The geochemistry of phosphorus in different granite suites of the Western Carpathians, Slovakia: the role of apatite and P-bearing feldspar

The geochemistry of phosphorus in different granite suites of the Western Carpathians, Slovakia: the role of apatite and P-bearing feldspar

Chemical Geology 205 (2004) 1 – 15 www.elsevier.com/locate/chemgeo The geochemistry of phosphorus in different granite suites of the Western Carpathi...

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Chemical Geology 205 (2004) 1 – 15 www.elsevier.com/locate/chemgeo

The geochemistry of phosphorus in different granite suites of the Western Carpathians, Slovakia: the role of apatite and P-bearing feldspar Igor Broska a,*, C. Terry Williams b, Pavel Uher a, Patrik Konecˇny´ c, Jaromı´r Leichmann d a

Geological Institute, Slovak Academy of Sciences, Du´bravska´ cesta 9, P.O. Box 106, 840 05 Bratislava, Slovakia b Department of Mineralogy, The Natural History Museum, Cromwell Road, London SW7 5BD, UK c Geological Survey of Slovak Republic, Mlynska´ dolina 1, 817 04 Bratislava, Slovakia d Department of Geology and Palaeontology, The Masaryk University, Kotla´rˇska´ 2, 611 37 Brno, Czech Republic Received 14 February 2002; received in revised form 16 June 2003; accepted 12 September 2003

Abstract The geochemical behaviour of phosphorus in granites, coupled with compositional variations in apatite, discriminate the different genetic suites of Variscan granitic rocks in the West-Carpathian orogenic belt. Meso-Variscan granites, mostly of Stype affinity, show a good correlation between SiO2 and P2O5, with decreasing amounts of P in the poorly and moderated fractionated granites, and increasing phosphorus in the most evolved and late differentiation products. The aluminium saturation index (ASI) correlates negatively with bulk P contents in I-type granites, and positively with P in S-type granites. The phosphorus content of alkali feldspar (mainly Kfs) is usually very low (typically < 0.05 wt.% P2O5), or not detected in the slightly differentiated granites. In the lateVariscan I/S-type granitoids, phosphorus is hosted mainly in the early-magmatic apatite, but is present also in the late K-feldspar (up to 0.15 wt.% of P2O5) that formed from the residual melts. In the postorogenic S-type granites, the bulk of the phosphorus occurs in alkali feldspar ( f 0.3 wt.% P2O5), with a minor proportion present in primary early-magmatic apatite. Clusters of small secondary apatite grains with a distinctive composition are distributed in alkali feldspar grains of the post-orogenic S-type granites. This apatite has formed post-magmatically from P released from P-rich alkali feldspar during decreasing temperature, by reaction with a fluid rich in volatiles (including F and B), and alkali and alkali earth metals. A-type granites have the lowest bulk phosphorus contents. Consequently, phosphate minerals are relatively rare in this granite type, and the alkali feldspar has negligible P2O5 contents. Except for Sr, the minor element contents in apatite partly correlate with the bulk composition of their host rocks and partly reflect some thermodynamic properties of melt. The Mn contents of apatite increase with the peraluminous character of the melt and with decreasing fO2 and so apatite from the S-type granites has significantly higher Mn contents than apatite from the I-type granites. Apatite from A-type granites is enriched in Fe and HREE, reflecting the higher bulk Fe and HREE content of this granite type. Apatite from specialized S-type granites is enriched in Y and HREE. In general, the Cl and S content of apatite is higher in the basic members of the I-type affinity granitic rocks. D 2004 Elsevier B.V. All rights reserved. Keywords: Geochemistry; Phosphorus; Primary apatite; Secondary apatite; Alkali feldspars; Variscan granites; Slovakia; Western Carpathians

* Corresponding author. Fax: +421-54-77-7097. E-mail address: [email protected] (I. Broska). 0009-2541/$ - see front matter D 2004 Elsevier B.V. All rights reserved. doi:10.1016/j.chemgeo.2003.09.004

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1. Introduction The contrasting behaviour of P in different granite suites, especially between typical S- and I-type granites, has been demonstrated in several papers (Bea et al., 1992; Chappell, 1999 and references therein), as has their different apatite compositions (Sha and Chappell, 2000; Belousova et al., 2001). The observed variability in the abundances of P between the strongly fractionated I- and S-type granites is related to a higher apatite solubility in peraluminous melts, P becoming progressively more abundant in the felsic S-type melts during fractionation of the granitic melt. London et al. (1990) interpreted the higher solubility of P in peraluminous silicous melts, and its relatively high concentrations in the alkali feldspar, to the elevated ASI (ASI = aluminium saturation index, molar [Al2O3/(Na2O + K2O + CaO)]). The fact that the solubility of apatite in metaluminous and peralkaline magmas is a function of melt composition and temperature was confirmed experimentally (Watson and Capobianco, 1981; Green and Watson, 1982; Harrison and Watson, 1983), as was the considerably higher apatite solubility in peraluminous melts, where the ASI>1.1 (Pichavant et al., 1992; Wolf and London, 1994). Simpson (1977) synthesized aluminium phosphorus feldspars with the generally formulae NaAl2PSiO8 and KAl2PSiO8 and initially postulated that P could be accommodated into alkali feldspars under geologically relevant conditions. Later, London (1992, 1998) demonstrated that the incorporation of P into feldspars involves the coupled substitution of Al3 + + P5 + for 2 Si4 +. This exchange is known as the berlinite substitution, where berlinite, AlPO4, is isostructural with quartz or the Si2O4 framework component of feldspars. Relatively high phosphorus contents have been recorded in alkali feldspars (Af) from many different peraluminous granitic suites, and London (1992) reported about 60 localities where the P contents in Af, including potassium feldspar (Kfs) and sodic plagioclase (Pl), ranged from 0.1 to 0.8 wt.%. In general, Kfs are richer in P (only a few localities have been recorded where the P contents are higher in plagioclase relative to Kfs), and so an increase of P in Kfs with differentiation appears to be a general phenomenon. The highest values of P in Af from a felsic magmatic system were reported from the Albu-

