Strmić Palinkaš et al.: The evolution of the čanište epidote-bearing pegmatite, fyro Macedonia: evidence from mineralogical and geochemical features 423  Geologia Croatica 65/3 423–434 7 Figs. 5 Tabs. Zagreb 2012 The evolution of the čanište epidote-bearing pegmatite, Republic of Macedonia: evidence from mineralogical and geochemical features  Sabina Strmić Palinkaš1, Vladimir Bermanec1, Ladislav A. Palinkaš1, Blažo Boev2, Robert A. Gault3, Walter Prochaska4, Ronald J. Bakker4 1 Institute of Mineralogy and Petrology, Department of Geology, Faculty of Science, University of Zagreb, Horvatovac 95, HR-10000 Zagreb, Croatia; (sabina.strmic@inet.hr) 2 Faculty of Mining, Geology and Polytechnic, Goce Delčev University, Krste Misirkov bb, P.O. Box 201, MK-2000 Štip, Republic of Macedonia 3 Research Division, Canadian Museum of Nature, P.O. Box 3443, Station D, Ottawa, Ontario K1P 6P4, Canada 4 Department of Applied Geosciences and Geophysics, Mineralogy and Petrology Group, University of Leoben, Peter-Tunner-Strasse 5, A-8700 Leoben, Austria doi: 104154/gc.2012.31 Geologia CroaticaGeologia Croatica Ab STrA CT The epidote-bearing Čanište pegmatite and adjacent Upper Carboniferous granodiorites cut Precambrian gneisses, on the western slopes of the Selečka Mts., the Eastern Pelagonian zone, Republic of Macedonia. The pegmatite ex- hibits zonal internal structure with the following sub-units: the wall zone (amazonite microcline ± biotite, quartz), the first intermediate zone (epidote + haematite + grossular + muscovite + quartz + almandine ± zircon, beryl, mi- crocline, quartz), the second intermediate zone (albite + quartz ± microcline) and the core (massive quartz). Accord- ing to the microprobe data epidote belongs to clinozoisite subgroup with the formula (Ca1.96–1.99Mn0.02–0.03Fe2+ 0.00–0.02) (Al2.17–2.46Fe3+ 0.51–0.82Ti0.00–0.01)(Si2O7)(Si0.99–1.00Al0.00–0.01O4)O(OH). The occurrences of almandine and zircon with low U, Th and REE content, are indicative of weakly evolved granitic/granodioritic rocks. The absence of aplites suggests steady pressure conditions during the course of pegmatite crystallization. Microthermometric data combined by the two-feldspar geothermometer gained pressure from 4.8 to 5.6 kbar for the second intermediate zone. The wall zone, composed of amazonite microcline, crystallized at a temperature between 650 and 760 °C. A drop in melt tem- perature to below 550 °C, under the oxygen fugacity between 10–22 and 10–19.5 bar, was the principal trigger for crys- tallization of minerals in the first intermediate zone. The residual fluid, depleted in Ca, Fe and K, and enriched in water, Na and Si, caused deposition of the second intermediate zone (albite + quartz) at temperatures between 445 and 465 °C. The massive quartz core crystallized in the very last stage of the pegmatite evolution (T ≈ 400–480 °C) from melt residue enriched in silica, water and CO2 content. Keywords: magmatic-hydrothermal transition, granodiorite, pegmatite, epidote, fluid inclusions, Pelagonian zone, Republic of Macedonia 1. INTrODUCTION The Čanište pegmatite is situated approximately 150 km south of Skopje, Republic Macedonia, on the western slopes of the Selečka Mts. which represent a part of the Eastern Pelagonian tectono-stratigraphic unit of the Dinaride-Hell- enides (Fig. 1). The Pelagonian Massif exposes Precambrian crystalline basement made of ortho- and paragneisses, mi- caschists and amphibolites and comprises numerous pegma- tites, which differ according to their size, mineralogical fea- Geologia Croatica 65/3Geologia Croatica 424 Figure 2: Paragenetic sequence of the Čanište epidote-bearing pegma- tite. tures, internal structures and the degree of fractionation (e.g. IVANOV et al., 1966; ZEBEC & RADANOVIĆ-GUŽVICA, 1992; JOVANOVSKI et al., 2003). This pegmatite attracts attention due its peculiar Ca-en- riched mineral assemblage with the unique occurrence of up to 2 metre long epidote crystals (BERMANEC et al., 2001). Epidote is not a common pegmatitic mineral and it has been recorded only within several epidote-bearing pegmatites elsewhere (e.g. FRANZ & SMELIK, 1995; JANECZEK, 2007, LIEBSCHER et al., 2007; COTA et al., 2010, SWAN- SON & VEAL, 2010). Furthermore, the Čanište pegmatite exhibits a zonal mineral distribution that allows a detailed investigation of fluid inclusions within minerals from the different stages of the pegmatite crystallization. Although the zonal pegmatites are common, and fluid inclusions rep- resent relicts of fluids involved in the crystallization proc- esses, only a few publications present the fluid inclusion data systematically collected across the distinct pegmatite zones (e.g. LONDON, 1986, 1990; THOMAS & SPOONER, 1988, 1992; FUERTES-FUENTE et al. 2000; BEURLEN et al., 2001; SIRBESCU et al., 2008). The pegmatites are related to the late stage of magmatic crystallization. While the importance of volatiles and