290 °C. Raman spectroscopy of fluid inclusions showed significant contents of Cu2+ and SO42 – indicative of the mineralization and
of Li+, and B3+indicative of magmatic fluid contribution. Raman ratios, i.e., logO2/H2O indicate mixing with meteoric water. Stable
isotope analyses of vein quartz yielded δ18OH2O and δDH2O values of the hydrothermal fluid from 1.2 to 11.6 and –73.2 to – 52.4
per mil, respectively, and δ30Si from – 0.6 to 0.0 per mil. All are consistent with a dominant magmatic origin of ore fluids. The
physicochemical conditions of the ore deposition were pH = 3.6 – 5.5, logfS2 = – 9.7 to –7.3 and logfO2 = – 31.3 to – 34 for 330° and
210 °C and pressures 135 bars. The volatile–rich nature of the Paros pluton, the presence of granitophile elements such as Li+ and
B3+ in fluid inclusions in the vein quartz, the high salinities of the fluid inclusions, the initial high T (> 400 °C) of the mineralizing
event and the magmatic signature of stable isotopes in mineralized vein quartz suggest that mineralizing fluids were derived from
the leucogranite.
Key words: Paros leucogranite, Antiparos epithermal mineralization, fluid inclusions, Raman, stable isotopes
possible genetic link with the Paros leucogranite which is of a succession of Alpine nappes, overlying a Hercynian
located 12 km away. To achieve this objective we deter- meta-igneous basement which consists of gneisses and
mined the petrochemistry and mineral chemistry of the schists (Jolivet et al. 2010, Van Hinsbergen & Schmid
leucogranite, and estimated the physicochemical condi- 2012). These lithologies are intruded by Miocene plutons
tions of ore formation with the aid of fluid inclusion mi- (Altherr & Siebel 2002, Bolhar et al. 2010). On Paros,
crothermometry and Raman analyses, and stable isotope zircon U-Pb dating of ortho- and para-gneisses yield typi-
analyses of vein quartz. cal Hercynian igneous crystallization ages that range from
300 to 315 Ma (Engel & Reischmann 1998, Bargnesi et
al. 2013).
Regional geology The basement is overlain by the Cycladic Blueschist
Unit (CBU). The CBU represents lithologies of a Meso-
The islands of Antiparos and Paros are part of the Cy- zoic continental margin which comprises a Pre-Alpidic
clades Blueschist Belt located in the central Aegean basement, i.e., the Basal Unit (Avigad & Garfunkel 1991)
(Blake et al. 1981). The Cyclades Blueschist Belt consists overlain by a volcanosedimentary sequence (Bröcker &
Fig. 1. Geological map of Paros and Antiparos (Adapted from Kevrekidis 2013).
The Agios Georgios argentiferous galena deposit on Antiparos Island, Cyclades, Hellas 3
Fig. 2. Structural map of the Agios Georgios area (box in the inset) showing the anticline which concentrated the mineralizing fluids.
Schmidt nets of foliation and joints used by mineralizing fluids. A1 to A11 mark metalliferous veins.
Franz 2005). The CBU is locally overthrusted by the Up- part of Paros. Kinematic markers at the fault plane indi-
per Unit which is composed of ophiolites (Katzir et al. cate a top-to-the-NE sense of movement (Gautier & Brun
1996, Jolivet et al. 2010). 1994). The hanging-wall comprises part of the Upper Unit
The CBU has undergone at least two metamorphic composed of Pliocene sedimentary rocks and an ophiolite
events. The first was is dated between ~ 53 to ≤ 40 Ma, slice covered by Cretaceous limestones (Sánchez-Gómez
by 40Ar/39Ar radiometric data from white mica, with con- et al. 2002).
ditions equivalent to eclogite and epidote-blueschist fa- Antiparos and Paros are separated by a narrow graben
cies (Wijbrans & McDougall 1986 and 1988, Ring et and it is likely that these two are part of a former single
al. 2001). Metamorphic temperatures ranged from 450° island. The lithology of the two islands is almost identical
to 550 °C and the pressures were equal to 12 – 20 kbars (Figs. 1 and 2). Antiparos is dominated by CBU schists
(Ring et al. 2001). The second metamorphic event has and marbles, but, it has less marbles than Paros and is
been dated between ≥ 25 and ~12 Ma, by 40Ar/39Ar radi- completely devoid of basement gneiss (Figs. 1 and 2).
ometric data from muscovite (Keay et al. 2001, Bolhar On Paros an S-type leucogranite and pegmatitic dykes
et al. 2010). The temperatures during this event peaked intrude the entire sequence (Fig. 1, e.g., Thapsana site).
at 670° to 700 °C and pressures ranged from 4 to 7 kbars Antiparos displays no exposed granitic intrusions with the
(Wijbrans & McDougall 1986, 1988, Bröcker & Franz exception of a few pegmatitic dykes, of similar mineral-
2005). Greenschist-facies retrogression of the CBU rocks ogy to those on Paros, encountered during fieldwork in
partially overprinted and locally destroyed the high-pres- this study. Early Pliocene rhyolites occupy the southern
sure assemblages of the first metamorphic event (Mat- part of the island (Innocenti et al. 1982) (Fig. 2).
thews & Schliestedt 1984, Schliestedt & Matthews
1987). Miocene granitic intrusions were emplaced dur-
ing and immediately after the second metamorphic event The Agios Georgios vein system
(Altherr et al. 1982, Altherr & Siebel 2002). In Paros,
the intrusive event was dated at 15.5 ± 0.3 Ma based on The Agios Georgios vein system is hosted in biotite-mus-
238 206
U/ Pb radiometric data (Bargnesi et al. 2013). covite schists and marbles of the CBU (Tombros 2008,
Kevrekidis 2013). The main tectonic element in the area
of Agios Georgios is an open anticline (Fig. 2) whose axis
Geology of Antiparos and Paros plunges at shallow to moderate angles towards the SSE
(Kevrekidis 2013, Evans & Fischer 2012). Foliation dips
On Paros, the CBU consists of gneisses, amphibolites, towards WSW to SSE at shallow to moderate angles and
schists and marbles and the Upper Unit is composed of to ENE at moderate to steep angles. Formation of the anti-
meta-dolerites, marbles, calc-schists and phyllites (Papan- cline caused a decrease of lithostatic pressure in the axial
ikolaou 1980 and 2009, Gautier & Brun 1994, Sánchez- hinge zone, which may have drawn hydrothermal fluids
Gómez et al. 2002). A low angle ductile to brittle normal into the area of Agios Georgios (Evans & Fischer 2012,
fault is exposed at the top of the CBU in the northeastern Kevrekidis 2013). The tectonic domain in the Agios Geor-
4 E. Kevrekidis et al.
gios area consists of a conjugate system of NE-trending Crustification is present in quartz veins which are
sinistral and NW-trending dextral strike-slip faults. There more than 10 cm wide. Two zones of crustification, re-
are two main systems of joints. The first trends NNW and ferred to here as Type A and B bands, have been dis-
dips steeply towards the ENE, while the second trends tinguished based on mineralogy, grain size and texture.