rquerque batholith in Spain, where P2O5 concentrations reached 2.6 wt.% (London et al., 1999), and from the Podlesı´ granite in the Krusˇne´ Hory Mts. (Erzgebirge) with up to 2.5 wt.% P2O5 (Fry´da and Breiter, 1995). Elevated P contents were also observed in Kfs from rare-element granitic pegmatites, e.g. microcline from the Tanco pegmatite, Canada contains up to 0.6 wt.% P2O5. Geologically, apatite is a ubiquitous accessory mineral in magmatic rocks, and many studies have shown apatite to be one of the most important minerals affecting, e.g. REE trends in these igneous rocks (Nash, 1972; Gromet and Silver, 1983; Piccoli and Candela, 2002). Apatite is remarkable tolerant to structural distortion and chemical substitution, and consequently is extremely diverse in composition. The apatite structure allow for numerous substitutions, including many cations (e.g. K, Na, Ba, Sr, Mn, Fe, Y, REEs, U, etc.) that substitute for Ca in the structure, and anionic complexes (i.e. SO42 , SiO44 , CO32 , etc.) that replace PO43 (Hughes and Rakovan, 2002; Pan and Fleet, 2002). Sha and Chappell (2000) demonstrated that apatite could discriminate between the S- and I-type granite suites, and variations in traceelement contents of apatite have correlated with I-type granites in the Mt. Isa Inlier with parameters such as SiO2 content, oxidation state, ASI and total alkali content (Belousova et al., 2001). The aim of this research is to find the context of the known P behaviour in felsic melt and corresponding apatite chemistry. This investigation has an aspiration to turn the respect to P discrimination character and connection between the bulk rock phosphorus geochemistry and apatite composition in the S-, I- and Atype granites. The work indicates how deeply apatite reflects the chemical characteristics and some physical conditions of the parental rocks.

2. The occurrence and typology of the WestCarpathian Variscan granitic rocks The Western Carpathians form part of the Alpine – Carpathian orogenic belt that has undergone a classical Mesozoic –Cenozoic Alpine orogenic evolution. Pre-Alpine, Variscan magmatic activity is represented by several intrusions of granitoid plutons, separated tectonically from the principal crustal-scale and base-

I. Broska et al. / Chemical Geology 205 (2004) 1–15

ment-bearing West-Carpathian Alpine superunits: Tatric, Veporic and Gemeric (Plasˇienka et al., 1997). The Tatric and Veporic Superunits comprise relatively large granitic plutons that outcrop throughout the region, whereas only small granitic bodies are emplaced in the Gemeric Superunit (Fig. 1). Basement rocks are comprised of Lower Paleozoic metapelites – metapsammites (phyllites to paragneisses) and metaigneous rocks (mainly amphibolites and metarhyolites). Recently, the emplaced granites have been sub-divided into five principal types: (1) Early Variscan (Devonian) S-type metagranites (orthogneisses), (2) Meso-Variscan (Late Devonian to Lower Carboniferous) S- to I-type granites to (leuco)tonalites, (3) Late-Variscan (Upper Carboniferous) I-type tonalites to granodiorites, (4) Post-Variscan (Permian) A-type leucogranites, granite porphyries and rhyolites plus specialized (rare-element) S-type granites and granite porphyries, and (5) Pre Alpine (Early to

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Middle Triassic) leucogranites and rhyolites (Uher and Broska, 2000; Broska and Uher, 2001). This classification is based on combined mineralogical, geochemical and geochronological criteria, as well as isotopic data (Petrı´k and Kohu´t, 1997). In this study, we report on the geochemical behaviour of P in granite types (2) to (5). 2.1. Meso-Variscan orogenic S-type granites The Meso-Variscan monazite-bearing granites represent the most abundant granite type of the Western Carpathians (Fig. 1). They show a S-type affinity and are characterized by calc-alkaline compositions and low contents of Mg, Ca, Sr, Ba, Zr and REE when compared with I-type granites (Table 1). The aluminum saturation index (ASI) varies between 1.2 and 1.6. Monazite-(Ce), ilmenite, zircon, apatite (locally smoky coloured), almandine and xenotime-(Y) are typical

Fig. 1. Schematized geological map of the West-Carpathian Palaeozoic crystalline basement showing the distribution of the I-, S-, A- and specialized S-type granitic rocks. Abbreviations of the mountain ranges: MK—Male´ Karpaty, PI—Povazˇsky´ Inovec, T—Tribecˇ, Zˇ—Zˇiar, MF— Mala´ Fatra, VF—Vel’ka´ Fatra, SMM—Suchy´, Mala´ Magura, NT—Nı´zke Tatry, VT—Vysoke´ Tatry, CˇH—Cˇierna Hora, SOM—Slovak Ore Mountains.

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Table 1 Chemical analyses of representative bulk rock samples from the principal suites of the West-Carpathian granites Sample

ZK-48

Z-4/89

T-88

T-60

GZ-2

GZ-1

BP-20/91

Granite

S-type

S-type

I-type

I-type

spec. S-type

spec. S-type

A-type

Mts.

M. Karpaty

Zˇiar

Trı´becˇ

Trı´becˇ

Slovak Ore Mts.

Slovak Ore Mts.

Upohlav

SiO2 TiO2 Al2O3 Fe2O3 MnO MgO CaO Na2O K2O P2O5 Total V Cr Co Ni Zn Rb Sr Zr Nb Ba Nd Pb Th U Y La Ce Pr Nd Sm Eu Gd Tb Dy Ho Er Tm Yb Lu

69.67 0.40 15.64 2.71 0.05 0.85 2.61 3.88 3.10 0.13 99.23 34 15 4 tr. 58 119 289 170 11 830 33 14 12 1 14.07 32.32 64.45 7.35 27.21 5 1.08 3.97 0.52 2.85 0.51 1.38 0.19 1.26 0.19

72.95 0.19 14.62 1.59 0.04 0.36 1.19 4.21 3.18 0.12 98.63 17 4 1 tr. 50 101 261 98 8 844 22 28 7 3 10.96 25.38 50.97 5.86 22.56 4.32 0.7 3.21 0.43 2.25 0.39 0.97 0.13 0.83 0.13

64.63 0.79 16.30 4.40 0.07 1.77 3.55 4.22 2.34 0.28 98.69 93 20 11 5 77 72 852 240 13 1105 44 17 10 5 15.18 43.66 87.9 10.21 38.47 6.45 1.58 4.61 0.6 3.11 0.57 1.49 0.21 1.27 0.19