incom- patible elements in enriched melts is generally accepted, there are still numerous open questions about the mechanism of their deposition. The majority of authors consider that water-saturated magmas are responsible for the principal mineralogical characteristics of pegmatites (e.g. JAHNS & BURNHAM, 1969; BURNHAM & NEKVASIL, 1986; NA- BELEK et al., 2010). In contrast, LONDON et al. (1989) Figure 1: Geological setting of the Čanište epidote-bearing pegmatite, Republic of Ma cedonia (after MOST, 2003). WMZ – Wes tern Macedonian zone; PM – Pelagonian mas sif; VZ – Vardar zone; SMM – Serbo-Ma cedonian massif. Strmić Palinkaš et al.: The evolution of the čanište epidote-bearing pegmatite, fyro Macedonia: evidence from mineralogical and geochemical features Geologia Croatica 425 Figure 3: a) Photomicrographs of microcline from the wall zone; b) the transition from the first intermediate zone comprising epidote, hematite, muscovite and quartz into the second intermediate zone with albite and quartz. Abbreviations: Ab – albite; Ep – epidote; Hem – hematite; Mic – mi- crocline; Ms – muscovite; Qtz – quartz. and LONDON (1990, 2008) explain the formation of pegm- atites by disequilibrium crystallization from water unsatu- rated magmas, emphasizing the role of fluxing elements such as B, F, and P. The aim of this study is to interpret the evolution of melt- fluid in the late magmatic system responsible for deposition of the Čanište epidote-bearing pegmatite. A fluid inclusion study complemented by calculated thermodynamic equilibria of the mineral paragenesis shed light on the P-T-X conditions when the pegmatite formed. 2. GEOLOGICAL SETTING The Pelagonian tectono-stratigraphic unit is a ca. 420 km long and 60 km broad in the NNW-SSE striking part of the central Hellenides (Fig. 1), exposing Precambrian crystalline basement made of ortho- and paragneisses, micaschists and amphibolites. Granitoids intruded the Pelagonian basement during: I) Upper Carboniferous and II) Late Permian – Early Triassic magmatic events (MOST, 2003). According to the QAP classification, Pelagonian granitoids range from granite to quartz-diorite, but are mainly granodioritic in composi- tion (DUMURDZANOV, 1985; MOST, 2003). The Upper Carboniferous granodiorite (299 ± 1 Ma, U/Pb zircon age dating; MOST, 2003) underwent compressional deformation and developed a greenschist to amphibolite-grade metamor- phic overprint. A Late Permian – Early Triassic granodiorite (~245 ± 1 Ma, U/Pb zircon age dating; MOST, 2003) is rep- resented by massive intrusive bodies within the Eastern Pel- agonian zone, including the Selečka Mts. The relicts of con- comitant metamorphism are not preserved. A sedimentary sequence, comprising carbonate and clastic rocks, was de- posited during Triassic and Jurassic times. The geological structure of the Pelagonian zone is mostly a consequence of polyphase tectonometamorphic events during convergence of the Apulian and European plates between the Upper Ju- rassic and Upper Tertiary times (MOST, 2003). The Čanište pegmatite is one of numerous pegmatite oc- currences within the Eastern Pelagonian zone. The pegma- tites vary in size from a few decimetres wide and tens of metres long to larger bodies tens of metres wide by hundreds of metres long. They differ according to the mineralogical features, the internal structures and the fractionation degree as well. Beside epidote-bearing ones (Čanište and Dunje lo- calities), the most interesting are those enriched in uranium and thorium mineralization (Alinci and Crni Kamen locali- ties; e.g. IVANOV et al., 1966; RADUSINOVIĆ & MARK OV, 1971; BERMANEC et al., 1988, 1992; ZEBEC & RADA- NOVIĆ-GUŽVICA, 1992). The Čanište lens-shaped, up to 10 m wide pegmatite body, cuts Precambrian gneisses (DUMURDZANOV, 1985; MOST, 2003). The well developed internal zonation of the pegmatite is illustrated by an idealized paragenetic sequence (Fig. 2). Equigranular subhedral amazonite microcline is the main constituent of the wall zone (Fig. 3a), whereas quartz and biotite are accessory minerals. The first intermediate zone consists of giant epidote crystals (up to 2 m long; Fig. 3b), microcline, haematite, muscovite, garnet, quartz, and minor zircon and beryl (Fig. 3c). The second intermediate zone, composed of albite, quartz and minor microcline grades (Fig. 3c) into the monomineralic massive quartz core. 3. ANALYTICAL METHODS Feldspar, epidote, quartz, garnet and zircon crystals were separated for X-ray powder diffraction (XRD) and electron- microprobe analyses. The XRD analyses were conducted on oriented samples using a Philips diffractometer PW 3040/60 X’Pert PRO (45 kV, 40 mA) with CuKα monochromatised Geologia Croatica 65/3Geologia Croatica 426 radiation (λ=1.54056 Å) and θ-θ geometry. Samples were scanned between 4 and 63 ° 2θ with 0.02 ° step per 0.5 min- ute. The goniometer was calibrated against a quartz standard. Phase