Eur. J. Mineral.

2009, 21, 335346

Published online December 2008

Evolution of rare-metal granitic magmas documented

by quartz chemistry
Karel BREITER1, * and Axel MULLER2

1
Geological Institute of Czech Academy of Science, v.v.i., Rozvojova 269,
CZ-165 00 Praha 6, Czech Republic
*Corresponding author, e-mail: breiter@gli.cas.cz
2
Geological Survey of Norway, NO-7491 Trondheim, Norway

Abstract: The study documents changes in the chemical composition of igneous quartz during evolution of two contrasting late-
Variscan granite suites in the Erzgebirge/Krusne Hory Mts., Czech Republic. Quartz is the chemically most resistant rock-forming
mineral in granitoids, so trace-element signatures in quartz preserve its magmatic character during all common post-magmatic
alterations. Six quartz populations were optically distinguished in each of the studied granite suites: a highly peraluminous
phosphorus-rich (S-type) from Podles, and slightly peraluminous P-poor (A-type) from Hora Svate Kateriny. Contents of Li, Be, B,
Al, Ge, P, K, Na, Ca, Ti, Mn, and Fe were determined in situ in all quartz types using laser ablation inductively coupled plasma mass
spectrometry, LA-ICP-MS. Of all the determined elements, only Ti decreases with increasing fractionation. Al reached the highest
contents in all samples (1001200 lg g 1), followed by Ti, Li, and K (in the range of 10100 lg g 1). The Ti vs. Al diagram is the
most tting indicator of the evolution of the melt from which the quartz crystallised. Al enters the quartz lattice according to coupled
substitution Si4+ M Al3+ + (Li, K, H)+. No rst-hand correlation between Al in quartz and the peraluminosity of the melt was found.
Contents of Al increase from the early to the late quartz populations, by factors of 3 in Podles and 10 in Katerina, despite the
aluminium saturation index of both granite systems increasing only slightly or becoming stable: 1.201.35 in Podles and 1.05 in
Katerina. The contents of B, Be, Ge, Fe, Mn, and P in quartz are usually lower than 10 lg g 1 and their abundances are generally
positively correlated with whole-rock chemical compositions. Erratic, high contents of Fe and Mn in quartz from marginal pegmatite
may be attributed to inltration of uid from the exocontact during quartz crystallisation.
Key-words: quartz, LA-ICP-MS, trace element analysis, rare metal granite, Erzgebirge, Krusne Hory.

1. Introduction dance in the melt, the partitioning between different phases

Whole-rock chemistry and mineralogy are commonly used
for the description, classication, and petrogenetic recon-
struction of silica-oversaturated rocks (Raimbault et al.,
1995; London, 1996; Forster et al., 1999; Reyf et al.,
2000). The chemistry of rock-forming minerals, such as
quartz, feldspar and mica often reveals detailed information
about crystallisation processes and fractionation trends
(London, 1992; Charoy et al., 1995; Breiter et al., 2002;
Muller et al., 2005). However, feldspar and mica in granites
are commonly altered, in particular in highly fractionated
granites, due to late- to post-magmatic interaction with deu-
teric and hydrothermal uids. Quartz is more resistant in this
environment, with the consequence that the magmatic trace-
element signature is commonly preserved (e.g., Muller et al.,
2000; Rufni et al., 2002).
Recent developments in micro-beam techniques allow the
precise in situ determination of trace-element concentrations
in quartz (e.g., Watt et al., 1997; Flem et al., 2002; Muller
et al., 2003; Larsen et al., 2004). Generally, the concentra-
tion of trace elements in quartz is controlled by their abun-
and the thermodynamic conditions in the system. However,
understanding of the processes controlling trace-element
uptake into the quartz lattice is still not advanced. The total
content of Al, Ti, Ge, Fe, and Li in igneous quartz has been
used to discriminate between magmas of different origin, or
in order to better understand the fractionation process
(Lyakhovich, 1972; Suttner & Leininger, 1972; Schron
et al., 1988; Gurbanov et al., 1999; Larsen et al., 2000,
2004; Gotze et al., 2004; Jacamon & Larsen, in review).
Wark & Watson (2006) established the Ti-in-quartz geother-
mometer, which allows the calculation of the magma tem-
perature at different stages of quartz growth (Wark et al.,
2007; Wiebe et al., 2007). However, the potential of quartz
chemistry to reveal changes in thermodynamic and chemical
conditions during magma evolution is considerably higher,
as indicated by Muller et al. (2000, 2002, 2003) and
Jacamon & Larsen (in review).
The aim of this study is to document the trace-element evo-
lution of igneous quartz during its evolution from moderate
to highly evolved granite compositions. The late-Variscan,
highly peraluminous phosphorus-rich (P-rich) granites of