74.30 0.12 13.87 1.12 0.02 0.25 0.89 4.26 4.00 0.12 99.08 10 1 tr. tr. 20 113 193 60 8 602 23 29 9 0 11.1 17.73 36.15 4.37 16.35 3.45 0.6 2.79 0.4 2.27 0.42 1.13 0.16 1.05 0.14

67.47 0.05 17.84 1.49 0.03 0.05 0.35 4.59 4.30 0.33 96.62 1 tr. 3 5 70 868 15 46 16 29 8 tr. 17 4 10.24 3.55 10.49 1.1 3.83 1.58 0.03 1.56 0.39 2.17 0.33 0.78 0.11 0.67 0.08

71.21 0.04 16.14 1.53 0.02 0.24 0.30 5.92 1.25 0.21 96.88 3 tr. 8 5 78 173 30 33 4 42 0 tr. 15 3 8.12 2.84 6.82 0.92 3.17 1.27 0.02 1.28 0.3 1.73 0.24 0.62 0.09 0.55 0.06

71.64 0.25 13.74 3.08 0.03 0.28 0.76 3.51 5.05 0.07 98.70 16 17 2 5 59 216 63 374 17 1294 61 28 22 3 39.82 68.66 112.49 17.73 68.52 14.16 1.76 11.51 1.71 9.64 1.7 4.57 0.69 4.54 0.66

Data by soultion ICPMS.

accessory phases. The granite origin is interpreted to have been from biotite and/or muscovite dehydration melting of upper crustal quartzo-feldspathic rocks, such as greywackes, due to crustal thickening and prograde metamorphism (Petrı´k, 2000). This event occurred during Early Carboniferous collision, f 370 – 350 Ma ago (according to U – Pb zircon,

Rb – Sr isochron and U –Th – Pb monazite dating, e.g. Petrı´k and Kohu´t, 1997 and references therein). 2.2. Meso to Late-Variscan orogenic I-type granites Meso to Late-Variscan I-type, allanite-bearing granites are metaluminous to slightly peraluminous

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(ASI = 0.9 – 1.1) biotite (leuco)tonalites to granodiorites, rarely biotite to muscovite– biotite granites (Fig. 1). The typical primary accessory mineral assemblage is represented by zircon, magnetite, allanite-(Ce), titanite, epidote and locally also calcic amphibole. This assemblage, together with Mg-rich and Fe3 +-bearing biotite, and Zr and REE geothermometries indicates a relatively high-temperature, water-rich and high oxygen fugacity ( fO2) regime during magma crystallization in comparison with the S-type granite group (Petrı´k et al., 1994; Petrı´k and Broska, 1994). Locally, the presence of magmatic microgranular mafic enclaves is typical for this granite suite. U –Pb isotope zircon dates, and electron microprobe monazite dating yielded two main age intervals: f 360 –340 and 310 – 290 Ma. The origin of these granites has been interpreted as partial melting of underplated intermediate to mafic magma in the extension regime after the main collisional events (Petrı´k, 2000; Broska and Uher, 2001). 2.3. Post-orogenic A-type granites Small intrusions of metaluminous to peraluminous post-orogenic A-type biotite leucogranites (ASI = 0.9– 1.5), granite porphyries and microgranites occur in the Veporic, Gemeric and Transdanubic Superunits (Hungary). Some of these A-type granites occur also as exotic boulders in the Pieniny Klipen Belt Cretaceous to Eocene flysch sequences. U –Pb zircon dates give Lower Permian to Early Triassic ages of their solidification, ca. 280– 240 Ma (Uher and Puskharev, 1994; Putisˇ et al., 2000). These granites have abundant K-feldspar, or partly exsolved K- and Na-feldspars (hypersolvus to transsolvus textures), that is reflected in the bulk rock chemistry by high K and Na, and low Ca contents. Other geochemical characteristics include high Fe/Mg ratios (the biotite is annite-rich), high Zr and REE contents, but low P, V and Sr concentrations. Zircon and allanite-(Ce) are abundant, particularly in the hypersolvus to transsolvus members, whereas the subsolvus A-type granites locally contain also xenotime-(Y) and monazite-(Ce) (Uher and Broska, 1996). These post-orogenic intrusions are considered to have crystallized from water-poor and F-rich magmas, generated in an extensional, extensive heat flow environment, controlled by strike – slip tectonics (Uher and Broska, 1996).

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2.4. Post-orogenic specialized S-type granites The specialized S-type granites in the West-Carpathian area (the Spisˇ –Gemer type) are represented by biotite – muscovite to muscovite leucogranites, and rare granite porphyries. They form small granite bodies, Permian in age (270 –250 Ma according to zircon and monazite mineral dates, and Rb – Sr whole-rock data, e.g. Finger and Broska, 1999; Poller et al., 2002), which occur only in the Gemeric Superunit (Fig. 1). These granites are typically enriched in Rb, Sn, F and P-locally up to 0.4 wt.% P2O5. ASI values exceed 1.2, with an average of 1.6. The cupolas of the Spisˇ – Gemer granites are often enriched in volatiles, and locally, greisenization and albitization processes are characteristic, and topazbearing granites are partially developed. The accessory minerals include tourmaline (schorl to foitite), almandine, topaz, zircon, apatite, locally also rare monazite-(Ce), xenotime-(Y), cassiterite, wolframite, and Nb –Ta phases (e.g. Faryad and Dianisˇka, 1989; Broska et al., 1998; Uher et al., 2001). Zircon of S8 typology dominates and is a distinguishing feature of these granites (Jakabska´ and Rozlozˇ nı´k, 1989; Broska and Uher, 1991). These granites also contain very high initial Sr isotope ratios (>0.720, Kova´ch et al., 1986), which indicates a mature continental metasedimentary feldspar and muscovite-rich protolith which gave rise to high K, Rb and B contents in the granites. The unusual characteristics of the mineralisation of these S-type granites gave rise to the name specialised S-type granite (Uher and Broska, 1996).