identification was performed using X’Pert Highscore software package (PANanalytical, 2004) in support with ICDD-PDF 2 database (2004). Unit cell parameters were calculated with the least-square refinement program UNIT- CELL (HOLLAND & REDFERN, 1997). The chemical composition of selected samples was esti- mated by the JEOL 733 electron microprobe equipped with the Tracor Northern 5500 and 5600 automation. An accelerat- ing voltage of 15 kV and a beam current of 20 nA were used in the analyses. Beam diameter varied with the mineral phase analyzed: 2 mm for zircon, garnet and epidote and 20 mm for feldspars. The following standards were used: albite (Na, Al, Si), sanidine (K), gehlenite (Ca), almandine (Fe), rutile (Ti), tephroite (Mn), zircon (Zr), diopside (Mg), sanbornite (Ba), rubidium microcline (Rb), pollucite (Cs), crocoite (Pb), syn- thetic REE phosphates (La, Ce, Pr, Nd, Sm, Gd, Er, Yb), syn- thetic yttrium iron garnet (Y), synthetic hafnon (Hf), synthetic UO2 (U) and synthetic ThO2 (Th). Minimum detection limits for all analyzed range from 200 to 300 ppm. Fluid inclusion investigations were carried out on mi- crocline, albite, epidote and quartz crystals. Microthermo- metric measurements of fluid inclusions were performed us- ing a Linkam THMS 600 stage mounted on an Olympus BX 51 microscope using 10x and 50x Olympus long-working distance objective lenses for visible light. Two synthetic fluid Table 1: Representative microprobe analyses, calculated formulas and distribution of the key cation sites for epidote from the first intermediate zone of the Čanište epidote-bearing pegmatite. PT 1 PT 2 PT 3 PT 4 PT 5 PT 6 PT 7 PT 8 PT 9 Chemical composition (wt. %) SiO2 36.82 36.74 37.36 36.86 36.79 36.88 37.45 37.07 37.66 TiO2 < d.l. 0.09 < d.l. 0.08 < d.l. < d.l. 0.09 0.07 0.12 Al2O3 22.98 22.80 22.84 22.50 22.63 22.57 26.19 24.33 26.10 Fe2O3 12.87 13.06 13.06 13.11 13.33 13.07 8.90 11.20 8.78 MnO 0.44 0.41 0.44 0.55 0.49 0.49 0.25 0.36 0.25 CaO 22.64 22.73 22.78 22.77 22.62 22.36 23.32 22.99 23.17 H2O** 1.84 1.84 1.85 1.84 1.84 1.83 1.88 1.86 1.88 TOT 97.59 97.67 98.33 97.71 97.70 97.20 98.08 97.88 97.96 Structural formula (atom. %) Si4+ 3.00 2.99 3.02 3.00 3.00 3.02 2.99 2.99 3.01 Ti4+ 0.00 0.01 0.00 0.00 0.00 0.00 0.01 0.00 0.01 Al3+ 2.21 2.19 2.18 2.16 2.17 2.18 2.46 2.31 2.46 Fe3+ 0.79 0.80 0.78 0.80 0.82 0.78 0.53 0.68 0.51 Fe2+ 0.00 0.00 0.02 0.00 0.00 0.02 0.00 0.00 0.02 Mn2+ 0.03 0.03 0.03 0.04 0.03 0.03 0.02 0.02 0.02 Ca2+ 1.98 1.98 1.97 1.99 1.98 1.96 1.99 1.99 1.98 CATS 8.00 8.00 8.00 8.00 8.00 8.00 8.00 8.00 8.00 Distribution of ions on key sites A1 Mn2+ 0.03 0.03 0.03 0.04 0.03 0.03 0.02 0.02 0.02 Fe2+ 0.00 0.00 0.02 0.00 0.00 0.02 0.00 0.00 0.02 Ca2+ 0.97 0.97 0.95 0.96 0.97 0.94 0.98 0.98 0.97 A2 Ca2+ 1.01 1.01 1.02 1.03 1.01 1.02 1.01 1.01 1.02 M1 Al3+ 0.99 0.99 0.95 0.97 0.99 0.96 0.99 0.99 0.98 M2 Al3+ 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 M3 Fe3+ 0.79 0.80 0.78 0.80 0.82 0.78 0.53 0.68 0.51 Ti4+ 0.00 0.01 0.00 0.00 0.00 0.00 0.01 0.00 0.01 Al3+ 0.21 0.19 0.22 0.19 0.18 0.22 0.46 0.32 0.48 T Si4+ 3.00 2.99 3.02 3.00 3.00 3.02 2.99 2.99 3.01 Al3+ 0.00 0.01 0.00 0.00 0.00 0.00 0.01 0.01 0.00 < d.l. – below detection limit * Total iron content given as Fe2O3 K, Na and Mg are below detection limits ** Determined by stoichiometry Strmić Palinkaš et al.: The evolution of the čanište epidote-bearing pegmatite, fyro Macedonia: evidence from mineralogical and geochemical features Geologia Croatica 427 inclusion standards (SYN FLINC; pure H2O and mixed H2O- CO2) were used to calibrate the equipment. The precision of the system was ±2.0 °C for homogenization temperature, and ±0.2 °C in the temperature range between –60 and +10 °C. The laser Raman spectroscopy, used for the semiquan- titative analysis of CO2 and N2 in the CO2-rich phases of fluid inclusions, was performed on the Dilor LabRAM in- strument. A laser beam is focused through an Olympus BX 40 microscope onto the fluid inclusion of interest. The ob- jective lenses of 50x and 100x magnification, combined with a confocal optical arrangement, enable a spatial resolution in the order of a cubic micrometer. Frequency-doubled Nd- YAG green laser (532 nm, 100 mV) was employed. Meas- urements can also be performed at temperature range be- tween –190 and 600 °C, using the Linkam THMSG 600 heating-cooling stage described above. Bulk ion compositions of fluid inclusions were estab- lished by ion chromatographic analysis applying the tech- nique modified after BOTTREL et al. (1988). About 1 g of cleaned grains and 5 ml of double-distilled and de-ionized water were ground with an agate mortar and pestle to fine powder. The milky solution produced was centrifuged to separate the leachate from the sample. A Dionex DX-500 system with a micromembrane suppressor and pulsed am- perometric detector was used for analyses of anions and cat- ions. Detection limits are in the 0.1 ppb (mg/l) range. 