WNW and dips SSW at moderate angles. The generalized sequence of vein crustification (Table
The Agios Georgios vein system consists of eleven 10), from the vein margins to the center is: (Type A): fine-
steeply dipping quartz veins (Fig. 2). Both marbles and to medium-grained drusy milky quartz (> 70 vol.%) with
schists are cut by two generations of syntaxial veins, angular to subrounded fragments of marble and schist.
an older NE-trending set filled with milky quartz and a This band contains also epidote, ankerite, calcite, chlo-
younger set of clear quartz veins trending NW (Fig. 2). rite, sericite and rare orthoclase, albite, as vein filling,
These veins developed parallel to the planes of folia- and (Type B): medium- to coarse-grained clear quartz,
tion and joints, and also along the lithological contacts smithsonite (≤ 20 vol.%), barite (≥ 30 vol.%) and fluo-
between marble and schist, forming extensive stock- rite, which display well-developed open-space filling and
works. Milky quartz veins range up to 80 cm in width, dogtooth textures.
and contain sphalerite, pyrite and chalcopyrite (10 vol.%). Alteration haloes occur around quartz veins, with
The clear quartz veins form tension gashes up to 50 cm widths ≥ 30 cm, developed as discontinuous borders and
in width within the center of the milky quartz veins, and linear selvages in marbles and schists of the CBU. The
they contain galena (≤ 10 vol.% with Ag 800 – 2000g/t) as alteration assemblages define two successive zones: an
the main ore mineral (Tombros 2008, Kevrekidis 2013). inner milky quartz-epidote zone with ankerite, dolomite,
Table 1. Chemical analyses of Paros leucogranites and a mafic inclusion (2). Major elements in wt.%, trace elements in ppm. Below detec-
tion limit: (b.d.). Not determined: (n.d.).
wt.% 1 2 3 4 5 6 7 8 9 10 11 12
SiO2 70.64 55.02 67.67 75.4 74.04 72.35 67.91 70.7 71.2 68.5 70.44 78.04
TiO2 0.31 0.53 0.75 0.03 0.06 0.28 0.57 0.48 0.33 0.6 0.31 0.07
Al2O3 14.86 19.88 14.38 14.93 14.87 15.42 16.7 15.5 15.6 16.2 15.83 12.87
Fe2O3 2.17 4.82 3.91 0.53 0.63 1.72 3.02 2.62 2.25 3.37 1.94 0.71
MnO 0.04 0.05 0.05 0.08 0.01 0.03 0.03 0.02 0.03 0.33 0.04 0.02
MgO 0.56 0.78 1.23 0.08 0.16 0.37 0.86 0.79 0.7 1.07 0.37 0.08
CaO 1.99 3.5 4.56 1.21 1.1 1.94 2.74 2.6 2.08 2.94 2.27 0.86
Na2O 3.48 4.91 2.97 4.24 3.26 3.6 3.51 3.07 4.25 3.24 4.47 3.24
K2O 4.36 6.34 2.89 3.87 5.24 4.19 3.84 4.21 2.56 3.43 4.15 4.36
P2O5 0.11 0.03 0.19 0.04 0.05 0.09 0.17 0.14 0.11 0.18 0.09 0.03
LOI 0.64 4.16 0.89 0.3 0.28 0.39 0.54 0.48 0.65 0.52 0.51 0.44
Total 99.15 99.99 99.49 100.31 99.41 99.98 99.34 100.16 99.82 99.58 99.9 100.27
Sc 3 b.d. 6 6 5 8 9 6 3 6 6 11
V 8 51 33 10 10 17 24 21 20 20 13 8
Cr 20 n.d. n.d. 8 b.d. 24 2 b.d. b.d. b.d. 4 1
Co 2 4 6 b.d. b.d. 3 6 33 43 42 2 b.d.
Ni 20 n.d. n.d. b.d. b.d. 0 1 b.d. b.d. 1 0 0
Cu 80 20 10 b.d. b.d. b.d. 1 b.d. b.d. 4 b.d. b.d.
Zn 60 60 70 17 21 34 50 49 60 67 43 39
Ga 23 n.d. n.d. 20 20 22 23 19 23 24 22 15
Rb 185 84 140 214 207 214 159 170 127 151 190 164
Sr 244 354 413 68 159 242 383 367 254 412 253 43
Y 28 5 13 28 36 11 15 15 18 16 9 55
Zr 191 1676 422 57 47 169 318 315 203 346 179 49
Nb 9 64 19 8 24 9 9 10 13 11 10 8
Ba 717 1376 445 87 438 552 976 992 422 875 552 110
Th 17.2 2.5 18.3 8 13 14 19 20 13 17 11 9
Pb 48 5 29 n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d.
The Agios Georgios argentiferous galena deposit on Antiparos Island, Cyclades, Hellas 5
Table 2. Rare Earth analyses of Paros leucogranites and a mafic inclusion (Numbers of specimens as in Table 1).
ppm 1 2 3 4 5 6 7 8 9 10 11 12
La 38 9.7 65 10 10 17 35 34 21 31 21 13
Ce 71 17 126 18 10 32 74 62 42 59 37 33
Pr 7.54 n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d.
Nd 26 64 50 8 2 9 24 23 18 19 12 15
Sm 4.7 1.2 9.4 n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d.
Eu 0.83 0.43 1.25 n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d.
Gd 3.3 n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d.
Tb 0.5 0.2 1.1 n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d.
Dy 2.6 0.9 5.9 n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d.
Ho 0.5 n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d.
Er 1.4 n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d.
Tm 0.2 n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d.
Yb 1.3 0.7 2.7 n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d.
Lu 0.8 0.11 0.39 n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d.
LaN/LuN 0.54 0.99 1.89 – – – – – – – – –
LaN/YbN 2.16 1.02 1.78 – – – – – – – – –
Y/Ho 28 – – – – – – – – – – –
Fig. 3. Compositional features of the Paros leucogranite whole-rock samples. a – Most samples of the Paros leucogranites plot in the
peraluminous field on the SiO2-A/CNK diagram (A/CNK equals molar Al2O3/(CaO+Na2O+K2O), metaluminous and peraluminous fields
from Maniar & Piccoli 1989); b –In the Y vs. Nb discrimination diagram samples from the Paros leucogranite plot in the Volcanic Arc and
Syncollisional fields (VAG: Volcanic Arc Granite, syn-GOLG: Syn-Collisional Granite, ORG: Orogenic Granite and WPG: Within Plate
Granite, fields from Pearce et al. 1984); c – Paros leucogranites display LREE-enrichment. Plagioclase fractionation is depicted by the
distinct negative Eu anomaly on these profiles. Normalization values from Nakamura (1977).
6 E. Kevrekidis et al.
Fig. 4. The composition of minerals in the Paros leucogranite. a – Amphiboles evolve from these of magnesio-hornblendes towards horn-
blende-actinolite (Act: Actinolite, Tsch: Tschemarite, Hbl: Hornblende, Tsi: Tetrahedral silicon, fields from Leake 1978); b – Biotite plots
near the divide between biotite and phlogopite (fields from Guidotti 1984). c – Feldspar compositions from the leucogranite are mostly
andesine-oligoclase plagioclases, with oligoclase rims. K-feldspars plot near the orthoclase apex.