0935-1221/09/0021-1907 $ 5.40
DOI: 10.1127/0935-1221/2009/0021-1907
2009 E. Schweizerbartsche Verlagsbuchhandlung, D-70176 Stuttgart
336 K. Breiter, A. Muller
the Podles stock in the western Erzgebirge/Krusne Hory and
the mildly peraluminous phosphorus-poor granites of the
Hora Svate Kateriny stock were chosen for the study. Simi-
larities and differences in trace-element distribution in quartz
during the evolution of one highly peraluminous (S-type) and
the other slightly peraluminous (A-type) uorine-enriched
granite magma are demonstrated. Processes responsible for
the different trace-element signatures and for controlling
the chemical trends in igneous quartz are discussed. Particu-
lar attention is paid to phosphorus.
2. Geological setting of the granite systems
The Erzgebirge/Krusne Hory Mts. represent one of the most
typical areas of late-Variscan magmatic activity in Europe,
culminating with multiple intrusions of highly evolved
FLiSnW-rich granitic magmas. Two types of ore-bearing
granite pluton can be distinguished according to their chem-
ical composition and relative age (Breiter et al., 1991, 1999;
Breiter & Seltmann, 1995; Forster et al., 1999):
i. Highly peraluminous, P-rich granites (S-type), repre-
sented here by the Podles stock, western Erzgebirge,
are enriched in F, P, Li, Rb, Cs, Sn, Nb, Ta, U and
W, and poor in Th, Zr and REE; their age is 325
320 Ma;
ii. Slightly younger (320310 Ma) only mildly peralumi-
nous phosphorus-poor granites (A-like type), repre-
sented here by the Hora Svate Kateriny stock, are
enriched in F, Li, Rb, Cs, Sn, Nb, Ta, U and W, but also
in Th, Zr and REE.
Both granite types intruded at shallow levels (3-1 km?) as
documented by numerous eruptive breccia pipes in and
above the stocks. The mildly peraluminous granites
were preceded and followed by voluminous rhyolite
volcanism.
2.1. The Podles granite system
The Podles granite stock represents the most highly fraction-
ated part of the Nejdek-Eibenstock pluton in the western
Erzgebirge/Krusne Hory Mts. (Breiter et al., 2005). The stock
(outcrop 400 200 m) is composed of albiteprotolithio-
nitetopaz granite (stock granite, 1st evolution stage) bor-
dered by a layer of marginal pegmatite (stockscheider).
The stock granite is intercalated with several at layers of
albitezinnwalditetopaz granite (dyke granite, 2nd evolution
stage) with magmatic layering and unidirectional solidica-
tion textures (UST). The stock granite is strongly peralumi-
nous (A/CNK 1.151.30), enriched in incompatible
elements such as Li, Rb, Cs, Sn, Nb, W, and poor in Mg,
Ca, Sr, Ba, Fe, Sc, Zr, Pb, and V. The rock is rich in phospho-
rus (0.40.8 wt.% P2O5) and uorine (0.61.8 wt.% F). The
dyke granite is even more enriched in Al (A/CNK 1.201.35),
P (0.61.5 wt.% P2O5), F (1.42.4 wt.%), Na, Rb, Li, Nb and
Ta. Post-magmatic processes are very weakly developed.
2.2. The Hora Svate Kateriny granite system
The Hora Svate Kateriny granite forms a stock, about 100 m
in diameter, situated at the village of Hora Svate Kateriny
(Katharinaberg, Mt. St. Catharine, hereafter called Katerina),
in the central, Czech part of the Erzgebirge/Krusne Hory area
(Breiter, in review). The granite was forcefully intruded into
shallow levels. It contains numerous xenoliths of country
rock (orthogneiss and amphibolite without any marks of
resorption) and, in the form of narrow dykes, penetrated its
surroundings and cemented orthogneiss and amphibolite
breccia. Two phases of intrusion can be distinguished textur-
ally: (i) medium-grained biotite granite forms the major part
of the stock. The ne-grained, rapidly cooled matrix of
amphibolite breccias belongs to this phase. The medium-
grained granite was later brecciated and cemented with
(ii) ne-grained leucogranite with only scarce grains of dark
mica. UST commonly evolved around clasts of medium-
grained granite, indicating high contents of uids and deep
undercooling of later-intruded portions of magma. Granites
of both stages are slightly peraluminous (ASI = 1.05) and
are enriched in uorine (about 0.5 wt.% F), Rb (about
9001200 lg g 1), Nb (6080 lg g 1), Ta (1015 lg g 1),
Th (3050 lg g 1), Zr (100160 lg g 1) and Be (519
lg g 1). Mineralogically, granites of both stages are com-
posed of quartz, K-feldspar, albite and Li-bearing biotite.
The main accessory phases are uorite and zircon, with
scarce xenotime, monazite, thorite and chernovite. Apatite
is completely absent due to the low content of phosphorus
(< 0.1 wt.% P2O5 WR). All the types of granite were affected
by strong reaction with post-magmatic uids.
3. Description of quartz generations
Samples chosen for this study of quartz chemistry represent
different evolutional stages of granites from both localities.
The samples and related quartz generations are dened
and summarized in Tables 1 and 2.
Three quartz populations can be distinguished in the
Podles stock granite (intrusion stage 1a): early drop-like to
semi-euhedral quartz phenocrysts (15 mm; PQ1), ne-
grained crystalline anhedral groundmass quartz (0.12 mm;
PQ2) and pegmatitic stockscheider quartz (0.55 cm;
PQ3). The stockscheider forms a 520 cm thick layer at
the contact of the granite stock roof with the host rock.
The stockscheider PQ3 lls interstices between comb
K-feldspar crystals. The sub-horizontal bodies of dyke gran-
ite (intrusion stage 2) contain drop-like snowball quartz (0.2
1.5 mm; PQ4) and later comb quartz in layered textures
(0.52 cm; PQ5). The snowball quartz is evenly distributed
as small drops in the ne-grained albite-matrix of the dyke
granite. The comb quartz forms, together with fan-like zinn-
waldite and comb K-feldspar, a number of at layers of UST
within the dyke granite. The distal part of the dyke granite
was locally brecciated. Comb quartz (13 mm, PQ6) rims
some of the breccia clasts.
The medium-grained biotite granite of Katerina (intrusion
stage 1) contains apparently simply anhedral groundmass
 Quartz chemistry of rare-metal granites 337

Table 1. Description of quartz samples from Podles (UST unidirectional solidication texture; quartz gener. quartz generation).