3. Analytical techniques Alkali feldspar was analysed using a Cameca SX 100 electron microprobe at the Geological Survey of the Slovak Republic operated at 15 kV, 20 nA and with a beam diameter 2 Am. For the measurement of low levels of P in feldspar a wavelength-dispersive technique was essential because of the high background levels at the P Ka line. Phosphorus was measured for 60 s at the peak position using a highsensitivity PET crystal. Synthetic and natural standards were used for quantification. Apatite was analysed using a Cameca SX50 electron microprobe at

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the National History Museum, London. Operating conditions were 15 kV, 25 nA beam current and a beam diameter of 1– 5 Am, depending on the apatite grain size. Care was taken in the determination of F and a PC1 (multi-layer crystal) was used to eliminate the potential interference from the P 3rd-order line. The cathodoluminescence study was performed for apatite distribution in fieldspars by a hot cathode HC2LM, Simon Neuser apparatus with an accelerating voltage of 14 kV and beam current of 10 AA mm 2 at the Masaryk University, Brno.

4. Results and discussion 4.1. Phosphorus distribution in the Variscan WestCarpathian granites 4.1.1. Orogenic granites with S-type affinity The P2O5 vs. SiO2 diagram for the bulk samples (Fig. 2a) illustrate that the poorly to moderately fractionated granites (generally < 70 wt.% SiO2) decrease in P2O5 and increase in SiO2. In contrast, for most of the evolved West-Carpathian S-type granites (i.e. >70 wt.% SiO2), both P2O5 and SiO2 contents increase, a trend that can also be seen in the ASI against P2O5 diagram (Fig. 3a). In the S-type granites, the observed increase in P2O5 in the highly differentiated members of granites is connected to an overall increase in phosphorus solubility with increasing excess of Al (Pichavant et al., 1992). The increase in P is the result of fractionation of the melt toward a more aluminous composition until saturation of Al-bearing phase occurs, and is the reason for the positive correlations observed between ASI and Si, and ASI and P (Wolf and London, 1994; London et al., 1999; Chappell and White, 1998; Chappell, 1999). We believe also that an increase in the activity of the alkalines contributes to the solubility of P in the felsic melts. It follows from the increasing of P solubility, or its concentration in the late differentiated granitic members of the S-type suites, sometimes accompanied with only a slight increasing of peraluminousity, but more pronounced increase in the alkaline activity (Fig. 3a). In the S-type granites, P is enriched in the late-magmatic, highly evolved and fluid-rich leucogranitic members, and can be incorporated into the alkali feldspars during solidification of peraluminous melt. Thus, early magmatic feldspars

Fig. 2. Plot of P2O5 vs. SiO2 for whole rock samples. (a) Lower Carboniferous orogenic S-type granites, (b) Lower to Upper Carboniferous orogenic I-type granites, (c) Permian to Triassic post-orogenic A-type granites, (d) Permian post-orogenic specialized S-type granites.

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in phosphorus (up to 0.13 wt.% of P2O5, sample T60, Table 2). These values are similar to those of the S-type granites. 4.1.3. Post-orogenic A-type granites The A-type granites form a distinctive group containing the lowest concentration of whole-rock P, and lowest modal proportion of apatite, in comparison to the I-, S- and specialized S-type granites (Fig. 2c). The very low P2O5 contents ( V 0.2 wt.%) in the A-type group is similar to that observed in A-type granites from other localities world-wide, and reflects their origin from the older (meta)igneous rocks after main collisional orogenesis (e.g. Clemens et al., 1986; Whalen et al., 1987; Patino Douce, 1997), where fractionation of the felsic protolith produced a depletion in P in the melt forming these granite types. As a result, phosphate minerals apatite, monazite-(Ce) or xenotime-(Y) are rare, and P is not detected in the alkali feldspars of the A-type group (Table 2).

Fig. 3. (a) Plot of ASI vs. P2O5 for the Variscan S-type, specialized S-type and A-type West-Carpathian granitic rocks, (b) ASI vs. P2O5 plot of the Variscan I-type West-Carpathian granitic rocks. The arrows show fractionation trends.

have P contents below microprobe detection limit ( < 0.01% P2O5) compared with the late differentiated members where the P content reaches 0.2 wt.% P2O5 (Table 2). 4.1.2. Orogenic granites with I-type affinity Tonalites to granodiorites with I-type affinity are the most apatite-rich rocks within the Variscan WestCarpathian granite suites. Less differentiated, more basic members contain up to 0.45 wt.%, P2O5 but the latest, more differentiated I-type granites and aplitic dikes have much lower P2O5 contents, typically f 0.1 wt.% (Fig. 2b). This decrease in P results from the fractionational crystallization of apatite during formation of the more basic members, illustrated by the observed decreasing trend in the plot of P2O5 against ASI (Fig. 3b). However, in the I-type group, late-magmatic interstitial K-feldspar formed from Al-rich residual melts slightly enriched

4.1.4. Post-orogenic specialized S-type granites Alkali feldspar is the dominant host phase for P in these granites, especially in their topaz-bearing facies. The P2O5 content in the K-feldspar is variable up to 0.3 wt.% (Fig. 2d, Table 2), whereas albite contains only 0.01 – 0.1 wt.% P 2O5. The majority of alkali feldspar in the highly evolved granites have much higher concentrations of P, up to 0.4 wt.% P2O5. However, some of the alkali feldspar grains contain very small (typically < 10 Am size), late to post-magmatic exsolved apatite crystals, and these feldspar grains have significantly lower contents of P2O5. Nevertheless, apatite is volumetrically very low in the specialized S-type granites ( < 0.01 vol.%), and the bulk of the P is distributed both as primary apatites and in the dissolved form in the alkali feldspars. Additionally, these highly evolved granites contain P-bearing topaz that contains up to 0.15 wt.% of P2O5 and detectable levels of P in some zircons. 4.2. Apatite distribution and composition 4.2.1. Primary-magmatic apatite Apatite is abundant in the I-type granites, and less common in the S-specialized, S- and A-type granites.