calcite, rhodochrosite, siderite, pyrite, sericite, chlorite Superprobe 8600-L instrument equipped with wavelength
and albite; and an outer clear quartz-barite-fluorite zone dispersive spectrometers (WDS) with EDS and SEM facil-
with galena, rare kaolinite and Mn- and Fe-oxides and hy- ities. Electron microprobe work on petrographic polished
droxides. thin sections was carried-out at an acceleration voltage of
15 kV, a beam current of 20 nA and a beam diameter of 5
μm at 20s counting times. Online ZAF corrections were
Analytical methods done utilizing the CAMECA software. Shorter counting
times (10s) were used to avoid devolatilization of the al-
A total of twelve samples of Paros leucogranite have been kalies from the feldspars. Natural and synthetic feldspars,
analyzed for major and trace elements (Table 1) including diopside, rutile, chromite, hematite, spessartine, fluorite
REE (Table 2). Analyses were carried out by ACTLABS and vanadinite were used as standards. For the feldspars,
laboratory at Ancaster, Ontario, Canada, by ICP and ICP/ the detection limits are: 0.03 wt.% for Si, 0.05 wt.% for
MS methods using code 4Litho research. Detection limits Ti, 0.02 wt.% for Al, 0.04 wt.% for Fe, 0.02 wt.% for Mg,
are 0.001 wt.% for TiO2 and MnO and 0.01 wt.% for the 0.03 wt.% for Ca, 0.07 wt.% for Na, 0.03 wt.% for K and
rest of major elements; 1 ppm or better for Sc, Be, Co, Ga, 0.03 wt.% for Ba. For biotite and amphibole, the detection
Nb, Sb, Cs, Hf, Ta, Tl, Bi, Sn, Th, U and W; 2 ppm for Sr, limits are: 0.03 wt % for Si, 0.06 wt.% for Ti, 0.06 wt.%
Y and Rb; 3 ppm for Ba and 4 ppm for Zr; 5 ppm for V for Cr, 0.03 wt.% for Al, 0.05 wt.% for Fe, 0.05 wt.% for
and Pb; 10 ppm for Cu, 20 ppm for Cr and 30 ppm for Zn. Mn, 0.02 wt.% for Mg, 0.04 wt.% for Ca, 0.03 wt.% for
Detection limits are 0.05 ppm for Pr, Eu, Tm and Lu and Na, 0.02 wt.% for K, 0.09 wt.% for F and 0.01 wt.% for
0.1 ppm for the rest of the REE. Cl.
Mineral chemistry was determined by electron mi- Operating conditions for sulfide minerals were an
croprobe at McGill University, Montréal, using a JEOL accelerating voltage of 20 kV and a beam current of
The Agios Georgios argentiferous galena deposit on Antiparos Island, Cyclades, Hellas 7
Table 3. Microprobe single point chemical analyses of amphibole from the leucogranite of Paros (from sample 1 of Table 1).
wt.% 1 2 3 4 5 6 7 8 9 10
SiO2 47.07 46.53 45.69 47.13 48.23 48.80 48.82 49.79 44.87 45.58
TiO2 0.90 0.98 1.14 0.94 0.81 0.73 0.72 0.64 1.07 1.15
Al2O3 7.33 6.90 7.77 6.60 5.88 5.46 5.29 4.69 8.44 8.01
FeO 14.78 14.73 14.96 14.37 13.71 13.63 13.57 13.27 15.39 15.17
Cr2O3 0.08 0.05 0.06 0.10 0.02 0.08 0 0.01 0.29 0.09
MnO 0.76 0.96 0.84 0.90 0.96 0.93 0.99 0.99 0.80 0.83
MgO 13.33 13.30 12.70 13.56 14.10 14.40 14.44 14.89 12.34 12.54
CaO 11.61 11.47 11.53 11.55 11.52 11.59 11.65 11.57 11.63 11.51
Na2O 1.48 1.45 1.54 1.34 1.25 1.16 1.13 1.05 1.35 1.46
K2O 0.78 0.77 0.89 0.74 0.61 0.55 0.55 0.47 0.94 0.90
Total 98.13 97.13 97.12 97.23 97.09 97.33 97.16 97.37 97.12 97.24
Number of ions on the basis of 23 oxygen atoms
Si 6.95 6.95 6.85 7.01 7.14 7.20 7.21 7.31 6.74 6.83
Al 1.05 1.05 1.15 0.99 0.86 0.81 0.79 0.69 1.26 1.17
Fe3+ 0 0 0 0 0 0 0 0 0 0
Ti 0 0 0 0 0 0 0 0 0 0
Sum T 8.00 8.00 8.00 8.00 8.00 8.00 8.00 8.00 8.00 8.00
Al 0.22 0.17 0.22 0.17 0.17 0.14 0.13 0.12 0.24 0.24
Cr 0.01 0.01 0.01 0.01 0 0.01 0 0 0.03 0.01
Fe3+ 0 0 0 0 0 0 0 0 0 0
Ti 0.10 0.11 0.13 0.11 0.09 0.08 0.08 0.07 0.12 0.13
Mg 2.93 2.96 2.84 3.01 3.11 3.17 3.18 3.26 2.77 2.80
Fe2+ 1.73 1.76 1.81 1.71 1.63 1.60 1.61 1.55 1.84 1.82
Mn 0 0 0 0 0 0 0 0 0 0
Ca 0 0 0 0 0 0 0 0 0 0
Sum C 5.00 5.00 5.00 5.00 5.00 5.00 5.00 5.00 5.00 5.00
Mg 0 0 0 0 0 0 0 0 0 0
Fe2+ 0.09 0.09 0.07 0.08 0.07 0.08 0.07 0.08 0.10 0.08
Mn 0.10 0.12 0.11 0.11 0.12 0.12 0.12 0.12 0.10 0.11
Ca 1.81 1.79 1.83 1.81 1.81 1.81 1.81 1.80 1.80 1.82
Na 0 0 0 0 0 0 0 0 0 0
Sum B 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00
Ca 0.02 0.04 0.02 0.03 0.02 0.03 0.03 0.02 0.08 0.03
Na 0.42 0.42 0.45 0.39 0.36 0.33 0.32 0.30 0.39 0.42
K 0.15 0.15 0.17 0.14 0.12 0.10 0.10 0.09 0.18 0.17
Sum A 0.59 0.61 0.64 0.56 0.49 0.46 0.46 0.41 0.66 0.63
30 nA. Twenty seconds counting time was used for all ele- sample was also analyzed for δ34S in the latter lab. Oxy-
ments, except Ag (100s) and As (50s). Pyrite, sphalerite, gen was released from milky and clear quartz using the
galena, chalcopyrite, Ag-metal, Au-metal, diopside, spes- BrF5 extraction technique of Clayton & Mayeda (1963)
sartine, stibnite and synthetic CoNiAs were used as stand- and Friedman & O’neil (1977). Hydrogen was released by
ards. Detection limits in wt.% were: 0.042 for Ag, 0.054 thermal crushing from fluid inclusions and structurally
for Zn, 0.048 for Fe, 0.061 for Sb, 0.022 for S, 0.066 for bound waters to minimize fractionation effects as their
As, 0.072 for Cu, 0.037 for Au, 0.046 for Co, 0.207 for Pb, water contents were ≥ 0.2 wt.% (≥ 1000 μmol H2 per mg
0.049 for Ni, 0.036 for Cd and 0.031 for Mn. sample) (De Groot 2004). In order to optimize our re-
Out of the thirteen mineralized quartz samples from sults, we have used areas for analyses in the quartz sam-
the Agios Georgios veins, three were analyzed solely for ples examined under the microscope which primary fluid
δ18Ο at the Stable Isotope Research Laboratory, Univer- inclusions predominate. Silicon isotopes was measured
sity of Indiana, USA. The remaining ten samples were using the SiF4 technique of Ding (2004). Sulfur was re-
also analyzed for δ18Ο, δD and δ30Si at the Chinese Acad- leased as SO2 after the method of Fritz et al. (1974). The
emy of Geological Sciences, Beijing, China. A chalcocite isotopic ratios are reported in standard δ notation per mil
8 E. Kevrekidis et al.
relative to SMOW for oxygen and hydrogen, NBS-28 for spar-plagioclase-quartz-magnetite, S-type leucogranite
silicon and CDT for sulfur. Analytical precision was bet- (Fig. 3a) , with dioritic enclaves (Table 3). The overall
ter than ± 0.2 per mil for δ18Ο, ± 1 per mil for δD, ± 0.1 per peraluminous character of the Paros leucogranite is also
mil for δ30Si and ± 0.2 per mil for δ34S. reflected in its accessory mineralogy of sillimanite, tour-
Lead isotopic compositions of four vein quartz sam- maline, Li-muscovite, apatite and garnet. The tectonic dis-
ples, representing sulfide grains in the veins, were deter- crimination diagram of Pearce et al. (1984) places the Pa-
mined at the Chinese Academy of Geological Sciences, ros leucogranite in the volcanic arc environment (Fig. 3b).