Intrusion Sample no. Granite facies Quartz description Quartz gener. Zr/Hf assoc.
stage zircon
1a 2754 Stock granite Sub-euhedral quartz phenocrysts PQ1 2738
(15 mm); ne-grained PQ2
groundmass quartz (0.12 mm)
1a 3763 Marginal pegmatite of the Interstitial pegmatitic quartz PQ3 3145
stock granite (stockscheider) (0.55 cm)
2 3916, 3920 Dyke granite Snowball quartz (0.21.5 mm) PQ4 2835
2 3880 Dyke granite Late comb quartz in UST layers PQ5 1719
(0.52 cm)
2 3740 Brecciated dyke granite Comb quartz (15 mm) growing PQ6 1014
(fragments of mica-rich early facies around granite clasts
cemented with late mica-poor facies)
Note: The atomic Zr/Hf ratios of associated zircon are from Breiter et al. (2006). Late interstitial zircons equilibrated with the same melt as
appropriate quartz population and may serve as another indicator of melt evolution.

Table 2. Description of quartz samples from Katerina (UST unidirectional solidication texture; quartz gener. quartz generation).

Intrusion stage Sample no. Granite facies Quartz description Quartz Zr/Hf assoc.
gener. zircon
1 4471 Aplitic granite of the Drop-like quartz phenocrysts KQ1 3748
marginal breccia (0.52 mm)
1 3097 Medium-grained granite Anhedral groundmass quartz KQ2 2633
(main type of the 1st stage) (0.23 mm)
2a 4554 Fine-grained granite Euhedral quartz phenocrysts KQ3a 2040
(main type of the 2nd stage) (13 mm)
2a 4555 Altered ne-grained granite Broken sub-euhedral quartz xenocryst (> 3 cm) KQ3b 3846
2a 4475B Layered granite with UST Early comb quartz in UST layers (0.53 mm) KQ4 2432
2a 4475A Layered granite with UST Early comb quartz in UST layers (0.510 mm) KQ4 2030
2b 4548 Layered granite with UST Drop-like groundmass quartz (0.21 mm) KQ5 10
2b 4546 Layered granite with UST Late comb quartz in UST layers (0.32 cm) KQ6 1227