3. rESULTS 3.1. Mineralogy and chemical composition of minerals The wall zone consists of amazonite microcline with the fol- lowing unit cell characteristics a= 8.348(5) Å, b = 13.333(8) Å, c = 7.062(5) Å, α = 91.15(7)°, β = 116.25(9)°, γ = 88.22 (1)° and V = 720.56(3) Å3. Minor biotite and quartz occur as well. The first transitional zone represents mineralogically the most diverse unit of the Čanište pegmatite. It comprises euhedral columnar crystals of epidote, up to 2 m long, em- bedded in a medium- to coarse-grained matrix of haematite, muscovite, quartz, albite, microcline and garnet. Zircon and beryl grains occur sporadically. The epidote lattice parameters, calculated on the basis of XRD patterns, (a= 8.890(2) Å, b = 5.634(2) Å, c = 10.147 (2) Å, β = 115.40(2)° and V = 459.1(2) Å3) correspond well to the data previously reported for epidote from other local- ities (e.g. BONAZZI & MENCHETTI, 1995). According to the electron-microprobe data (Table 1) and classification pro- posed by ARMBRUSTER et al. (2006), epidote from the Čanište pegmatite belongs to the clinozoisite subgroup with a general formula of Ca2Al2Fe3+(Si2O7)(SiO4)O(OH). The structural formula and the key cation sites calculated on the basis of Σ(A+M+T)=8 are listed in Table 1. Garnet crystals are not very common. They vary in size, reaching up to 2 cm and have a deep red color. The cell pa- rameters, calculated from diffraction lines using the least- squares method, are a = 11.713(2) Å and V = 1607(1) Å3. The molar proportions of garnet end-members were calcu- lated from the electron microprobe data (Table 2) according to the procedure published by LOCOCK (2008). Grossular, with 39.9 – 40.7 mole %, represents the principal garnet con- Table 2: Representative microprobe analyses, calculated formulas, distribu- tion of the key cation sites and the end-member contents for garnets from the first intermediate zone of the Čanište epidote-bearing pegmatite. PT 1 PT 2 PT 3 Chemical composition (wt. %) SiO2 37.00 37.38 37.14 TiO2 0.35 0.36 0.32 Al2O3 20.07 20.18 19.97 Fe2O3 1.65 1.56 1.71 FeO 16.87 16.67 16.66 MnO 6.91 6.57 6.70 CaO 15.98 15.94 15.75 MgO 0.27 0.29 0.30 TOT 99.10 98.95 98.55 Structural formula (atom. %) Si4+ 2.97 3.00 2.99 Ti4+ 0.02 0.02 0.02 Al3+ 1.90 1.91 1.90 Fe3+ 0.10 0.09 0.10 Fe2+ 1.13 1.12 1.12 Mn2+ 0.47 0.45 0.46 Ca2+ 1.38 1.37 1.36 Mg2+ 0.03 0.04 0.04 CATS 8.01 7.98 7.99 O 12 12 12 Distribution of ions on key sites X Fe2+ 1.12 1.12 1.13 Mn2+ 0.47 0.45 0.46 Ca2+ 1.38 1.37 1.37 Mg2+ 0.03 0.03 0.04 Y Ti4+ 0.02 0.02 0.02 Al3+ 1.87 1.88 1.88 Fe3+ 0.10 0.09 0.10 Fe2+ 0.01 0.00 0.00 Z Si4+ 2.97 3.00 2.99 Al3+ 0.03 0.00 0.01 The end-members content (mole %) Spessartine 15.9 15.2 15.5 Pyrope 1.1 1.2 1.2 Almandine 38.0 38.1 38.1 Grossular 39.9 40.7 40.0 Andradite 5.1 4.8 5.2 Geologia Croatica 65/3Geologia Croatica 428 Table 3: Representative microprobe analyses and calculated formulas for zircon from the first intermediate zone of the Čanište epidote-bearing pegmatite. Zircon PT 1 PT 2 PT 3 Chemical composition (wt. %) ZrO2 64.73 64.83 64.93 HfO2 2.71 2.79 2.81 SiO2 32.36 32.50 32.46 TOT 99.80 100.12 100.20 Structural formula (atom. %) Zr4+ 0.976 0.974 0.975 Hf4+ 0.024 0.025 0.025 Si4+ 1.000 1.001 1.000 CATS 2.000 2.000 2.000 O 4 4 4 Y, La, Ce, Pr, Nd, Sm, Gd, Er, Yb, Ti, Th and U are below detction limits. stituent. The proportion of almandine is estimated within a range between 38.0 and 38.1 mole %. Spessartine content spans between 15.2 and 15.9 mole %. Andradite and pyrope contents vary up to 5.2 and 1.2 mole %, respectively. Pinkish, several cm long, zircon crystals display the fol- lowing unit cell parameters: a = 6.811(4) Å, b = 5.988(6) Å and V = 261.7(3) Å3. Its chemical composition and structural formula, calculated on the basis of four atoms of oxygen per formula unit, are summarized in Table 3. Albite and quartz represent the principal constituents of the second transitional zone. Amazonite microcline occurs sporadically. Blocky white albite occurs in the form of crys- tals up to 10 cm in size. The unit cell parameters, calculated from diffraction lines using the least-squares method, are a= 8.142(6) Å, b = 12.784(3) Å, c = 7.165(4) Å, α = 94.158(9)°; β = 94.158(9)°, γ = 87.741(0)° and V = 665.0(9)Å3. Ama- zonite microcline, locally intergrown with albite, displays the following unit cell characteristics a= 8.584(4) Å, b = 12.980 (6) Å, c = 7.219(3) Å, α = 90.79(6)°, β = 115.96(3)°, γ = 87.60(4)° and V = 721.5(4) Å3. The chemical composi- tion and structural formulae of feldspar from the second in- termediate zone are reported in Table 4. The formulae were calculated on the basis of eight oxygen atoms per formula unit. The feldspars from the Čanište pegmatite are very ho- mogeneous. The plagioclase composition averages about Ab- 98An1Or1 with a total range of variation less than 1 mole% Ab. The alkali feldspar has compositions