Beijing, China using an England Nu Plasma High Res- The amphibole (Table 3) is magnesio-hornblende and
olution Multi-Collector-Inductively Coupled Plasma- biotite (Table 4) plots near the phlogopite composition
Mass Spectrometer (MC-ICP-MS). Long-term repeated (Figs. 4a and 4b). The plagioclases have oligoclase to
measurements of lead isotopic ratios of standard NBS andesine and the alkali-felspars orthoclase compositions
981 yielded 206Pb/204Pb = 16.9397 ± 0.0111, 207Pb/204Pb (Table 5, Fig. 4c).
= 15.4974 ± 0.0089, and 208Pb/204Pb = 36.7147 ± 0.0262 The trends in major and trace element variations
(errors are reported at ± 2 σ). suggest the leucogranite magma evolved via fractional
Microthermometric measurements were obtained on crystallization of plagioclase (Figs. 5d, e, g, p and REE
doubly polished quartz wafers 50 –100 μm thick, using a profiles), amphibole (Fig. 5a, b, c, d, h, r), titaniferous
LINKAM MDSG600 heating-freezing stage coupled to a magnetite and ilmenite (Fig. 5a, c, h, j, l, m, r), apatite
ZEISS microscope in the Department of Earth Sciences (Fig. 5d, i), zircon (Fig. 5j) and probably allanite (Fig. 5a,
and Resources, China University of Geosciences, Beijing, d, g, q), and retention of biotite and alkali feldspar (Fig
China. Up to 30 inclusions were examined in each sam- 5e, f). The indicated kink in Nb concentration at 70 wt.%
ple. Temperatures were measured with an alumel-chromel SiO2 is attributed to uptaking of Nb in the zircon structure
thermocouple, and the readings were calibrated with syn- (Fig. 5l). The Paros leucogranite was emplaced at pres-
thetic inclusions at – 56.6 °C (triple point of CO2), 0.0 °C sures of 1.4 to 4.1 kbars or crustal depths of 4.1 to 8.8 km
(melting point of ice), and +374.1 °C (critical point of (Table 9) based on pressures calculated from the Altotal in
H2O). Measurements were accurate to within ± 0.1 °C and hornblende geobarometer (Schmidt 1992), which was ap-
freezing-heating rates were maintained between 0.2° and plied on ten different zoned hornblende crystals from the
5 °C/min. Microthermometric data were reduced using same thin section (Table 3). Depths were derived from
the software FLINCOR, for the system H2O-NaCl, em- these pressures based on the average lithostatic gradient
ploying the equations of Brown & Lamb (1989), Zhang & of 3 kbar/km. Application on the Ti-in-biotite (Table 4)
Frantz (1990) and Darling (1991). geothermometer of Henry et al. (2005) and the Al-in-
Fluid inclusion laser Raman spectroscopy analyses hornblende geothermo-barometer of Vyhnal et al. (1991)
were carried out in the Beijing Research Institute of Ura- utilizing the experimental calibrations of Schmidt (1992),
nium Geology, Beijing, China, using a Renishaw RM-
provided magmatic temperatures of 657° to 738 °C and
2000 Raman spectroscopy microscope. The same quartz
676° to 759 °C, respectively. Additionally, magnetite-il-
wafers prepared for microthermometry were also used for
menite pairs in the same thin section (Table 6) provided a
Raman analyses. The Raman work was done before heat-
similar spread of magmatic temperature values.
ing runs in order to avoid losses from decrepitation. The
The experimental work of Scaillet et al. (1995) ar-
instrument recorded peaks in the range of 100 – 4000 cm–1
gues that the leucogranite liquidus for these pressures is
full-band with a resolution of 1– 2 cm–1, and the laser beam
≤ 700 °C depending on the volatile content. The Paros
spot size was about 1 μm. The inclusions were analyzed
leucogranite magma was water saturated as shown by the
for the most common gases, monoatomic and polyatom-
presence of pegmatites and miarolitic cavities. For such
ic ions and molecules. Their relative concentrations (in
melts and at magmatic temperatures of ~700 °C the water
mol %) were calculated based on equations adopted from
content of the Paros leucogranite is estimated at 7 wt.%
Frezzotti et al. (2012) and the cross-sectional scattering
H2O following the methodology of Liu et al. (2005).
coefficients of Dhamelincourt (1979).
Therefore this is a granite rich in volatiles (-OH, B, F) a
composition reflected in its accessory mineralogy of Li-
Results rich muscovite, tourmaline and apatite which establishes
its potential for hydrothermal ore deposition. A summary
The leucogranite of Paros of the inferred conditions of emplacement of the Paros
leucogranite in given in Table 9. The distance of the Paros
The Miocene granitic intrusion of Paros is mainly a pluton from the Agios Georgios deposit is ~12 km, which
light grey hornblende-Li-rich muscovite-biotite-K feld- is comparable to the distance of 16 km between the Tinos
The Agios Georgios argentiferous galena deposit on Antiparos Island, Cyclades, Hellas 9
Fig. 5. Harker diagrams for major (wt.% ) and trace (ppm) elements. The trends (highlighted by hand-fit lines) are consistent with the evolu-
tion of the Paros leucogranite magmas via extensive crystal fractionation. See text for details.
10 E. Kevrekidis et al.
Table 4. Microprobe single point chemical analyses of biotite from the leucogranite of Paros (from sample 1 of Table 1).
wt. % 1 2 3 4 5 6 7 8 9 10 11
SiO2 36.95 36.14 36.19 36.59 36.83 36.64 35.14 36.09 35.30 37.04 37.32
TiO2 3.71 3.43 3.51 3.63 3.48 3.44 3.65 3.62 3.50 3.49 2.97
Al2O3 13.94 13.62 13.83 14.02 13.76 13.44 13.47 13.93 13.11 13.66 13.69
FeO 16.03 16.55 16.94 16.00 16.19 16.31 16.31 16.66 16.31 16.12 16.08
MnO 0.57 0.54 0.53 0.59 0.63 0.57 0.55 0.50 0.52 0.57 0.66
MgO 13.94 12.75 13.43 13.88 14.04 13.36 13.04 13.67 12.67 14.00 14.52
CaO 0.04 0.22 0.05 0.01 0.07 0.06 0.14 0.07 0.15 0.03 0.04
Na2O 0.20 0.66 0.49 0.19 0.19 0.34 0.48 0.36 0.68 0.18 0.15
K2O 9.95 9.31 9.61 9.83 9.83 9.58 9.59 9.73 9.27 10.06 10.09
Cr2O3 0.15 0 0.01 0.22 0.15 0.02 0 0 0 0.17 0.13
Total 95.49 93.22 94.59 94.95 95.17 93.76 92.48 94.64 91.52 95.33 95.64
Number of ions on the basis of 24 oxygen atoms
Si 5.84 5.87 5.80 5.82 5.85 5.90 5.78 5.78 5.85 5.87 5.89
Al IV 2.16 2.13 2.20 2.19 2.16 2.10 2.23 2.22 2.15 2.13 2.11
Total 8.00 8.00 8.00 8.00 8.00 8.00 8.00 8.00 8.00 8.00 8.00
Al VI 0.43 0.47 0.42 0.44 0.42 0.45 0.38 0.41 0.41 0.42 0.01
Ti 0.44 0.42 0.42 0.43 0.42 0.42 0.45 0.44 0.44 0.42 0.35
Fe2+ 2.12 2.25 2.27 2.13 2.15 2.20 2.26 2.23 2.26 2.14 0.09
Mn 0.08 0.07 0.07 0.08 0.09 0.08 0.08 0.07 0.07 0.08 3.42
Mg 3.28 3.09 3.21 3.29 3.32 3.21 3.20 3.26 3.13 3.31 0.01
Ca 0.01 0.04 0.01 0 0.01 0.01 0.02 0.01 0.03 0.01 0.05
Na 0.06 0.21 0.15 0.06 0.06 0.11 0.15 0.11 0.22 0.06 0.05
K 2.01 1.93 1.97 1.99 1.99 1.97 2.01 1.99 1.96 2.03 2.03
Cr3+ 0.02 0 0 0.03 0.02 0 0 0 0 0.02 0.02
Total 8.44 8.47 8.52 8.45 8.47 8.44 8.55 8.52 8.52 8.47 8.00
Table 5. Microprobe single point chemical analyses of feldspars Ore mineralogy and ore chemistry
from the leucogranite of Paros (from sample 1 of Table 1). Samples
1 to 5 are plagioclase and 6 is a K-feldspar.