quartz (0.23 mm). However, the quenched, ne-grained
aplitic facies of the biotite granite cementing amphibolite
breccias, has drop-like quartz phenocrysts (0.52 mm).
Because of their small size the phenocrysts (KQ1) cannot
be distinguished from the younger anhedral groundmass
quartz (KQ2) in the medium-grained facies. The ne-
grained leucogranite (intrusion stage 2a) contains euhedral
and slightly larger phenocrysts (13 mm; KQ3a). Large
(> 3 cm) broken, sub-euhedral crystals occur occasionally
in the leucogranite adjacent to the phenocrysts. The large
crystals are interpreted as pegmatitic xenocrysts (KQ3b)
which presumably originate from the quenched margin of
the magma reservoir. Several generations of UST layers of
comb quartz (0.510 mm; KQ4) are developed within the
ne-grained leucogranite. The younger sub-facies of the leu-
cogranite (intrusion stage 2b) contains drop-like groundmass
quartz (0.21 mm; KQ5) and comb quartz (0.32 cm; KQ6)
in UST layers.
4. Method
Firstly, scanning electron microscope cathodoluminescence
was applied to several quartz crystals from each population
to conrm the primary magmatic origin of the quartz without
signicant hydrothermal overprinting. Laser-ablation induc-
tively coupled plasma mass spectrometry, LA-ICP-MS, was
applied for the in situ determination of Li, Be, B, Al, Ge, P,
K, Na, Ca, Ti, Mn and Fe in quartz. The ICP-MS used in this
study is a double focusing sector eld instrument (model-
ELEMENT-1, Finnigan MAT, Bremen, Germany) combined
with a Finnigan MAT UV laser probe. The 266-nm laser had a
repetition rate of 20 Hz, and pulse energy of 1.51.6 mJ with
continuous ablation on an area of approximately
180 200 lm. The laser beam was adjusted to give a spot
size of approximately 20 lm. External calibration was done
using four silicate glass reference materials produced by the
National Institute of Standards and Technology (NIST
SRM 610, NIST SRM 612, NIST SRM 614, NIST SRM
616). In addition, the standard reference material NIST
1830, soda-lime oat glass (0.1 wt.% Al2O3) from NIST,
the high purity silica BCS 313/1 reference sample from the
Bureau of Analysed Samples, UK, the certied reference
material pure substance No. 1 silicon dioxide SiO2 from
the Federal Institute for Material Research and Testing,
Berlin, Germany and the QzTu synthetic pure quartz
monocrystal provided by Andreas Kronz from the
Geowissenschaftliches Zentrum Gottingen (GZG), Germany,
were used. Each measurement consists of 15 scans of each
isotope, with a measurement time varying from 0.15 s per
338 K. Breiter, A. Muller
scan of K in high resolution to 0.024 s per scan of, e.g. Li in
low resolution. An Ar-blank was run before each standard and
sample measurement. The background signal was subtracted
from the instrumental response of the standard before normal-
isation against the internal standard. This was done to avoid
memory effects between samples. A weighted linear regres-
sion model including several measurements of the different
standards was applied for calculation of the calibration curve
for each element.
The procedure by Muller et al. (2008) has been applied to
calculate the P concentrations in quartz. Muller et al. (2008)
noticed that the multi-material calibration curve obtained
from a suite of reference materials (NIST SRM 610, 612,
614, 1830, BAM No. 1 amorphous SiO2 glass) does not
dene a precise regression line, which suggested that some
of the reference values may be inaccurate. Furthermore, the
calibration curve does not pass through the origin of the
[(cps 31P/cps 30Si) conc. Si] vs. P concentration diagram,
which is caused by the method-related background. Ideally,
the calibration curve should go through the zero point of the
calibration diagram (intercept b = 0). Newly compiled phos-
phorus values for NIST SRM 610 (409 lg g 1), 612
(45.9 lg g 1), 614 (11.1 lg g 1) and 1830 (16.6 lg g 1)
have been applied, resulting in a better-dened LA-ICP-
MS calibration curve (Muller et al., 2008). The value of
the intercept b with the [(cps 31P/cps 30Si) conc. Si] axis
has been subtracted from the 30Si-normalized 31P ICP signal
for calibration of absolute P concentrations in quartz.
Ten successive measurements on the QzTu were used to
estimate the limits of detection (LOD). The LOD are based
on 3 standard deviation (3r) of the 10 measurements,
divided by the sensitivity, S; they are listed in Table 3.
The analytical error ranges within 10 % of the absolute
concentration of the element (Flem & Bedard, 2002; Flem
et al., 2002).
5. Trace elements in quartz
The concentrations of Li, Be, B, Al, Ge, Na, P, K, Ca, Ti,
Mn and Fe in igneous quartz from both the Podles and
Katerina granites are listed in Tables 3 and 4. Variations
of trace elements in quartz are illustrated in concentration
diagrams in Fig. 1. The contents of Ca, Na, and Mn
of quartz from both localities and also the content of P in
the Katerina samples are mostly below the limits of
detection.
The oldest quartz generations in both granite systems PQ1
and KQ1 occurring as quartz phenocrysts have highest aver-
age Ti contents of 60 and 38 lg g 1, respectively. The
phenocrysts represent the earliest stage of the Podles (PQ1)
and Katerina (KQ1) quartz crystallisation. The Ti in KQ1 is
highly variable, from 22 to 64 lg g 1, which is caused by
growth zones with different Ti contents. This feature is com-
mon in igneous quartz phenocrysts (Muller et al., 2000, 2002;
Wark et al., 2007; Wiebe et al., 2007). The anhedral ground-
mass quartz embedding the phenocrysts in the Podles (PQ2)
and Katerina (KQ2) rst-stage granites has much lower Ti
contents, of 28 and 13 lg g 1, respectively. Quartz genera-
tions KQ3 and KQ4 have moderate average Ti contents
(1332 lg g 1), representing the initial phases of the 2nd
intrusion stage. KQ5 and KQ6, representing the evolved
2nd stage, are even more depleted in Ti, with concentrations
below 10 lg g 1. In Podles, the stockscheider quartz
(PQ3) and quartz of the 2nd intrusion stage (PQ4, PQ5 and
PQ6) are poor in Ti as well, although with slightly higher
average contents (1116 lg g 1). Generally, the average Ti
content decreases from the older igneous quartz towards
quartz of the younger, more evolved granite facies (Fig. 1a).
The early quartz generations of Podles (PQ1PQ3) have
higher Al than the early quartz of Katerina (KQ1KQ4).
The difference is about 250 lg g 1. Al contents are compa-
rable in quartz generations KQ2KQ4 (144168 lg g 1)
and increase exponentially in KQ5 and KQ6 (299 and
698 lg g 1). An identical pattern is developed in Podles:
PQ1PQ3 have similar Al (415484 lg g 1) and Al
increases exponentially in PQ4, PQ5, to PQ6 (621, 780,
and 976 lg g 1). Some growth zones in the KQ6 and
PQ6 comb quartz contain more than 1000 lg g 1 Al. Such
high values are reported only from late-magmatic snowball-
textured quartz in highly evolved, F-rich albite granites
(Muller & Seltmann, 1999) and from hydrothermal quartz
(e.g., Mullis & Ramseyer, 1999).
The Al vs. Ti concentration diagram in Fig. 1a yields a
trend reecting the general evolution of the magma. In igne-
ous quartz, Ti decreases and Al increases exponentially with
increasing differentiation of the magma. However, the trends
are not continuous, looking at the scale of individual quartz
generations. Al and Ti can vary considerably in one quartz
generation due to compositional growth zoning.
The K content of Katerina quartz increases systemati-
cally with fractionation from KQ1 (2 lg g 1) to KQ6
(183 lg g 1). K correlates roughly linearly with Al, with
the exception of KQ6 values between 400 and 600 lg g 1
Al (Fig. 1b). In Podles, the average values for the different
quartz generations are in the range of 2030 lg g 1 and
there is no correlation with Al.
The trends of Li in quartz are similar in both granites systems
(Fig. 1c). Li increases systematically from 240 lg g 1
in older generations (KQ1KQ5, PQ1PQ3) to about
100 lg g 1 in the late quartz generations (KQ6, PQ4
PQ6). Li is highly variable in this late quartz, indicating com-
positional zoning. However, the Podles quartz is generally
more enriched in Li than the Katerina quartz. Li correlates
positively with Al. The correlation becomes more precisely
linear if K + Li is plotted against Al (all elements are
expressed in atomic proportions) (Fig. 2). The plot reveals
two distinctive trends for Katerina and Podles: the Katerina
quartz is richer in K and thus the K + Li vs. Al regression is
steeper than that of the Podles quartz. Comparison of the plots
in Fig. 1c and 2 reveals that the relatively low K in KQ6,
400600 lg g 1 Al, is compensated by higher Li.
Be concentrations in KQ1KQ3 are generally below the
limit of detection (0.13 lg g 1) but increase in KQ4,
KQ5, and KQ6 to 2 lg g 1, having a distinct correlation
with Al (Fig. 1d). Be is mostly below the limit of detection
in the Podles quartz. The Podles quartz is generally
 Quartz chemistry of rare-metal granites 339

Table 3. Trace element concentrations (lg g 1) of quartz from Podles. Concentrations were determined by LA-ICP-MS.