of Ab6Or94An0 with variation of less than 2 mole% Ab. Figure 4: Photomicrographs of representative primary fluid inclusions from different sub-units of the Čanište epidote-bearing pegmatite: a) hy- drosaline (L+V+S) inclusion recorded within mi- crocline from the wall zone; b) two-phase (L+V) inclusion hosted by microcline from the wall zone; c) two-phase inclusion (L+V) within epi- dote from the first intermediate zone; d) three- phase inclusion (L+V+S) contains accidentally trapped anisotropic solid phase, epidote from the first intermediate zone; e) inclusion with ac- cidentally trapped crystal, quartz from the sec- ond intermediate zone; f ) two-phase (L+V) in- clusions from the quartz core. Strmić Palinkaš et al.: The evolution of the čanište epidote-bearing pegmatite, fyro Macedonia: evidence from mineralogical and geochemical features Geologia Croatica 429 the criteria proposed by ROEDDER (1984). Primary fluid inclusions are sub-rounded to irregular in shape and up to 10 mm in size. Usually these inclusions occur in individual clus- ters or in isolation. Based on the number of phases, the pri- mary microcline-hosted fluid inclusions could be subdivided into two additional sets: 1) polyphase (L+V+S) and 2) two- phase (L+V) inclusions. Polyphase inclusions comprise up to 50 vol. % of solid phases, highly saline aqueous solution and vapour bubbles (Fig. 4a). Solid phases are usually transparent and inactive in Raman spectra. Salt melting temperatures from 450 °C up to 600 °C (the limit of the heating-freezing stage) suggest salinity higher than 53.3 wt. % NaCl equ. (BODNAR & VI- TYK, 1994). According to Raman microspectroscopy data the vapour bubbles contain only water vapour. Total homog- enization occurs by the vapour phase disappearance at tem- peratures higher than 480 °C. The part of fluid inclusions did not homogenize below the upper temperature limit of the heating stage (600 °C), and consequently the bulk fluid prop- erties and isochores can be calculated only for those inclu- sions with total homogenization below 600 °C (Fig. 6). Two phase inclusions contain liquid and vapour phases at room temperature (Fig. 4b). Degree of fill (F) varies be- tween 0.75 and 0.80. Eutectic temperature (Te) around –52 The partitioning of the albite component between coex- isting microcline and plagioclase solid-solutions can be em- ployed as a pressure-dependent geothermometer (WHIT- NEY & STROMER, 1977). Whereas temperature estimated from the two-feldspar geothermometer increases with pres- sure by l8 °C per kilobar (STROMER & WHITNEY, 1985), the formation temperature can be determined through a com- bination of the two-feldspar geothermometer with the fluid inclusion data (Fig. 6). 3.2. Fluid inclusion studies Fluid inclusions from the wall zone amazonite microcline were classified as either primary or secondary according to Table 4: Representative microprobe analyses and calculated formulas for feldspars from the second intermediate zone of the Čanište epidote-bear- ing pegmatite. Albite Amazonite microcline PT 1 PT 2 PT 3 PT 4 PT 5 PT 6 PT 7 PT 8 PT 9 Chemical composition (wt. %) Na2O 11.36 11.28 11.17 11.39 11.52 11.65 0.66 0.84 0.42 K2O 0.07 0.08 0.12 0.12 0.07 0.13 15.62 15.25 15.79 Rb2O < d.l. < d.l. < d.l. < d.l. < d.l. < d.l. 0.22 0.25 0.11 Cs2O < d.l. < d.l. < d.l. < d.l. < d.l. < d.l. 0.07 0.06 < d.l. CaO 0.31 0.29 0.72 0.21 0.15 0.14 < d.l. < d.l. < d.l. BaO < d.l. < d.l. < d.l. < d.l. < d.l. < d.l. < d.l. < d.l. 0.57 PbO < d.l. < d.l. < d.l. < d.l. < d.l. < d.l. 0.34 0.41 0.14 Al2O3 20.08 19.93 20.52 19.63 19.81 19.68 18.25 18.38 18.61 Fe2O3 < d.l. < d.l. 0.06 0.06 0.06 0.06 < d.l. < d.l. < d.l. SiO2 68.91 68.87 68.12 69.31 69.52 69.23 65.24 64.54 64.47 TOT 100.73 100.45 100.71 100.72 101.13 100.89 100.40 99.73 100.11 Structural formula (atom. %) Na+ 0.954 0.949 0.940 0.956 0.963 0.978 0.059 0.075 0.038 K+ 0.004 0.005 0.007 0.007 0.004 0.007 0.919 0.903 0.934 Rb+ 0.000 0.000 0.000 0.000 0.000 0.000 0.007 0.007 0.003 Cs+ 0.000 0.000 0.000 0.000 0.000 0.000 0.001 0.001 0.000 Ca2+ 0.015 0.013 0.034 0.010 0.007 0.006 0.000 0.000 0.000 Ba2+ 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.010 Pb2+ 0.000 0.000 0.000 0.000 0.000 0.000 0.004 0.005 0.002 Al3+ 1.025 1.020 1.050 1.002 1.007 1.004 0.992 1.006 1.016 Fe3+ 0.000 0.000 0.002 0.002 0.002 0.002 0.000 0.000 0.000 Si4+ 2.985 2.990 2.958 3.001 2.998 2.996 3.008 2.996 2.988 CATS 4.982 4.977 4.990 4.978 4.981 4.993 4.989 4.994 4.991 O 8 8 8 8 8 8 8 8 8 < d.l. – below detection limit Sr, Mn and P are below detection limits. Figure 5: Microthermometric data for fluid inclusions from different sub- units of the Čanište epidote-bearing pegmatite; a) Plots of ice-melting (Tm ice) and clathrate-melting (Tm CLAT) temperatures; b) Plots of homogeni- zation temperatures. Geologia Croatica 65/3Geologia Croatica 430 Figure 6: Pressure–temperature diagram summariz- ing the relevant information relating to the P–T his- tory of the Čanište epidote-bearing pegmatite. °C suggests CaCl2 and NaCl as the dominant dissolved salts (CRAWFORD, 1981). The final ice melting temperature (Tm ice) has been measured between –7.5 and –8.5 °C (Fig. 5a). The final ice melting temperatures and experimental data published by BODNAR (1993) for the system H2O–NaCl, indicate salinity ranges from 11.1 to 12.3 wt.