Metallic and vein filling hydrothermal minerals formed
wt % 1 2 3 4 5 6 in three mineralizing Stages, two hypogene (I, II) and
SiO2 61.06 61.45 60.51 61.22 63.74 65.15 one supergene (III) (Table 10). High temperature ore
Al2O3 24.36 23.93 24.56 24.29 22.42 18.51 and gangue minerals (390° to 285 °C) such as chalco-
CaO 5.96 5.71 6.27 5.92 3.75 0.09 pyrite (Table 7), bornite, tetrahedrite, sphalerite, pyrite,
Na2O 7.79 7.95 7.58 8.03 9.45 2.30 pyrrhotite, and magnetite formed before closure of the
K2O 0.45 0.39 0.47 0.34 0.32 13.86
veins (Fig. 7). Euhedral pyrite (Table 8) contains up to
Total 99.62 99.42 99.38 99.80 99.67 99.90 0.67 wt.% As, 0.13 wt.% Zn and 0.14 wt.% Cu and sub-
Number of ions on the basis of 32 oxygen atoms hedral chalcopyrite up to 0.15 wt.% Zn (Table 7). Milky
Si 10.88 10.96 10.82 10.89 11.29 11.96 quartz is the main high temperature hydrothermal quartz
Al 5.11 5.03 5.17 5.09 4.68 4.00 being deposited together with calcite and ankerite during
Ca 1.14 1.09 1.20 1.13 0.71 0.02 the whole extent of Stage I. Epidote, sericite and chlorite
Na 2.69 2.75 2.63 2.77 3.25 0.82
also precipitated in Stage I.
K 0.10 0.09 0.11 0.08 0.07 3.25
Stage II ore minerals, including argentiferous ga-
Total 19.92 19.91 19.93 19.96 20.00 20.05
lena (Table 8), argentite, native Ag and Au formed after
re-opening of the hydrothermal conduits, i.e., after the
temperature interval of 245° to 130 °C (Fig. 7). The main
leucogranite and the Panormos Bay polymetallic Au-Ag gangue mineral of Stage II is clear hydrothermal quartz
telluride mineralization with which it is thought to be as- with lesser smithsonite (Table 10). Barite is ubiquitous in
sociated (Tombros et al. 2007, 2010). Stage II and probably denotes the localized inundation of
The Agios Georgios argentiferous galena deposit on Antiparos Island, Cyclades, Hellas 11
Table 6. Microprobe single point chemical analyses of magnetite from the leucogranite of Paros (from sample 1 of Table 1).
wt % 1 2 3 4 5 6 7 8 9 10
SiO2 0.04 0.02 0.05 0.05 0.05 0.10 0.04 0.02 0.03 0.06
TiO2 0.07 0.42 0.45 0.05 0.59 0.15 0.03 0.11 0.13 0.13
Al2O3 0.13 1.17 0.20 0.17 0.59 0.48 0.12 0.15 0.21 0.31
FeO 30.76 29.92 30.31 30.65 30.43 30.48 30.78 30.75 30.61 30.49
Fe2O3 68.36 66.50 67.37 68.13 67.65 67.75 68.41 68.35 68.04 67.76
Cr2O3 0.33 0.45 0.68 0.28 0.50 0.27 0.20 0.41 0.46 0.19
MnO 0.14 0.17 0.195 0.15 0.41 0.12 0.13 0.14 0.14 0.17
MgO 0.02 0.04 0.03 0.02 0.01 0.03 0.01 0 0 0.04
Nb2O5 0.01 0 0.04 0 0.03 0.01 0 0.03 0 0
ZnO 0 0.65 0 0.04 0.05 0.12 0 0.05 0.08 0.06
V2O3 0.33 0.32 0.36 0.35 0.28 0.30 0.31 0.38 0.37 0.03
Total 100.18 99.66 99.68 99.88 100.60 99.79 100.04 100.37 100.06 99.25
Number of ions on the basis of 32 oxygen atoms
Fe3+ 15.82 15.39 15.66 15.80 15.55 15.70 15.85 15.79 15.76 15.80
Si 0.01 0.01 0.02 0.01 0.02 0.03 0.01 0.01 0.01 0.02
Ti 0.02 0.10 0.10 0.01 0.13 0.03 0.01 0.03 0.03 0.03
Al 0.05 0.42 0.07 0.06 0.21 0.17 0.04 0.05 0.07 0.11
Nb 0 0 0.01 0 0 0 0 0 0 0
V 0.08 0.08 0.09 0.09 0.07 0.07 0.08 0.09 0.09 0.01
Cr 0.07 0.10 0.15 0.06 0.11 0.06 0.04 0.09 0.10 0.04
Total 16.05 16.10 16.11 16.04 16.10 16.08 16.04 16.06 16.07 16.02
Fe2+ 7.91 7.69 7.83 7.90 7.78 7.85 7.92 7.89 7.88 7.90
Mn 0.03 0.04 0.05 0.04 0.11 0.03 0.03 0.03 0.04 0.04
Mg 0.01 0.02 0.01 0.01 0 0.01 0.01 0 0 0.02
Zn 0 0.15 0 0.01 0.01 0.03 0 0.01 0.02 0.13
Total 7.95 7.90 7.89 7.96 7.90 7.92 7.96 7.94 7.93 7.98
Table 7. Microprobe single point chemical analyses of chalcopyrite from the metalliferous veins of Agios Georgios deposit, Antiparos
(same sample as in Table 8.).
wt % 1 2 3 4 5 6 7 8 9 10 11 12
Fe 30.1 30.06 30.28 29.74 30.76 30.45 30.34 30.29 30.06 29.93 30.54 29.81
Zn 0.06 0.05 0.06 0.06 0.10 0.04 0.15 0.09 0.04 0.09 0.02 0.02
Cu 34.31 34.32 34.25 35.05 33.70 33.99 34.00 34.45 34.57 34.71 34.28 34.53
Ni 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.01 0.00
Co 0.01 0.00 0.03 0.00 0.00 0.01 0.02 0.00 0.02 0.00 0.02 0.02
S 35.04 34.95 34.82 34.36 34.86 35.07 34.92 34.90 34.97 35.25 34.74 35.47
As 0.01 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.01 0.00
Total 99.54 99.38 99.44 99.21 99.42 99.56 99.42 99.73 99.66 99.98 99.62 99.84
Number of atoms
Fe 1.06 1.06 1.07 1.05 1.08 1.07 1.07 1.06 1.06 1.05 1.07 1.06
Zn 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
Cu 0.94 0.94 0.93 0.95 0.92 0.92 0.93 0.99 0.94 0.95 0.93 0.94
Ni 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
Co 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
S 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00
As 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
Total 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00
12 E. Kevrekidis et al.
Table 8. Microprobe single point chemical analyses of pyrite, Ag-galena and argentite from the metalliferous veins of Agios Georgios
deposit, Antiparos (same samples as in Table 7.).