Li Be B Al Ge Na P K Ca Ti Mn Fe
LOD 0.77 0.13 1.26 7.2 0.13 13.5 3.5 1.5 28.0 0.9 0.20 0.41
1 1 1 1 1 1 1 1 1 1 1 1
Quartz generation lg g lg g lg g lg g lg g lg g lg g lg g lg g lg g lg g lg g
PQ1 25.67 0.49 8.40 403.0 0.95 < 13.5 < 3.5 86.7 < 28 56.5 2.38 < 0.41
34.76 0.46 1.68 407.1 0.95 < 13.5 < 3.5 29.0 < 28 62.8 0.58 2.83
39.89 0.43 1.74 424.3 0.77 < 13.5 4.0 20.6 < 28 61.7 < 0.2 1.18
32.79 0.47 2.53 425.9 0.97 < 13.5 < 3.5 16.0 < 28 59.2 1.52 2.77
Average 33.28 0.46 3.59 415.1 0.91 < 13.5 < 3.6 38.1 < 28 60.0 < 1.17 < 1.80
PQ2 38.02 0.43 3.86 475.9 1.19 < 13.5 4.8 45.1 < 28 42.4 < 0.2 3.73
34.89 < 0.13 4.03 484.8 0.95 < 13.5 < 3.5 4.3 < 28 15.6 < 0.2 0.72
26.47 0.30 14.15 522.8 1.37 < 13.5 4.7 31.8 < 28 37.4 1.74 2.83
33.87 0.20 11.87 452.8 0.82 < 13.5 4.0 61.1 < 28 14.8 < 0.2 1.31
Average 33.31 0.26 8.48 484.1 1.08 < 13.5 < 4.2 35.6 < 28 27.5 < 0.59 2.15
PQ3 17.76 3.22 12.89 445.6 1.21 < 13.5 < 3.5 82.7 < 28 18.2 7.03 97.97
30.07 1.39 6.19 355.4 1.13 < 13.5 < 3.5 28.0 < 28 17.4 4.51 36.09
28.66 0.16 5.35 372.0 1.18 < 13.5 < 3.5 8.3 < 28 15.3 2.57 13.44
33.95 0.24 9.39 401.2 1.56 < 13.5 < 3.5 33.4 < 28 11.1 2.30 35.68
Average 27.61 1.25 8.46 393.6 1.27 < 13.5 < 3.5 38.1 < 28 15.5 4.10 45.80
PQ4 38.53 < 0.13 7.85 629.0 1.85 < 13.5 4.7 28.7 < 28 11.3 0.72 < 0.41
45.70 0.15 5.74 512.1 1.39 < 13.5 < 3.5 32.4 < 28 7.9 < 0.2 < 0.41
59.70 0.19 3.64 664.8 1.79 < 13.5 < 3.5 20.4 < 28 11.5 < 0.2 1.83
54.34 0.13 4.82 668.0 1.71 < 13.5 < 3.5 15.5 < 28 13.1 0.34 0.74
55.45 0.16 4.76 590.4 0.91 < 13.5 5.3 20.8 < 28 8.4 < 0.2 0.62
58.25 0.14 3.98 663.1 1.66 < 13.5 5.8 19.7 < 28 13.5 < 0.2 2.93
Average 52.00 < 0.15 5.13 621.2 1.55 < 13.5 < 4.4 22.9 < 28 11.0 < 0.31 < 1.16
PQ5 90.87 0.19 1.92 801.2 1.22 < 13.5 < 3.5 21.8 < 28 9.0 < 0.2 1.08
109.17 1.11 4.22 897.2 1.73 < 13.5 4.2 30.8 < 28 14.4 < 0.2 2.46
99.35 0.16 15.03 746.5 1.86 < 13.5 < 3.5 10.2 < 28 12.7 < 0.2 1.22
83.86 0.20 6.09 658.1 2.25 < 13.5 < 3.5 < 1.5 < 28 8.7 < 0.2 1.50
67.67 0.15 5.18 533.0 1.84 < 13.5 < 3.5 < 1.5 < 28 12.3 < 0.2 1.21
71.38 0.17 1.60 491.0 1.50 < 13.5 < 3.5 6.4 < 28 9.1 1.20 1.46
123.87 0.18 5.47 826.9 1.70 < 13.5 < 3.5 < 1.5 < 28 15.4 0.61 2.36
116.14 0.23 6.41 971.4 2.46 < 13.5 6.3 < 1.5 < 28 12.0 1.55 1.29
132.35 0.15 6.13 996.1 1.59 < 13.5 < 3.5 < 1.5 < 28 15.0 < 0.2 1.28
116.82 0.14 5.80 885.6 1.77 < 13.5 < 3.5 < 1.5 < 28 16.3 < 0.2 2.10
103.91 0.19 5.32 959.2 2.18 < 13.5 < 3.5 30.0 < 28 12.7 < 0.2 3.10
90.90 < 0.13 < 1.26 659.5 1.78 < 13.5 < 3.5 5.1 < 28 11.9 0.81 1.13
103.86 0.16 27.58 978.1 1.99 < 13.5 8.4 27.4 < 28 14.5 < 0.2 1.92
96.60 0.20 9.52 782.7 1.93 < 13.5 < 3.5 4.2 < 28 15.0 < 0.2 4.03
99.70 0.20 3.14 843.0 1.57 < 13.5 < 3.5 21.5 < 28 9.0 1.20 0.91
31.79 < 0.13 3.90 762.2 1.58 < 13.5 < 3.5 62.9 < 28 14.6 < 0.2 1.38
Average 96.14 0.23 6.79 799.5 1.81 < 13.5 < 4.0 < 14.3 < 28 12.7 < 0.47 1.78
PQ6 108.73 0.16 < 1.26 802.4 1.19 < 13.5 9.8 12.6 < 28 7.3 < 0.2 0.87
109.41 2.11 7.40 1023.6 1.88 < 13.5 7.0 21.2 < 28 13.5 < 0.2 2.91
111.43 0.23 8.87 1045.6 1.83 < 13.5 8.6 35.8 < 28 15.2 < 0.2 < 0.41
91.71 0.17 3.08 974.9 1.82 < 13.5 7.6 60.2 < 28 11.7 0.49 2.03
84.09 2.00 8.33 860.7 1.92 < 13.5 6.9 53.5 < 28 10.5 0.46 2.10
113.36 0.24 2.24 1147.8 2.16 < 13.5 6.8 31.7 < 28 10.7 < 0.2 1.83
Average 103.12 0.82 5.20 975.8 1.8 < 13.5 7.8 35.8 < 28 11.5 < 0.29 < 1.69