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Table 2 Representative microprobe analyses (in wt.% oxide) of alkali feldspar grains from the S-, I-, A and specialized S-type granites of the Western Carpathians Type

I type

I type

S-type

S-type

Spec. S-type

Spec. S-type

A-type

A-type

DD-20

GZ-2

BP-19

BP-20

0.16 63.96 18.41 0.00 0.00 0.31 16.59 99.43

0.03 63.95 18.33 0.00 0.03 0.39 16.71 99.44

0.00 64.07 18.43 0.00 0.04 0.26 16.41 99.20

0.00 64.73 18.50 0.00 0.02 0.44 16.29 99.97

Sample

DG-77

T-60

GMK-1

Zˇ-4

P2O5 SiO2 Al2O3 CaO FeO Na2O K2O Total

0.04 64.22 18.45 0.00 0.00 0.89 15.48 99.10

0.13 63.76 18.14 0.00 0.05 0.66 16.37 99.11

0.04 63.08 18.52 0.00 0.00 0.69 16.08 98.42

0.19 64.15 18.72 0.00 0.02 1.47 15.39 99.93

Calculated on the basis 8 O P 0.002 Si 2.989 Al 1.012 Ca 0.000 Fe 0.000 Na 0.081 K 0.919 Total 5.003 XOr 0.919 XAb 0.081

0.005 2.983 1.001 0.000 0.002 0.060 0.977 5.028 0.942 0.058

0.002 2.970 1.028 0.000 0.000 0.063 0.966 5.029 0.938 0.062

0.007 2.966 1.020 0.000 0.001 0.132 0.908 5.033 0.873 0.127

0.001 0.000 2.984 2.989 1.008 1.013 0.000 0.000 0.001 0.002 0.036 0.023 0.995 0.977 5.025 5.004 0.966 0.977 0.034 0.023 Localities: DG-77 Slovak Ore Mts., Hrinˇova´ (Bystre´); T-60 Tribecˇ, Zlatno; GMk-1 Male´ karpaty, Zˇel. Studnicˇka; Zˇ-4-Zˇiar, Brezany; Slovak Ore Mts., Dlha´dolina; GZ-2 Slovak Ore Mts., Hnilec; BP-19, 20 Pieniny Klippen Belt.

In all of the granite types, apatite is mainly located in biotite, with only minor amounts occurring in plagioclase and in interstitial positions. This apatite is considered as a primary accessory mineral that has crystallized as an early magmatic phase. Sr in primary apatite from the orogenic granites (I- and S-types), as a function of the felsic melt fractional differentiation, directly correlates with the host rock composition (correlation coefficient Sr in apatite/rock is close to 0.8). In the post-orogenic specialized S-type granites, where alkali feldspar dominates and albite has very low An contents, primary apatite is relatively more abundant. Apatite from the I-type granites contains significantly lower concentrations of Mn and Fe than apatite from S-type granites (Fig. 4), where MnO contents exceed 0.4 wt.% (Table 3). This increase in Mn content in apatite of the more felsic granitic rocks is a function of an increase in the Mn/Fe and Mn/Ca ratios with fractionation. According to Sha and Chappell (2000), the higher content of Mn and Fe in apatite of S-type magma correlates with a higher Al-content and lower oxygen fugacity. Thus in S-type magmas,

0.006 2.980 1.011 0.000 0.000 0.028 0.986 5.012 0.972 0.028

0.000 2.993 1.008 0.000 0.001 0.039 0.961 5.003 0.961 0.039 DD-20

divalent Mn2 + and Fe2 + cations are relatively more abundant, and subsequently better available to substitution for Ca2 + in apatite than the oxidised form of these elements. The highest contents of MnO in apatite were observed in the specialized S-type granites with concentrations typically 1– 2 wt.% MnO (Fig. 4, Table 3), but locally exceeding 4 wt.%. The highest Fe content in 1– 2 wt.% MnO or 0.1 Mn apfu (Fig. 4, Table 3) some apatites of the A-type granites is due to a primary enrichment in Fe within these granites (Broska and Uher, 2001). Apatite from the I-type granitoids is slightly enriched in sulphur relative to the other granitic types. Some apatite crystals, especially those from the more basic granitic rocks (i.e. tonalites of the Tribec and Slovak Ore mountains—Sihla type), contain up to 0.5 wt.% SO3, and is consistent with the increased contents of sulphides (mainly pyrite) in these rocks. Sulphur is accommodated into the apatite structure by coupled substitution with Si (SiSP 2) Piccoli and Candela (2002). Increased sulphur contents in apatite from I-type granites corre-

I. Broska et al. / Chemical Geology 205 (2004) 1–15

9

Table 3 (a) Representative microprobe analyses (in wt.% oxide) of apatite from the principal granite suites of the Western Carpathians Granite

I-type

I-type

I-type

I-type

S-type

S-type

S-type

S-type

Sample

GB-3

ZK-38

T-88

VT-5

T-87

GMK-1

VF-612

Z-4

Mts. Apatite

Slovak Ore Mts. Mala´ Fatra Primary Primary

Tribecˇ Primary

Vysoke´ Tatry Tribecˇ Primary Primary

Male´ Karpaty Vel’ka´ Fatra Zˇiar Primary Primary Primary

SO3 P2O5 SiO2 Al2O3 La2O3 Ce2O3 Pr2O3 Nd2O3 Sm2O3 Gd2O3 Dy2O3 Er2O3 Yb2O3 Y2O3 ThO2 UO2 CaO PbO FeO MnO MgO SrO Na2O F Cl OH Total O = F,Cl

0.15 40.80 0.10 b.d. 0.03 0.12 0.02 0.03 0.02 0.01 0.01 0.02 b.d. 0.12 n.d. n.d. 55.16 b.d. 0.10 0.08 0.00 0.11 0.01 2.63 0.11 0.41 100.49 1.13

0.09 42.50 0.04 b.d. 0.03 0.05 0.02 0.05 0.02 0.03 0.02 0.05 0.02 0.07 0.03 0.04 54.11 0.01 0.05 0.13 0.01 0.08 0.12 1.65 0.09 0.84 100.13 0.71

0.17 41.05 0.50 b.d. 0.13 0.29 0.01 0.10 0.03 n.d. n.d. n.d. n.d. 0.11 n.d. n.d. 55.06 n.d. 0.16 0.11 0.03 0.07 0.02 2.88 0.14 0.32 101.18 1.24

0.00 42.12 0.02 0.04 0.04 0.06 0.08 0.10 0.02 0.00 0.00 0.00 0.00 0.12 0.03 0.18 54.54 b.d. 0.14 0.23 0.01 0.12 0.12 2.81 0.03 0.38 101.18 1.19

b.d. 40.92 0.39 b.d. 0.05 0.29 0.01 0.03 0.01 n.d. n.d. n.d. n.d. 0.10 n.d. n.d. 54.52 n.d. 0.72 0.36 0.01 0.03 0.14 2.45 0.07 0.56 99.96 1.05

b.d. 41.99 0.03 0.04 0.03 0.03 0.14 0.05 0.00 n.d. n.d. n.d. n.d. 0.11 0.06 0.06 55.09 n.d. 0.16 0.07 b.d. 0.05 0.05 2.01 0.05 0.70 100.73 0.86