wt % Pyrite Pyrite Pyrite Pyrite Pyrite Pyrite Galena Galena Galena Galena Argentite
Fe 46.88 46.77 46.53 46.03 46.22 46.72 0.02 0.05 0.01 0.05 0.03
Pb 0.00 0.00 0.00 0.00 0.00 0.00 83.51 84.54 86.00 86.15 0.25
Cu 0.07 0.07 0.09 0.10 0.14 0.09 0.09 0.19 0.19 0.28 3.24
Zn 0.00 0.02 0.02 0.02 0.13 0.03 0.00 0.00 0.00 0.00 0.00
Ag 0.00 0.00 0.00 0.00 0.00 0.00 2.90 1.17 0.26 0.17 82.19
Co 0.01 0.02 0.00 0.02 0.01 0.04 0.00 0.00 0.00 0.00 0.00
Ni 0.00 0.00 0.00 0.01 0.00 0.00 0.00 0.00 0.00 0.00 0.00
Sb 0.00 0.00 0.00 0.00 0.00 0.00 0.09 0.13 0.01 0.00 0.00
As 0.00 0.00 0.00 0.64 0.67 0.63 0.09 0.01 0.00 0.00 0.01
Te 0.00 0.00 0.00 0.00 0.00 0.00 0.01 0.03 1.19 1.66 0.89
S 53.43 53.30 52.81 53.80 53.39 53.04 13.25 13.83 12.49 11.67 12.52
Total 100.39 100.18 99.45 100.63 100.56 100.54 99.96 99.95 100.15 99.98 99.13
Number of atoms
Fe 1.00 1.00 1.00 1.00 1.00 1.00 0.00 0.01 0.00 0.00 0.00
Pb 1.00 1.00 1.00 1.00 1.00 1.00 0.94 0.96 0.99 0.98 0.00
Cu 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.01 0.01 0.02 0.13
Zn 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
Ag 0.00 0.00 0.00 0.00 0.00 0.00 0.06 0.03 0.00 0.00 1.87
Co 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
Ni 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
Sb 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
As 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
Te 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.02 0.03 0.02
S 2.00 2.00 2.00 2.00 2.00 2.00 1.00 1.00 0.98 0.97 0.98
Total 3.00 3.00 3.00 3.00 3.00 3.00 2.00 2.00 2.00 2.00 3.00
CO2 have V/V+L ratios between ~ 60 % and ~80 % and and consist of aqueous liquid+vapor+daughter crystals
are ellipsoidal in shape and may host CO2 clathrates, (iii) (Fig. 6). The presence of halite or calcite daughter crystals
Type S-L-V inclusions have filling percentages of ~30 % is a rare occurrence within the inclusions. The secondary
fluid inclusions belong solely into the L-V category and
are considerably poorer in the gaseous phase.
Table 10. Ore Paragenesis and crustification banding of hydrother- Final ice melting temperatures for the V-L and L-V
mal minerals from Agios Georgios deposit, Antiparos. inclusions in milky and clear quartz range from –11.7°
Bands A B to – 3.1 °C and – 8.4° to – 2.9 °C, respectively. These val-
Mineral stages Stage I Stage II Stage IΙΙ ues correspond to salinities of 5.4 to 15.7 and from 4.8 to
A
T (°C) 391-275 245-131 ≤ 100
12.2 wt.% NaCl equivalent (Fig. 7, Table 11). The melting
temperatures of clathrate in and L-L-V inclusions are be-
Milky quartz ▃▃▃▃▃▃▃▃▃
Clear quartz ▃▃▃▃▃▃
tween 4.5 ° and 6.1 °C, which indicates salinities of 6.9
Epidote ▃ to 9.3 wt.% NaCl equivalent (Fig. 7, Table 11) using the
Sericite ▃ equation of Darling (1991). The homogenization temper-
Chlorite ▃ atures for L-V and V-L fluid inclusions in milky and clear
Calcite ▃▃ quartz are between 275° and 408 °C and 131° to 245 °C,
Ankerite ▃▃▃▃ respectively (Fig. 7, Table 11). The L-L-V fluid inclusions
Smithsonite ▃▃▃ ▃▃▃▃ homogenized to liquid between 347° and 408 °C, whereas
Barite ▃▃▃▃
the CO2 subphases homogenized to liquid or vapor be-
Fluorite ▃
Pyrite ▃▃▃
tween 30.5° and 32.1 °C. The halite dissolution tempera-
Pyrrhotite ▃ tures (Thhalite ≥ Th) have been used to calculate the salinity
Magnetite ▃ of the ore fluid. These temperatures were ~ 346 °C which
Sphalerite ▃▃▃▃ correspond to 30.5 wt.% NaCl equivalent (Lecumberri-
Chalcopyrite ▃▃ Sanchez et al. 2012). In order to constrain the density and
Bornite ▃ pressure of entrapment of the fluid we have applied the
Tetrahedrite ▃▃ software FLUIDS (Bakker 2012) on the H2O-NaCl-CO2
Galena ▃▃▃▃▃▃▃
system. Their densities range from 0.75 to 0.91 g/cm3, re-
Argentite ▃
Native Au ▃
spectively. The high porosity and abundance of vugs in
Native Ag ▃ the marbles, the brittle character of the mineralized frac-
Covellite ▃ ▃▃▃▃ tures and the open-space filling textures of clear quartz
Anglesite ▃▃▃ veins suggest that the trapping pressures were closer to
Cerussite ▃▃▃ the hydrostatic pressure. The pressures for the L-V and
Chalcocite- ▃▃▃▃ V-L and S-L-V inclusions vary from ~100 to 135 bars.
Digenite
Goethite ▃▃▃▃ As suggested by Rhoedder (1984) and Goldstein &
Malachite ▃▃▃▃ Reynolds (1994) no pressure correction was applied to
Azurite ▃▃▃▃ the homogenization temperatures because evidence for
Pyrolusite ▃▃▃▃ CO2-effervescence suggests that the fluid inclusions were
A Temperatures obtained from fluid inclusions and various gase-
trapped along the CO2 solvus. Evidence for phase sepa-
ous- (e.g, H2S, CO2/H2S, CH4/CO2, CO2, H2 and CO2/N2) and ration includes the observed coexistence of L-L-V, L-V
liquid-phase geothermometers (e.g., adiabatic-Si, Na-Li and Na-K- and clathrate bearing inclusions along with L-V and V-L
Ca) (Tables 12 a and b).
Table 11. Fluid inclusion microthermometric measurement results from Agios Georgios deposit, Antiparos.
Sample Mineral N Phases Tmice Th Tmhalite/ Salinity
(°C) (°C) Tmclathate (wt. % NaCl equiv)
(°C)
AAG-3 Milky quartz (stage I) 23 L-V and V-L –11.7 to -3.3 275 to 400 – 5.4 to 15.7
AAG-3 Milky quartz (stage I) 3 L-L-V – 347 to 408 4.5 to 6.1 6.9 to 9.3
AAG-3 Milky quartz (stage I) 1 S-L-V –9.1 321 346 30.5
AAG-1 Clear quartz (stage II) 29 L-V –6.3 to -2.9 131 to 245 – 4.8 to 12.2
Abbreviation: Th = Homogenization temperature, Tm, ice = Final ice melt temperature and Tm = final salt melt temperature.
14 E. Kevrekidis et al.
Table 12 a. Gaseous phase compositions (in mol %) of individual fluid inclusions and calculated content ratios from Agios Georgios de-
posit, Antiparos.