characterised by low Fe (Fig. 1e), which varies between
< 1.2 and 4 lg g 1. However, PQ3 has remarkably high
Fe, with an average of 46 lg g 1, which is associated with
elevated Mn (27 lg g 1; Table 3). Fe concentrations in
KQ1KQ5 are in the range of < 1.2 and 4 lg g 1 but
increase in KQ6 to 14 lg g 1. The high Fe in KQ6 corre-
lates linearly with high Al.
Concentrations of P are mostly below the limit of detection
(3.5 lg g 1) in the Katerina quartz and in most of the
Podles quartz (PQ1PQ5). However, quartz in PQ6, which
is the sample with the highest whole-rock P2O5 content, has
elevated P contents of 710 lg g 1. There might be a trend
of increasing P with increasing Al in quartz because PQ6
also has high Al (Fig. 1f).
In the Katerina samples, Ge concentrations increase linearly
from KQ1 (0.8 lg g 1) to KQ5 (3.4 lg g 1) with increasing
Al (Fig. 1g). Ge contents of the most fractionated quartz,
KQ6, are not on the same trend. Ge in the Podles quartz is
340 K. Breiter, A. Muller

Table 4. Trace element concentrations (lg g 1) of quartz from Katerina. Concentrations were determined by LA-ICP-MS. Quartz analyses
contaminated by uid or mineral inclusions, recognizable in this study by extraordinary high Al, K, Na and/or Fe are marked with *.

Li Be B Al Ge Na P K Ca Ti Mn Fe
LOD 0.77 0.13 1.26 7.2 0.13 13.5 3.5 1.5 28 0.9 0.2 0.41
1 1 1 1 1 1 1 1 1 1 1 1
Quartz generation lg g lg g lg g lg g lg g lg g lg g lg g lg g lg g lg g lg g
KQ1 26.21 < 0.13 1.26 93.5 0.64 < 13.5 < 3.5 < 1.5 < 28 29.2 0.20 2.25
36.31 0.37 1.69 166.1 0.93 < 13.5 < 3.5 < 1.5 < 28 21.9 < 0.2 3.04
26.45 < 0.13 1.44 109.1 0.61 < 13.5 < 3.5 < 1.5 < 28 25.2 < 0.2 2.01
28.50 < 0.13 < 1.26 103.1 0.63 < 13.5 < 3.5 2.09 < 28 63.6 < 0.2 2.07
24.19 < 0.13 < 1.26 114.1 0.68 < 13.5 < 3.5 < 1.5 < 28 62.4 0.52 2.95
33.12 0.34 3.15 134.6 1.12 < 13.5 < 3.5 < 1.5 < 28 24.0 < 0.2 2.17
Average 29.13 < 0.20 < 1.68 120.1 0.77 < 13.5 < 3.5 < 1.6 < 28 37.7 < 0.25 2.42
KQ2 10.51 0.29 4.93 156.1 1.11 15.74 < 3.5 15.3 < 28 9.4 0.32 0.93
10.03 0.13 1.45 162.5 1.09 < 13.5 < 3.5 14.8 < 28 13.1 0.35 1.36
3.32 0.17 1.49 146.5 1.18 < 13.5 < 3.5 12.5 < 28 11.0 < 0.2 2.60
14.13 < 0.13 < 1.26 163.7 1.10 < 13.5 < 3.5 8.5 < 28 11.8 < 0.2 1.95
17.74 < 0.13 < 1.26 183.3 0.95 < 13.5 < 3.5 12.5 < 28 8.0 < 0.2 1.47
3.78 0.17 < 1.26 152.2 1.26 < 13.5 < 3.5 16.6 < 28 10.5 0.24 2.88
11.00 < 0.13 < 1.26 136.4 0.86 < 13.5 < 3.5 8.7 < 28 13.6 < 0.2 2.45
20.23 < 0.13 < 1.26 127.3 0.88 < 13.5 < 3.5 6.6 < 28 18.9 < 0.2 1.62
22.15 < 0.13 < 1.26 133.0 0.95 < 13.5 < 3.5 5.6 < 28 23.1 < 0.2 2.24
9.08 0.14 < 1.26 164.5 1.18 < 13.5 < 3.5 19.8 < 28 12.9 < 0.2 1.45
Average 12.20 < 0.16 < 1.67 152.6 1.06 < 13.7 < 3.5 12.1 < 28 13.2 < 0.23 1.90
KQ3a 9.58 < 0.13 1.65 135.0 1.01 < 13.5 < 3.5 14.9 < 28 9.7 < 0.20 4.95
3.27 < 0.13 < 1.26 100.6 0.90 < 13.5 < 3.5 8.5 < 28 21.8 < 0.20 2.24
9.02 < 0.13 1.40 178.5 1.23 < 13.5 < 3.5 16.9 < 28 11.7 0.35 2.85
8.10 0.16 1.54 149.8 1.07 < 13.5 < 3.5 18.2 < 28 13.1 0.42 2.18
8.63 0.15 1.55 159.4 1.19 < 13.5 < 3.5 24.6 < 28 10.9 0.50 1.25
5.90 0.18 1.39 159.9 1.02 < 13.5 < 3.5 20.1 < 28 12.6 < 0.20 1.62
Average 7.42 < 0.15 1.47 147.2 1.07 < 13.5 < 3.5 17.2 < 28 13.3 < 0.31 2.52
KQ3b 33.63 < 0.13 < 1.26 163.1 1.12 < 13.5 < 3.5 29.7 < 28 41.9 0.65 8.24
32.27 < 0.13 < 1.26 156.8 1.00 < 13.5 < 3.5 3.9 < 28 31.9 < 0.20 2.01
32.35 < 0.13 < 1.26 139.2 1.05 < 13.5 < 3.5 1.8 < 28 33.6 < 0.20 1.59
35.18 < 0.13 < 1.26 125.2 1.13 < 13.5 < 3.5 < 1.5 < 28 31.0 < 0.20 2.20
36.99 < 0.13 < 1.26 147.7 1.21 < 13.5 < 3.5 5.1 < 28 27.3 0.28 2.32
36.65 < 0.13 < 1.26 156.4 1.18 < 13.5 < 3.5 < 1.5 < 28 21.8 0.24 1.83
35.16 < 0.13 < 1.26 142.3 1.15 < 13.5 < 3.5 < 1.5 < 28 21.7 0.26 1.57
35.06 < 0.13 < 1.26 122.4 1.24 < 13.5 < 3.5 < 1.5 < 28 18.1 0.38 1.71
Average 34.66 < 0.13 < 1.26 144.1 1.14 < 13.5 < 3.5 < 5.8 < 28 28.4 < 0.30 2.68
KQ4 25.27 0.28 1.92 197.7 1.87 < 13.5 < 3.5 23.8 < 28 33.2 < 0.2 1.78
30.26 0.32 2.16 197.4 2.15 17.28 < 3.5 39.2 < 28 36.6 < 0.2 7.13
27.67 0.33 < 1.26 223.1 2.18 < 13.5 < 3.5 14.1 < 28 41.4 < 0.2 2.28
24.84 0.24 < 1.26 169.6 2.13 < 13.5 < 3.5 10.9 < 28 33.6 < 0.2 2.95
16.07 < 0.13 < 1.26 107.7 0.84 < 13.5 < 3.5 4.0 < 28 20.3 < 0.2 1.55
25.53 0.32 < 1.26 162.8 1.97 < 13.5 < 3.5 7.7 < 28 30.2 < 0.2 2.75
34.92 0.44 1.61 792.9 2.18 45.81 < 3.5 293.2 < 28 53.9 0.89 35.55*
33.89 0.29 < 1.26 504.4 2.29 70.03 < 3.5 158.8 < 28 41.3 0.35 6.80*
11.21 0.23 < 1.26 296.6 2.23 70.69 < 3.5 164.1 < 28 30.5 < 0.2 3.00*
29.48 0.27 < 1.26 157.4 1.93 < 13.5 < 3.5 6.1 < 28 30.1 < 0.2 3.10
Average 24.81 0.26 < 1.37 169.7 1.82 < 13.5 < 3.5 11.1 < 28 31.5 < 0.20 2.40
KQ4 22.07 0.22 2.10 126.1 1.63 < 13.5 < 3.5 7.8 < 28 21.6 < 0.2 0.67
9.95 0.26 1.42 142.0 1.48 < 13.5 < 3.5 9.4 < 28 21.2 < 0.2 0.84
22.00 0.27 1.26 152.8 1.71 < 13.5 < 3.5 6.4 < 28 19.3 < 0.2 0.80
24.80 0.32 < 1.26 184.1 2.71 < 13.5 < 3.5 11.6 < 28 40.5 < 0.2 1.41
20.40 0.42 < 1.26 213.8 2.58 < 13.5 < 3.5 17.7 < 28 37.7 < 0.2 1.07
20.42 0.22 1.32 170.6 2.33 < 13.5 < 3.5 10.3 < 28 28.2 < 0.2 0.78
17.60 0.24 < 1.26 165.3 2.01 65.08 < 3.5 67.0 < 28 27.6 0.33 4.58*
14.67 0.28 < 1.26 184.5 1.86 < 13.5 < 3.5 14.7 < 28 28.9 0.20 1.09
25.72 0.30 < 1.26 163.8 2.28 < 13.5 < 3.5 10.8 < 28 21.6 < 0.2 1.45
25.16 0.29 < 1.26 151.9 2.02 15.89 < 3.5 10.4 < 28 18.6 < 0.2 1.51
Average 20.58 0.29 < 1.38 165.5 2.07 < 13.5 < 3.5 11 < 28 26.4 < 0.20 1.07
 Quartz chemistry of rare-metal granites 341