% NaCl equ. Total homogenization (TH) occurs between 440 and 460 °C by vapour-bubble disappearance (Fig. 5b). Bulk fluid den- sity, utilizing the equation of state proposed by ARCHER (1992) through the BULK software (BAKKER, 2003), spans from 0.809 to 0.863 g/cm3. The isochores were calculated with the ISOC software (BAKKER, 2003) utilizing the equa- tions of BOWERS & HELGESON (1983) and BAKKER (1999) (Fig. 6). The secondary inclusions in the wall zone amazonite microcline lie along curved trails, display irregular shape and comprise two phases (L+V). Their size below 5 mm pre- cludes microthermometric measurements. Epidote is the only mineral from the first intermediate zone that hosts fluid inclusions large enough for microther- mometric measurements. Primary fluid inclusions occur ei- ther isolated or as clusters. They are two-phase (liquid + va- pour) up to 15 mm in size, with an elongated, rounded or irregular shape (Fig. 4c). Some inclusions enclose birefrin- gent insoluble solids (Fig. 4d). The solids might be crystals trapped accidentally during the formation of fluid inclusions, rather than daughter minerals, judging by their inconsistent phase ratios. The vapour phase occupies around 20% of the total volume. Raman microspectroscopy only revealed the presence of water. Initial melting temperature between –42 and –62 °C sug- gests the presence of divalent cations, most likely Ca, Fe and Mg (BARKER, 1995). The final ice melting temperature spanning from –5.6 to –6.7 °C (Fig. 5a) indicates moderately saline fluids (8.7 and 10.1 wt.% NaCl equ.). Homogeniza- tion to a liquid phase occurs at temperatures between 180 and 210 °C (Fig. 5b). The calculated fluid density ranges from 0.925 to 0.961 g/cm3. The bulk leachate data of fluid inclusions in epidote sug- gest Cl– as major anion and Na+ and Mg2+ as the dominant cations (Table 5). Secondary inclusions, distributed along healed fractures of random orientation, were too small for microthermomet- ric measurements (less than 5 mm). Fluid inclusions were examined in quartz and albite from the second intermediate zone. The majority of the inclusions have a size below 10 mm. Primary inclusions occur as single, isolated inclusions, or as randomly oriented groups, and commonly mark zones of host crystal growth. These inclu- sions exhibit irregular to rounded shapes and contain liquid and vapour phases with consistent volumetric proportions (F ≈ 0.80). Frequently, inclusions comprise an insoluble solid phase, interpreted as accidentally trapped crystals (Fig. 4e). Raman microspectroscopy recorded only the presence of wa- ter, as for the samples from the first intermediate zone. Eutectic temperatures around –52 °C indicate a Ca-Na- Cl system (SHEPHERD et al., 1985). The temperatures of final ice melting ranging from –3.4 to –4.2 °C (Fig. 5a) cor- responding to salinity between 5.6 and 6.7 wt.% NaCl equ. Temperatures of homogenization into a liquid phase were recorded within an interval between 165 and 180 °C (Fig. Strmić Palinkaš et al.: The evolution of the čanište epidote-bearing pegmatite, fyro Macedonia: evidence from mineralogical and geochemical features Geologia Croatica 431 5b). Bulk fluid density, estimated from fluid inclusion data, spans from 0.931 to 0.951 g/cm3. Constructed isochores are shown in Figure 6. The intersection of isochores with the two-feldspar geothermometer published by WHITNEY & STROMER (1977), and corrected for pressure according to the procedure described by STROMER & WHITNEY (1985), revealed the formation temperature of the second intermedi- ate zone in the range between 445 and 465 °C under pressure between 4.8 and 5.6 kbar. Fluid inclusions from the monomineralic massive quartz core show irregular to rounded shapes and range in size up to 15 mm (Fig. 4f). They occur either isolated or in clusters of 5 to 10 inclusions arranged in three-dimensional, non- planar arrays. Inclusions comprise two phases (liquid and vapour) and have uniform degree of fill around 0.8. Micro- Raman spectroscopy measurements recognized the presence of CO2 within the vapour phase. Due to poor optical quality, an initial melting temperature (eutectic temperature, Te) was not detected. The formation of the CO2 clathrate phase additionally hampers interpretation of low temperature microthermometric data. Cla th rate melting temperature (Tm clat) in the interval between +8.1 and +8.9 °C (Fig. 5a) corresponds to a salinity of 2.2 to 3.8 wt.