Sample Mineral CH4C CO2B, C H2O O2 N2 H2SA, B H2 logCO2 logCO2/ logCO2/ logCO2 logO2/
/N2 CH4 H2O /H2S H2O
AAG-3 Milky quartz n.d. 7.56 92.2 n.d. n.d. n.d. 0.24 – – – 1.09 – –
AAG-3 Milky quartz n.d. 2.24 96.73 n.d. n.d. n.d. 1.03 – – – 1.64 – –
AAG-3 Milky quartz 0.05 11.21 86.71 0.02 0.01 0.04 1.89 3.05 2.35 – 0.89 2.45 – 3.64
AAG-1 Clear quartz 0.11 5.68 92.65 0.09 0.07 0.06 1.34 1.91 1.71 – 1.21 1.98 – 3.01
AAG-1 Clear quartz 0.07 17.2 82.51 0.05 0.04 0.05 0.08 2.63 2.39 – 0.68 2.54 – 3.22
Table 12 b. Liquid phase compositions (in ppm) of the same individual fluid inclusions and calculated content ratios from Agios Georgios
deposit, Antiparos.
Sample Mineral Si+2, A K+, C Al+3 B+3 Li+, B Ca+2, C Na+, B, C CO3 – 2 logNa+/ logK+/ logCa+2/ logLi+/
K+ Ca+2 Na+ Na+
AAG-3 Milky quartz 1020 103 96 72 6.5 134 11 0.4 – 0.97 – 0.11 – 0.11 – 0.23
AAG-3 Milky quartz 1370 88 76 n.d. n.d. 354 180 3.2 – 0.69 – 0.60 – 0.60 –
AAG-3 Milky quartz 1090 65 56 57 n.d. 105 1308 12.3 – 0.70 – 0.21 – 0.21 –
AAG-1 Clear quartz 670 20 n.d. n.d. n.d. 215 214 18.5 1.03 – 1.03 – 1.03 –
AAG-1 Clear quartz 950 250 174 69 1,7 192 13 24.6 – 0.28 – 0.89 – 0.89 – 0.88
In a sample obtained from milky and clear quartz were detected Li +1 and Mn2+of 6.5 and 1.7 and 75 and 89 ppm, respectively. Also in
milky quartz Ti2+ and Cu2+ and SO42 – were detected up to 1.3, 1.4 and 2.6 ppm, respectively.
We have used the adiabatic Si-A of Fournier & Potter (1982), the Na-LiB- of Fouillac & Michard (1981) and the Na-K-Ca geothermom-
eterC of Fournier & Truesdell (1973) for both milky and clear quartz. The log Ca + 2.06 values are positive and T ≥ 100 °C and so
Na
β = ¾.
12 b). The cation ratios logNa+1/K+1, logK+1/Ca+2, logK+1/ 345 °C. Stage II-clear quartz has deposited from 206° to
Mn+2and logLi+1/Na+1 for milky and clear quartz fluid in- 236 °C.
clusions range from – 0.97 to +1.03, –1.03 to +0.32, – 0.32
to +1.03, and – 0.89 and – 0.22, respectively. The logCa+2/
Mn+2 values were obtained only on clear quartz and range Isotopes
from – 0.87 to 0.46. Additionally, the logCO3 – 2/SO4 – 2 Oxygen, hydrogen and silicon isotopes
ratios in milky quartz are +0.33. The logNa+1/K+1 and
logK+1/Ca+2 ratios of the Antiparos ore fluid are identi- Oxygen and hydrogen isotope compositions were deter-
cal to the ones related to magmatic-dominated geothermal mined on the same samples of milky and clear vein quartz.
analogues (Giggenbach 1991). Also traces of Cu+2 and B+3 The δ18O values of milky quartz from band A range from
detected in the liquid phase support this hypothesis. 7.7 to 9.3 per mil. The measured δDH2O values from fluid
Based on the Raman results application on various gas- inclusion waters were – 61.2 to – 52.4 per mil (Table 13).
eous- (e.g., the H2S- and CH4/CO2- of Giggenbach 1991, Clear quartz veins (band B) display δ18O values of 6.5
the CO2/H2S- of Nehring & D’amore 1984 and the CO2-, to 12.1 per mil and δDH2O values from –73.2 to – 57.2 per
the H2- and the CO2/N2-geothermometers of Arnórsson mil. The corresponding δ18OH2O values of the ore fluids
& Gunnlaugsson 1985, Table 12 a) and liquid-phase geo- in equilibrium with milky quartz (based on temperatures
thermometers (e.g., the adiabatic Si- of Fournier & Pot- obtained from fluid inclusions, Table 11) range from 1.2 to
ter 1982, the Na-Li- of Fouillac & Michard (1981) and 2.8 per mil (Fig. 8). Also the δ18OH2O values of the miner-
the Na-K-Ca-geothermometer of Fournier & Truesdell alizing fluid in equilibrium with clear quartz range from
1973 (Table 12 b), has shown that stage I-milky quartz 5.4 to 11.6 per mil (Fig. 8). Lastly, a quartz sample of Pa-
has precipitated at temperatures ranging from 302° to ros leucogranite yielded δ18O values of 9.6 per mil. The
16 E. Kevrekidis et al.
Table 13. Stable and lead isotope data from the vein quartz of Agios Georgios deposit, Antiparos.
Sample Mineral T1 δ18OV-SMOW δ18ΟΗ2Ο δDH2O δ30SiNBS-28 206Pb/204Pb 207Pb/204Pb 208Pb/204Pb
corresponding δ18OH2O value of the ore fluids in equilib- position as all granites reported by Savage et al. (2012),
rium with Paros leucogranite was 5.0 per mil and δDH2O i.e., δ30SiNBS = – 0.23 ± 0.15 per mil.
values of – 66.7 per mil, at 400 °C (Table 13).
The obtained δ30SiNBS values of milky quartz veins are Lead isotopes
almost constant at – 0.5 to – 0.4 per mil (Fig. 9, Table 13).
Additionally, clear quartz veins display δ30SiNBS values Four whole rock lead isotope results were obtained from
which range from – 0.6 to 0.0 per mil (Table 13). The vein milky and clear quartz veins related to ore stages I and
quartz from Antiparos has the same silicon isotope com- II. Their 206Pb/204Pb, 207Pb/204Pb and 208Pb/204Pb ratios
The Agios Georgios argentiferous galena deposit on Antiparos Island, Cyclades, Hellas 17
are displayed in Table 13. We also show previously pub- in the data probably reflects closure of the vein system due
lished data from Stos-Gale et al. (1996) for comparison. to precipitation of milky quartz (Fig. 7). This effectively
Based on the 206Pb/204Pb versus 207Pb/204Pb uranogenetic deterred hydrothermal fluid circulation and further depo-
and the 206Pb/204Pb versus 208Pb/204Pb thorogenic plots sition, thus no or very few fluid inclusions were trapped
it is apparent that a most plausible source for lead is an during this period. When the fluid reaches a temperature
orogenic-setting pluton, i.e., the Paros leucogranite rather of ~ 240 °C an increase of pressure within the vein system
than leaching of Pb from the upper crustal Hercynian met- resulted in fracturing and reopening of the hydrothermal
amorphic basement (Fig. 9).
conduits which allows once again the free circulation of
the hydrothermal fluid. The ensuing decrease in pressure
may have caused boiling of the hydrothermal fluid which
Discussion
together with mixing and cooling enhanced deposition
Origin and evolution of the metalliferous of clear quartz and argentiferous galena. This is the main
hydrothermal fluid mineralization event (Stage II), which together with the
preceding Stage I characterize the deposit as “epither-
The fluid inclusion temperature vs. salinity diagram mal”. Deposition of hydrothermal quartz, as clear quartz,
(Fig. 7) suggests mixing between a high temperature continued until the fluid reached a temperature of ~130 °C
and high salinity fluid (possibly juvenile, i.e. intrusion
as depicted from primary fluid inclusions.