Table 4. Continued.

Li Be B Al Ge Na P K Ca Ti Mn Fe
LOD 0.77 0.13 1.26 7.2 0.13 13.5 3.5 1.5 28 0.9 0.2 0.41
1 1 1 1 1 1 1 1 1 1 1 1
Quartz generation lg g lg g lg g lg g lg g lg g lg g lg g lg g lg g lg g lg g
KQ5 41.26 1.01 2.19 264.1 2.14 < 13.5 < 3.5 43.3 < 28 7.9 0.80 3.24
24.74 0.37 < 1.26 239.9 1.40 < 13.5 < 3.5 32.2 < 28 6.4 0.37 2.92
32.18 1.42 2.93 327.2 3.43 < 13.5 < 3.5 32.2 < 28 7.8 0.82 2.85
62.84 1.10 2.46 1403.6 2.37 16.5 < 3.5 440.3 < 28 9.9 1.77 40.50*
51.45 1.21 2.27 295.6 5.68 < 13.5 < 3.5 40.4 < 28 4.2 0.84 2.55
46.14 1.17 2.69 368.2 4.37 < 13.5 < 3.5 52.0 < 28 2.9 1.63 3.74
Average 39.15 1.04 2.27 299.0 3.40 < 13.5 < 3.5 40.0 < 28 5.8 0.89 3.06
KQ6 108.89 1.22 1.93 999.1 1.94 17.68 < 3.5 132.4 < 28 4.7 0.54 11.26*
125.74 1.90 2.14 1082.0 2.70 14.02 < 3.5 183.0 < 28 4.1 1.36 14.32*
93.83 1.26 1.91 919.9 2.17 < 13.5 < 3.5 147.7 < 28 5.1 0.72 12.99*
103.36 1.03 1.71 496.8 2.38 16.03 < 3.5 7.4 < 28 4.0 0.76 6.12
90.45 0.70 1.39 576.1 1.80 24.58 < 3.5 11.6 < 28 4.7 0.48 7.71
98.05 0.72 < 1.26 449.5 1.89 < 13.5 < 3.5 7.8 < 28 5.3 0.41 5.74
101.26 1.45 1.41 641.0 2.05 < 13.5 < 3.5 78.9 < 28 5.5 0.77 8.91
83.95 0.61 < 1.26 417.0 2.08 < 13.5 < 3.5 22.5 < 28 4.0 0.54 5.47
Average 100.69 1.11 < 1.63 697.7 2.13 < 15.8 < 3.5 73.9 < 28 4.7 0.70 9.07