0.02 43.03 b.d. 0.02 0.03 0.12 0.04 0.02 0.02 b.d. 0.07 b.d. b.d. 0.22 b.d. 0.13 54.34 b.d. 0.17 0.22 b.d. 0.06 0.12 2.14 0.01 0.67 101.45 0.90

0.00 41.58 0.23 0.00 0.06 0.25 0.01 0.02 0.01 0.00 0.00 0.00 0.00 0.00 0.00 0.00 55.01 0.00 0.14 0.34 0.01 0.06 0.16 2.55 0.02 0.48 100.93 1.08

TOTAL XFApAp XClApAp XHApAp

99.36 0.72 0.02 0.27

99.42 0.45 0.01 0.54

99.93 0.78 0.02 0.20

99.99 0.76 0.00 0.24

98.91 0.64 0.01 0.35

99.87 0.54 0.01 0.45

100.54 0.57 0.00 0.42

99.85 0.69 0.00 0.31

Granite

SS-type

SS-type

SS-type

SS-type

SS-type

A-type

A-type

A-type

A-type

Sample

GK-8

GK-6

GZ-1

GK-8

DD-20

VG-89

VG-89

BP-14

BP-20

Mts. Apatite

Sl.Ore Mts. Primary

Sl.Ore Mts. Sl.Ore Mts. Sl.Ore Mts. Primary Secondary Secondary

Sl.Ore Mts. Sl.Ore Mts. Primary Primary

Sl.Ore Mts. Primary

Klippen belt Klippen belt Primary Primary

SO3 P2O5 SiO2 Al2O3 La2O3 Ce2O3 Pr2O3 Nd2O3 Sm2O3

b.d. 42.09 0.00 b.d. b.d. b.d. 0.13 b.d. b.d.

0.02 41.74 0.24 b.d. 0.01 0.14 0.02 0.09 0.07

b.d. 41.28 0.05 0.04 0.04 0.13 b.d. 0.05 0.01

0.02 41.16 0.35 0.00 0.00 0.18 0.10 0.26 0.00

0.02 0.02 40.60 39.78 0.19 0.40 0.02 0.02 0.26 0.19 0.47 0.53 0.12 0.23 0.36 0.38 0.06 0.15 (continued on next page)

b.d. 42.17 0.04 b.d. 0.02 0.06 0.02 0.06 0.03

b.d. 42.10 0.07 0.03 b.d. 0.19 0.03 0.05 0.06

b.d. 41.53 0.20 0.00 0.03 0.17 0.04 0.15 0.08

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I. Broska et al. / Chemical Geology 205 (2004) 1–15

Table 3 (continued) Granite

SS-type

SS-type

SS-type

SS-type

Sample

GK-8

GK-6

GZ-1

GK-8

Mts. Apatite

Sl.Ore Mts. Primary

Sl.Ore Mts. Sl.Ore Mts. Sl.Ore Mts. Primary Secondary Secondary

Sl.Ore Mts. Sl.Ore Mts. Primary Primary

Gd2O3 Dy2O3 Er2O3 Yb2O3 Y2O3 ThO2 UO2 CaO PbO FeO MnO MgO SrO Na2O F Cl OH Total O = F,Cl TOTAL XFApAp XClApAp XHApAp

n.d. n.d. n.d. n.d. 1.06 b.d. 0.37 51.87 n.d. 0.02 2.23 b.d. 0.38 0.49 2.98 b.d. 0.31 101.92 1.25 100.67 0.80 0.00 0.20

0.08 0.29 0.14 0.00 0.68 0.02 0.13 50.97 0.02 1.36 1.65 0.02 b.d. 0.30 1.87 0.04 0.74 100.63 0.79 99.83 0.51 0.01 0.48

b.d. b.d. b.d. b.d. b.d. b.d. b.d. 51.87 b.d. 0.82 3.31 b.d. 0.02 0.14 3.61 0.04 0.04 101.44 1.53 99.92 0.97 0.01 0.02

0.06 0.15 0.15 0.08 0.60 0.02 0.00 53.29 0.00 0.70 0.59 0.00 0.00 0.13 3.49 0.02 0.09 101.42 1.47 99.95 0.94 0.00 0.06

0.05 0.07 0.10 0.11 0.29 b.d. b.d. 54.42 0.02 0.37 0.11 0.01 0.05 0.15 3.18 b.d. 0.21 101.21 1.34 99.87 0.86 0.00 0.14

0.01 0.01 b.d. b.d. 0.02 b.d. b.d. 55.32 b.d. b.d. b.d. 0.02 0.10 0.02 2.54 b.d. 0.50 100.92 1.07 99.85 0.68 0.00 0.32

b.d. b.d. 0.04 b.d. 0.07 0.06 b.d. 55.10 0.00 b.d. 0.03 b.d. 0.01 0.04 3.20 b.d. 0.23 101.32 1.35 99.98 0.86 0.00 0.14

SS-type

A-type

DD-20

VG-89

0.11 0.13 0.09 0.11 0.53 0.05 0.12 53.35 0.00 0.69 0.55 0.01 0.03 0.17 2.68 0.02 0.42 101.24 1.13 100.10 0.73 0.00 0.27

A-type

A-type

A-type

VG-89

BP-14

BP-20

Sl.Ore Mts. Primary

Klippen belt Klippen belt Primary Primary

(b) Mean and standard deviations of apatite from the principal granite suites of the Western Carpathians I-type i = 98

P2O5 SiO2 CaO La2O3 Ce2O3 Pr2O3 Nd2O3 Sm2O3 Gd2O3 Dy2O3 Er2O3 Yb2O3 Y2O3 ThO2 UO2 Al2O3 SO3 FeO MnO MgO PbO SrO

Spec. S-type i = 50

A-type i = 37

Average

Stdev

Average

S-type i = 60 Stdev

Average

Stdev

Average

Stdev

41.89 0.16 56.11 0.04 0.13 0.02 0.04 0.02 0.03 0.05 0.02 0.02 0.09 0.04 0.06 0.01 0.10 0.10 0.12 0.01 0.01 0.08