related) and a low temperature, low salinity fluid. The
We estimated the partial pressures of dissolved gases
trend of fluid inclusion compositions offers a strong argu-
based the Herny’s law and the results of Raman analy-
ment for mixing with meteoric waters. Fluid inclusions
with considerably higher salinity, have the same trapping ses, adopting Henry’s law coefficients from Henley et al.
temperature as fluid inclusions with much lower salinity (1984). The partial pressures of CH4, CO2, H2O, O2, N2,
(Fig. 7). This suggests that CO2-effervescence occurred in H2S and H2 are estimated as 0 to 1.16, 7.8 to 94.6, 24.8 to
the fluid possibly due to wall-rock interaction (Tombros 29.02, 0 to 0.54, 0 to 0.1, 0.13 to 0.31 and 0 to 0.1 bars. The
et al. 2007). total pressures of the dissolved gases in the ore fluid range
The episode of the hydrothermal mineralization on from 38.3 to 120.8 bars (for milky and clear quartz veins),
Antiparos island begins with hydrothermal fluid at a tem- which correspond to a depth of phase separation varying
perature of ~ 400 °C. Between ~ 240° and ~ 290 °C, a gap from ~450 to 1600 m.
18 E. Kevrekidis et al.
provide the necessary pathways for fluids as it becomes conclusions. The Agios Georgios mineralization event
apparent by the presence of quartz and pegmatites lit-par- was initiated at temperatures in excess of 400 °C based on
lit and cross-cutting veins which have been observed in fluid inclusion data, and the chain of mineralizing events
the field and of the Agios Georgios anticline resulting in can be described as follows:
the circulation and concentration of the metalliferous flu- 1) In the early stage the hydrothermal fluids with a pH of
ids in the area (Kevrekidis 2013, Evans & Fischer 2012 3.6 invaded marble host rocks in fractures in the hinge
and references therein). zone of the Agios Georgios anticline causing CO2 ef-
Substantial evidence for the predominantly magmatic fervescence which is indicated by the presence of CO2
origin of the Agios Georgios mineralizing fluids is de- clathrates and by Raman ratios i.e., log(CO2/CH4) and
rived from the stable isotope data. Magmatic values of log(CO2/H2O) in fluid inclusions in precipitating early
all granites for δ30SiNBS are – 0.23 ± 0.15 (Savage et al. milky quartz.
2012). The average value for the higher temperature milky 2) A sealing of the hydrothermal system in the tempera-
quartz of Antiparos is δ30Si = – 0.28 per mil with a range ture interval of ~240 to 290 °C, presumably due to quartz
from δ30Si = – 0.4 per mil and for clear quartz the aver- precipitation, is indicated by the gap in fluid inclusion
age δ30Si = – 0.34 per mil ranging between – 0.6 to 0.0. populations in this temperature interval.
However, the δ30Si values that are ≤ – 0.5 per mil may rep- 3) At temperatures below 240 °C, re-opening of the sys-
resent leached-out silicon derived from the CBU schists. tem presumably by fracturing and pressure release caused
The average sulphur isotopic value in Agios Georgios boiling of the fluid increase of the pH of the fluid and
chalcocites of δ34S =+4.1 ‰ is also well within the range deposition of clear quartz and argentiferous galena during
for magmatic sulphur (Seal 2006). The δ 18O values of the epithermal stage (240 –130 °C). The lower temperature
clear quartz and milky quartz yield calculated δ18OH2O fluids used the same conduits as the earlier ones and this
values of the hydrothermal fluid between +1.2 to +11.0 is displayed in veins where clear quartz tension gashes are
per mil, overlapping the magmatic range from ~+5 to +10 enveloped by milky quartz.
per mil (Hedenquist & Lowenstern 1994). From Fig. 8 it 4) The precipitation of the ore and accompanying miner-
becomes apparent that most of the clear quartz isotopic als was effectuated by T drop which was partly induced
values plot together with the Paros leucogranite within the by mixing with meteoric waters especially at the high end
“Magmatic Box”. Quartz samples from the alteration zone of the temperature spectrum.
around the veins plot mostly in the box of “Metamorphic The following lines of evidence point towards a coeval
Waters”, as expected due to wall-rock interaction. High- relationship between the Agios Georgios mineralization
temperature milky quartz samples plot between the mag- and the Paros pluton:
DD The pluton is a leucogranite rich in volatiles (-OH, F,
matic box and the “meteoric H2O” line. This can be ex-
plained by the fact that initially the plumbing system was B, P) and incompatible elements reflected in its ac-
more open and unarmoured, allowing fluids of magmatic cessory mineralogy of tourmaline, apatite and Li-rich
origin to mixing with meteoric waters. muscovite. Similar elements have been found in the
The alluded coeval relationship between the Paros leu- fluid inclusions in hydrothermal quartz by Raman
cogranite magma and the Antiparos mineralizing fluid is spectroscopy.
DD The stable isotope values of δ18O 34
consistent with many other results from this study. Fluid in- H2O, δD, δ SH2S and
clusion data reveal that mineralization was initiated at high δ30Si have close to magmatic values. Late clear quartz,
temperatures of ~ 400 °C. A magmatic contribution is sug- which was least mixed with meteoric waters since it
gested by the Raman evidence of Li, B and F in the hydro- was shielded by milky quartz veins, plots in the “mag-
thermal fluid (Table 12 b). Therefore, based on the grounds matic box” in a diagram of δ18OH2O versus δDH2O per
of the presented geological and geochemical arguments we mil.
DD Finally, the initial high temperature of the mineraliz-
suggest that the Paros leucogranite was the source for the
Agios Georgios, Antiparos mineralizing fluids. ing fluids (> 430 °C) supports the thesis that the source
of heat and ore fluid is the Paros pluton.
Conclusions
Acknowledgements
This study of hydrothermal mineralization in the quartz
vein-hosted argentiferous galena deposit at Agios Geor- We would like to thank Prof. Dr. Giannis Koukouvelas,
gios as well as of the composition and emplacement con- Prof. Dr. Sotirios Kokkalas and Dr. Dimitrios Spanos for
ditions of the Paros leucogranite reaches the following their invaluable suggestions and comments in the field of
The Agios Georgios argentiferous galena deposit on Antiparos Island, Cyclades, Hellas 21
structural geology, which vastly contributed in the im- De Groot, P. A. (2004): Handbook of stable isotope analytical tech-
provement of the manuscript. The comments of journal niques: Stable Isotope Geochemistry. – 6th Edition, Elsevier Sci-
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Authors’ addresses:
Elias Kevrekidis (corresponding author), Department of Geology, University of Patras, Rion, Patras, 26504, Greece. e-mail: kevrekidis@
upatras.gr
Karen St. Seymour, Department of Geology, University of Patras, Rion, Patras, 26504, Greece: e-mail: [email protected]
Stylianos Tombros, Department of Geology, University of Patras, Rion, Patras, 26504, Greece. e-mail: [email protected]
Degao Zhai, State Key Laboratory of Geological Processes and Mineral Resources, China University of Geosciences, 100083, Beijing,
China. / School of Earth Sciences and Resources, China University of Geosciences, 100083, Beijing, China. e-mail: zhaidgcugb@gmail.
com
Jiajun Liu, State Key Laboratory of Geological Processes and Mineral Resources, China University of Geosciences, 100083, Beijing,
China. / School of Earth Sciences and Resources, China University of Geosciences, 100083, Beijing, China. e-mail: [email protected].
cn
Dimitrios Zouzias, Department of Geology, University of Patras, Rion, Patras, 26504, Greece. e-mail: [email protected]