% equ. NaCl. Homogenization of the carbonic phase proceeds into vapour phase around 28 °C. Total homogenization by va- pour-bubble disappearance occurs in a temperature range between 155 and 170 °C (Fig. 5b). Bulk fluid density, calcu- lated by the BULK software (BAKKER, 2003), ranges be- tween 0.882 and 0.892 g/cm3. The leachate data revealed the predominance of Na+, K+ and Cl– in the aqueous fluids responsible for the massive quartz core crystallization (Table 5). 4. DISCUSSION Magmatic differentiation by crystal fractionation generally results in the transition of low-volatile content silicate melt (producing normal igneous rocks), through hydrous silicate melt (producing pegmatites), to late-stage water-rich fluids (producing metal ore deposits) (ROEDDER, 1992). The ma- jority of fluid inclusion studies performed on pegmatites sug- gest crystallization from a water-saturated system and, con- sequently, immiscibility between the melt phase and volatile fluid (e.g. BEURLEN et al., 2001; THOMAS et al., 2011; THOMAS & DAVIDSON, 2012). The crystallization evolution of the Čanište epidote- bearing pegmatite, is reconstructed using thermodynamic mineral equilibria and fluid inclusion data. The pegmatite originates from intrusion of granodioritic melt into the Pel- agonian crystalline basement in the Upper Carboniferous (MOST, 2003). The melt that ultimately produced the Čanište pegmatite was relatively Fe-rich in its initial stage, as indi- cated by the crystallization of epidote, haematite and alman- dine. The complete absence of fluxes (B, P, F), and relatively high concentrations of compatible elements (e.g., Ca, Fe, Zr) are very different in comparison to common granitic systems, although similar chemistry has been related with leucotona- litic to quartz leucogabbroic pegmatites (NOVÁK & GA- DAS, 2010). The Čanište pegmatite exhibits a zoned internal structure with four distinctive zones: the wall zone, two in- termediate zones and the quartz core. Textural characteristics suggest primary crystallization from melt in order; wall zone → first intermediate zone → second intermediate zone → core. The progressive crystallization resulted in melt com- position changes. Concentrations of Ca, Fe and K decreased, and concentrations of Na and Si increased. Fluid inclusion data suggest subsequent crystallization under a steady de- crease of temperature and isobaric conditions. Furthermore, fluid inclusion study indicates that aqueous fluids played an important role in the genesis of the Čanište pegmatite. The CO2 content increased with progressive fractional crystalli- zation, and a significant amount of CO2 is present only in the very late stage of crystallization. The presence of primary highly saline aqueous inclu- sions in the wall zone microcline supports the magmatic or- igin of the entrapped fluid (e.g. ROEDDER, 1992). Coexist- ing polyphase (L+V+S) and two-phase (L+V) inclusions as well as large variation in salinity suggest the accidental en- trapment near the L/L+S interface of the P-T-X space (e.g. BAKKER & ELBURG, 2006). Whereas the trapping condi- tions might be estimated from the intersection of isochores constructed for two sets of simultaneously trapped fluid in- clusions, and assuming that two principal sets of primary inclusions are contemporaneous, only the minimum possible formation temperature and pressure (600 °C, 3.8 kbar; Fig. 6) can be defined due to lack of homogenization tempera- tures for high temperature polyphase inclusions. The absence of aplites indicates a nearly constant pressure during pegm- atite crystallization (e.g. NABELEK et al., 2010). Assuming a pressure of between 4.8 and 5.6 kbar, (estimated for the second intermediate zone by the combination of two-feldspar geothermometer and fluid inclusion data), the formation tem- perature of the wall zone then ranges from ca. 650 to 760 °C (Fig. 6). The formation temperature of the first intermediate zone in the interval between 445 and 550 °C is constrained from the microthermometric data obtained on epidote, assuming Table 5: The bulk leachate analyses for epidote and quartz from the Čanište epidote-bearing pegmatite. Li+ Na+ K+ Mg2+ Ca2+ F- Cl- Br- I- NO3 - SO4 2- aNa+/aK+ aNa+ 2/aCa2+ Sample Sub-unit mmol/L Epidote The 1st intermediate zone 3.50 75.9 40.0 61.5 0.02 14.1 148.7 0.2 0.00 2.1 2.0 2 230787 Quartz The quartz core 0.70 32.4 12.0 0.0 5.68 12.2 22.2 0.0 0.01 4.0 2.2 3 185 Geologia Croatica 65/3Geologia Croatica 432 Figure 7: Log fO –temperature diagram at 5.5 kbar pressure and aH2O = 1 for the sys- tem Ca–K-Fe–Al-Si–O–H showing proposed environments for formation of the first intermediate zone mineral assemblage (Hem + Ms + Otz + Alm + Mic). Mineral stabi- lity fields based on the equation: 2 Fe3Al2(SiO4)3 + 2 KAlSi3O8 + 2 H2O +3/2 O2 ↔ 3 Fe2O3 + 2 KAl2AlAi3O10(OH)2 + 6 SiO2 (almandine) (microcline) (haematite) (muscovite) (quartz) and thermodynamic data from KELLEY (1960), HELGESON et al. (1978), WAGMAN et