0.79 0.11 0.75 0.03 0.08 0.03 0.05 0.01 0.03 0.05 0.02 0.02 0.06 0.05 0.05 0.01 0.11 0.08 0.10 0.01 0.01 0.03

42.01 0.12 55.21 0.04 0.12 0.04 0.02 0.04 0.05 0.10 0.04 0.01 0.17 0.03 0.04 0.01 0.03 0.19 0.36 0.01 0.02 0.06

0.80 0.12 0.61 0.03 0.09 0.06 0.04 0.04 0.05 0.09 0.04 0.01 0.08 0.04 0.05 0.01 0.04 0.14 0.16 0.02 0.02 0.03

41.09 0.26 53.28 0.03 0.07 0.04 0.03 0.04 0.05 0.18 0.04 0.03 0.34 0.04 0.09 0.14 0.02 0.35 1.53 0.01 0.01 0.13

1.80 0.38 2.13 0.02 0.06 0.06 0.03 0.05 0.04 0.13 0.05 0.03 0.19 0.04 0.12 0.23 0.02 0.28 1.29 0.01 0.02 0.10

39.79 0.30 55.49 0.07 0.24 0.07 0.23 0.06 0.10 0.10 0.05 0.05 0.43 0.03 0.03 0.01 0.02 0.45 0.29 0.01 0.02 0.04

1.14 0.55 1.58 0.06 0.33 0.09 0.29 0.08 0.14 0.09 0.04 0.04 0.29 0.03 0.03 0.02 0.02 0.26 0.20 0.01 0.02 0.04

0.13 0.05 0.06 0.00 0.32 0.04 b.d. 54.28 0.02 0.96 0.12 0.01 0.00 0.06 2.80 b.d. 0.35 100.90 1.18 99.72 0.77 0.00 0.23

I. Broska et al. / Chemical Geology 205 (2004) 1–15

11

Table 3 (continued) (b) Mean and standard deviations of apatite from the principal granite suites of the Western Carpathians I-type i = 98

Na2O F Cl OH XFApAp XClApAp XHApAp

Spec. S-type i = 50

A-type i = 37

Average

Stdev

Average

S-type i = 60 Stdev

Average

Stdev

Average

Stdev

0.07 2.61 0.05 0.49 0.69 0.01 0.30

0.05 0.53 0.05 0.23 0.14 0.01 0.14

0.11 2.47 0.03 0.57 0.64 0.00 0.35

0.03 0.40 0.03 0.16 0.10 0.00 0.10

0.19 2.74 0.02 0.42 0.73 0.00 0.27

0.17 0.61 0.02 0.25 0.16 0.00 0.16

0.12 3.05 0.01 0.26 0.83 0.00 0.17

0.06 0.39 0.01 0.17 0.11 0.00 0.11

Calculated on the basis of 13 O. Abreviations: n.d. not determined; b.d. below detection limit. Apatite from the 11 representative I-type granite samples, nine samples from the S-type, six from the specialized S-types and three from the Atypes, has been used.

lates with a relatively oxidized magma (Tepper and Kuehner, 1999). The silicon content (or britholite molecule) in apatite is highest in apatites from the A-type granites with locally >2 wt.% of SiO2 (e.g. sample BP-20, Klipenn Belt). The fluorine and chlorine contents in apatite show some minor variations with granite type (Fig. 5, Table 3). Apatite of the A- and specialized S-type granites have the highest F contents, with some locally close to the ideal fluorapatite end-member stochiometry (XApF>0.95). The Cl content in apatite is generally very low (typically < 0.05%), but does show some

correlation with rock type, with an increase towards the I-type granite group and especially to their more basic (tonalite) members. The REE content in apatite is low, with SREE oxides typically < 0.5 wt.% (Table 3). In the I- and Stype granites, apatite is light-REE enriched. However, in the specialized S-type granite as well as in the Atype the apatite is relatively enriched in heavy-REE and Y (average value of 0.43 wt.% Y2O3), with locally, some apatite domains contain up to 2.0 wt.% Y2O3 (Fig. 6). Here late-stage fluid activity caused also the mobility of the REE, which resulted in the precipitation of secondary xenotime-(Y) (Fig. 6)

Fig. 4. Fe and Mn concentrations in apatites from the principal S-, I-, A- and specialized S-type granite groups of the Western Carpathians. The highest values, >0.03 Mn a.p.f.u. occur in apatite from fractionated granites of the Spisˇ-Gemer spec. S=type granite, Slovak Ore Mts. (Ss type granite).

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I. Broska et al. / Chemical Geology 205 (2004) 1–15

Fig. 5. End-member chlorapatite vs. fluoapatite from the Variscan West-Carpathian granites. The highest Cl content occurs in the I-type granitic rocks. Many of the apatite analyses from the S-, SS- and A-type granites contain Cl-end member below the detection limit.

Fig. 6. Backscattered electron image (BSE), Mn and Y element distribution maps of zoned apatite sample GK-8 (specialized S-type granite). Position A contains 0.01 wt.% MnO (Y2O3 is below detection), B contains 2.24 wt.% MnO, 1.15 wt.% Y2O3; limit C contains 0.84% MnO (Y2O3 is below detection limit). Newly-formed secondary xenotime-(Y) started to precipitation of the fine grained white mica (Fig. 7).

I. Broska et al. / Chemical Geology 205 (2004) 1–15

what is already known from the experiments (Harlow et al., 2002, Harlow and Fo¨rster, 2003). The apatite of the A-type granites are also relatively enriched in Y2O3 because of the high primary HREE contents in the A- and also specialized S-type granites. 4.2.2. Post-magmatic apatite Abundant tiny scattered crystals of apatites (typically < 10 Am in diameter) (Fig. 7) were observed within alkali feldspar (mainly albite) of the specialized West-Carpathian S-type granites. These fluorapatite crystals are considered to have formed as a result of subsolidus redistribution of the P released by the alkali feldspar during decreasing temperature and increasing fluid activity. Consequently, the albite grains hosting the exsolved apatites have significantly lower P contents (usually below the microprobe detection limit). The alkali feldspar is also a potential source of Ca for the fluorapatite, and the excess of Al (from the breakdown of the feldspar) resulted in precipitation of the fine-grained white mica (Fig. 7). It is also clear that F-bearing fluids played a significant role in the overall process of late-stage apatite formation, as indicated the presence of apatite in microfractures, especially in the topaz-bearing spe-

13

cialized S-type granites. Consequently, a combination of initial high-P feldspar, Ca-bearing albite and latemagmatic F-rich corrosive fluids gave rise to the conditions favourable for the exsolution (or alteration) and precipitation of fine-grained fluorapatite crystals locally disseminated mainly in the albites of the specialized S-type granites. In contrast to primary early-magmatic fluorapatite, the late to post-magmatic fluorapatite is closer to the stoichometric fluorapatite, with significantly lower Mn contents (typically < 0.5% oxides), and low concentrations of REE.

5. Conclusions The geochemistry of P, as well as the composition and distribution of apatite and P-bearing alkali feldspars, can be explained within the framework of contrasting granite suites, using as an example the Variscan magmatism of the Western Carpathians, Slovakia. (i) The fractionational crystallization of apatite in the I-type granites results in a decrease in P content within the bulk residual magma. Phosphorus also decreases with the aluminium saturation index

Fig. 7. Backscattered electron image to illustrate the redistribution of P in alkali feldspar: (a) BSE image (b) detail. This post-magmatic generation of apatite forms tiny crystals within alkali feldspar grains and in micro-cracks and fractures permeating the feldspar. The albite composition, after precipitation of apatite, contains only trace amounts of phosphorus. Sample: SS-granite type (locality Hnilec: GZ-1). White mica (Ms) also occurs due to an excess of Al from the feldspar. Scalebar 500 Am.

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I. Broska et al. / Chemical Geology 205 (2004) 1–15

(ASI) increase. The observed decrease in P in the granites with S-type affinity, resulting from the fractionation of P-bearing accessory phases (apatite, monazite, xenotime), is valid only for the more basic members (i.e. tonalites and granodiorites). With further fractionation, the Stype granites produced an increase in P activity in the more peraluminous melts, and the formation of P-bearing alkali feldspars (mainly Kfs). In general, the P content in the feldspar increases with the ASI parameter of the bulk rock. (ii) Apatite and REE accessory minerals, such as monazite and xenotime, are the main hosts for P in felsic melts. A significant contribution, however, can be alkali feldspars from the highly evolved specialized S-type granites, which can contain up to 0.4 wt.% P2O5; intermediate concentrations of P (0.01 –0.2 wt.% P2O5) are present in the late magmatic members of the Sand I-type suites, and the lowest concentrations in the A-type granites. (iii) Early magmatic apatite is abundant in the I-type granite; less abundant in the S-type, and relatively rare in the A-type and specialized S-type granite suites. Post-magmatic apatite crystals distributed within alkali feldspar grains were formed by the transformation of P-bearing alkali feldspar during interaction with F-rich fluids. (iv) The compositions of apatite from different granitic types are linked with the bulk chemical compositions of their host rocks mainly in Sr distribution. But apatite from the S-type granites, and particularly from the specialized S-type granites, is enriched in Mn relative to the I-type granites due to the different physico-chemical condition in these two type of the melt (I-type is more oxidized melt). An increase in Y and heavy REE in the specialized S-types, and further increase in the Atype granitic suite, is associated with an increase of these elements in their bulk rock compositions. Moreover, the elevated contents of Fe in apatite from A-type granites correspond to an Fe-enrichment of the parental rocks. Apatite from the basic members of the I-type granites contains the highest contents of Cl and S. (v) Apatite provides some discrimination parameters for the recognition of the I-, S- and A-type granite suites.

Acknowledgements The authors are greatly indebted to D. Garcia and D. London for their comments and useful suggestions that helped considerably to improve the manuscript. This study was supported by VEGA Grant #1143 (Slovak Acad. Sci.) and by the EU-IHP Programme for IB to visit the Natural History Museum, London. Authors thank I. Dianisˇka and P. Malachovsky´ for the sample DD-20 from borehole in Dlha¯ dolina. [RR] References Bea, F., Fershtater, G., Corretge´, L.G., 1992. The geochemistry of phosphorus in granite and the effect of aluminium. Lithos 29, 43 – 45. Belousova, E.A., Walters, S., Griffin, W.L., O’Reilly, S.Y., 2001. Trace-element signatures of apatites in granitoids from the Mt. Isa Inlier, northwestern Queensland. Aust. J. Sci. 48, 603 – 619. Broska, I., Uher, P., 1991. Regional typology of zircon and their relationship to allanite – monazite antagonism (on example of Hercynian granitoids of the Western Carpathians). Geol. Carpath. 42, 271 – 277. Broska, I., Uher, P., 2001. Whole-rock chemistry and genetic typology of the West-Carpathian Variscan granites. Geol. Carpath. 52, 79 – 90. Broska, I., Uher, P., Lipka, J., 1998. Brown and blue schorl from the Spisˇ – Gemer granite, Slovakia: composition and genetic relations. J. Czech Geol. Soc. 43, 9 – 16. Chappell, B.W., 1999. Aluminium saturation in I- and S-type granites and the characterization of fractionated haplogranites. Lithos 46, 535 – 551. Chappell, B.W., White, A.J.R., 1998. Development of P-rich granites by sequential restite fractionation and fractional crystallization: the Koetong Suite in the Lachlan fold belt. Acta Univ. Carol., Geol. 42, 23 – 27. Clemens, J.D., Holloway, J.R., White, A.J.R., Chappell, B.W., 1986. Origin of a-type granites: experimental constraints. Am. Mineral., 71317 – 71324. Faryad, S.W., Dianisˇka, I., 1989. Garnets from granitoids of the Spisˇsko – Gemerske´ Rudohorie Mts. Geol. Zb. Geol. Carpath. 40, 715 – 734. Finger, F., Broska, I., 1999. The gemeric S-type granites in southeastern Slovakia: late Palaeozoic or Alpine intrusion? Evidence from the electron-microprobe dating of monazite. Schweiz. Mineral. Petrogr. Mitt. 79, 439 – 443. Fry´da, J., Breiter, K., 1995. Alkali feldspars as a main phosphorus reservoir in rare-metal granites: three examples from the Bohemian Massif (Czech Republic). Terra Nova 7, 315 – 320. Green, T.H., Watson, E.B., 1982. Crystallization of apatite in natural magmas under high pressure, hydrous conditions, with particular references to ‘‘orogenic’’ rock series. Contrib. Mineral. Petrol. 79, 96 – 105.

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