al. (1982), SHOCK & HELGESON (1988) and ANOVITZ et al. (1993). Abbreviations: Hem – haematite; Ms – muscovite; Qtz – quartz; Alm – almandine; Mic – microcline). nearly constant pressure during the pegmatite crystallization (4.8–5.6 kbar, Fig. 6). The mineral assemblage comprising almandine, microcline, haematite, muscovite and quartz can be used as an indicator of oxygen fugacity. According to thermodynamic data published by KELLEY (1960), HELGE- SON et al. (1978), WAGMAN et al. (1982), SHOCK & HELGESON (1988) and ANOVITZ et al. (1993) and the following equation: 2 Fe3Al2(SiO4)3 + 2 KAlSi3O8 + 2 H2O +3/2 O2 ↔ (almandine) (microcline) 3 Fe2O3 + 2 KAl2AlAi3O10(OH)2 + 6 SiO2 (haematite) (muscovite) (quartz) oxygen fugacity during deposition of the first intermediate zone was between 10–22 and 10–19.5 bar (Fig. 7). Electron microprobe data were mostly used to calculate chemical formulas of selected minerals from the first inter- mediate zone. Whereas the epidote group comprises a wide- spread and chemically complex family of silicates the com- position of which can be represented as A2M3(T2O7)(TO4) O(OH) (A = Ca2+, Mn2+, Sr2+, REE3+; M = Al3+, Fe3+, Fe2+, Mn3+, Mg2+; T = Si4+, Al3+), the major issue was to estimate definite mineral formula. According to the data listed in Ta- ble 1, epidote from the Čanište pegmatite belongs to the clinozoisite subgroup with the formula (Ca1.96–1.99Mn0.02– 0.03Fe2+ 0.00–0.02)(Al2.17–2.46Fe3+ 0.51–0.82Ti0.00–0.01)(Si2O7) (Si0.99–1.00Al0.00–0.01O4)O(OH). The majority of analyzed points (PT1 – PT6) display Ps value [Ps = Fe3+/(Fe3++Al)] in the range between 26 and 29 supporting the magmatic origin of epidote (TULLOCH, 1986; SCHMIDT & POLI, 2004). The presence and relative proportions of various garnet end- members can give insights into conditions of formation. The garnet from the Čanište pegmatite is predominantly grossu- lar with subordinate almandine and spessartine components, minor andradite and a negligible pyrope content. Almandine- bearing mineral paragenesis generally points to the weakly evolved granitic/granodioritic rocks generated at great depths (e.g. GREEN, 1977; WHITWORTH, 1992). Zircon from the Čanište epidote-bearing pegmatite has a nearly stoichiomet- ric composition with a Zr/Hf atomic ratio between 39 and 41. The content of U, Th and REE, unusually low for the pegmatitic mineral assemblage, is indicative of the weakly differentiated pegmatitic system. Crystallization of minerals from the wall and the first in- termediate zone decreased activities of calcium, potassium and iron. Consequently, the residual melt has been enriched in water, silica and sodium. Increased sodium activity induced crystallization of the second intermediate zone mineral assem- blage with albite and quartz as the major constituents. Micro- cline occurs sporadically. As already mentioned, microther- mometric measurements connected with the two-feldspar geothermometer, constrain the second intermediate zone crys- tallization conditions at temperatures between 445 and 465 °C under pressure between 4.8 and 5.6 kbar (Fig. 6). The very last stage in the Čanište pegmatite genesis is represented by the crystallization of the massive quartz core. According to fluid inclusion data, the massive quartz core was produced under the influence of low-saline and CO2 enriched fluid at a temperature between 400 and 480 °C, assuming the formation pressure between 4.8 and 5.6 kbar (Fig. 6). 5. CONCLUSION Textural features and fluid inclusion data suggest that the Čanište epidote-bearing pegmatite formed as a result of sub- sequent and successive crystallization from a granodioritic melt. Mineral assemblages, especially the presence of al- mandine and U, Th, REE-depleted zircon, suggests a weakly differentiated pegmatitic system. The course of pegmatite crystallization was proceeding close to isobaric conditions. The formation pressure is esti- mated within the range of between 4.8 and 5.6 kbar (average at 5.2 kbar). The primary wall zone mineral assemblage (mi- crocline ± biotite, quartz) crystallized from the melt between 650 to 760 °C. Cooling of the melt below 550 °C at oxygen fugacity between 10–22 and 10–19.5 bar, caused deposition of the first intermediate zone (epidote + haematite + grossular + muscovite + quartz + almandine ± zircon, beryl, micro- cline, quartz). Progress of crystallization decreased activities of calcium, iron and potassium, and increased water, silica and sodium contents in the residual melt. The second inter- mediate zone comprises albite, which crystallized from the Strmić Palinkaš et al.: The evolution of the čanište epidote-bearing pegmatite, fyro Macedonia: evidence from mineralogical and geochemical features Geologia Croatica 433 Na-enriched melt. 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Manuscript received April 30, 2012 Revised manuscript accepted August 12, 2012 Available online October 30, 2012