in the range of 12 lg g 1 without any trends in relation to
other elements. B concentrations in the Katerina quartz are
all in the range of < 0.133 lg g 1, without associations to
other elements. The Podles quartz has a higher average B,
of 28 lg g 1 but also without associations to other elements
(Fig. 1h). The concentration of Na in all analysed quartz pop-
ulations from both localities is lower than the limit of detec-
tion, 13.5 lg g 1. Several exceptions to this are assumed to
be occasional uid inclusions met by the laser beam.
6. Discussion
The localities studied represent two contrasting types of
highly fractionated rare-metal-bearing granite system. The
granites from Podles (S-type) are much more aluminous
(ASI about 1.3) and relatively enriched in P, F, Cs, Ta and
U. The granites from Katerina (A-like type) are only slightly
peraluminous (ASI = 1.05) and relatively enriched in Th,
Zr, Y and REE (Table 5). Quartz crystallised as a common
mineral during all stages of magmatic evolution: from early
phenocrysts to late matrix and comb crystal. Thereafter,
crystallised quartz was stable in respect to all later magmatic
and hydrothermal alteration. This gives us the possibility to
cf. the evolution of quartz chemistry with fractionation in
two contrasting melts (cf. Gurbanov et al., 1999; Larsen
et al., 2000).
The Al vs. Ti plot (Fig. 1a) documents the evolution of the
melt very well. However, we found no direct correlation
between WR-concentrations of these elements and their con-
centrations in quartz. High Ti is characteristic for early
quartz phenocrysts crystallised in deeper magma reservoirs
prior to sub-surface granite emplacement (Schron et al.,
1988). High Al is typical for quartz which crystallised from
highly evolved and ux-enriched magma batches (Gotze
et al., 2004). The exponential increase of Al in igneous
quartz with increasing fractionation of the host granite has
been described by Muller et al. (2002).
The most Al-enriched quartz population in Podles is PQ6.
This is the youngest quartz type in the system crystallised in
the most uid-enriched domain of the dyke, where unmixing
of uid from cooled magma caused hydrofracturing, brecci-
ation, and rapid crystallisation (Breiter et al., 2005).
However, processes that control the uptake of Al into the
quartz lattice seem to be numerous (e.g., Muller et al., 2000,
2002, 2003). Jacamon & Larsen (in review) suggested that
Al in igneous quartz increases with increasing aluminium
saturation index (ASI) in the melt. However, in this case
we could not prove a correlation between Al in quartz and
the ASI of the granite host. The whole-rock Al content
and peraluminosity varied only slightly during the evolution
of each system (Table 5, documented in detail in Breiter
et al., 2005 and Breiter, in review), even though the Al con-
tent in quartz increases signicantly. On the other hand,
despite large difference in ASI between both systems
(1.05 vs. 1.3), Al reaches the maximum content of about
1000 lg g 1 in evolved facies of both systems.
The increasing Al can be explained by the increasing reac-
tivity of quartz crystal faces due to the higher OH concen-
tration in the melt and associated de-polymerisation of
aluminiumsilicate complexes (Mysen, 1987). The de-poly-
merised complexes can attach more easily to the reactive
crystal faces. Muller et al. (2000) observed an association
of high Al in quartz and the elevated water content of the
parent magma. However, there are two additional facts
which may affect Al uptake (Merino et al., 1989; Pankrath,
1988): (1) the relatively low crystallisation temperature
around the high/low-quartz transition, and (2) the high
growth rate of quartz due to melt undercooling, degassing
and/or depressurising at the sub-volcanic emplacement
level. The high growth rate results in disequilibrium growth
that, in turn, causes the attachment and incorporation of
342 K. Breiter, A. Muller

Fig. 1. Contents of trace elements in quartz (lg g 1) determined by LA-ICP MS: a Al vs. Ti; b Al vs. K; c Al vs. Li; d Al vs. Be;
e Al vs. Fe; f Al vs. P; g Al vs. Ge; h Al vs. B.

impurity clusters into the quartz lattice. Concentrations of
Al > 500 lg g 1 seems to be characteristic for low quartz
(Muller et al., in review).
Li is well correlated with Al in quartz from both studied
localities (Fig. 1c) and the availability of Li in the melt
may play some role in the incorporation of Al into quartz
lattices. The content of Li in quartz increased with fraction-
ation in both systems and is generally positively correlated
with an increase in Li in the rocks (Table 5). On the other
hand, the most Li-enriched quartz populations from both
localities have similar Li-contents (80130 lg g 1)
although the whole-rock Li contents in the rocks differ sig-
nicantly (0.13 wt.% Li2O in Katerina vs. 0.33 wt.% Li2O
in Podles). In conclusion, Li may play only a second-order,
supporting role in incorporation of Al into quartz.
The late quartz populations (snow-ball quartz and matrix
quartz) were in equilibrium with the residual melts, e.g.,
melt enriched namely in water and uorine. Differences in
contents of Si, Al and alkalis between the intruding melt
and its residual part were insignicant (Breiter et al.,
2005). The highest Al values were in both localities found
in comb quartz, i.e., in quartz which grows extremely rap-
idly in a uid-rich environment. This may be the important
factor in facilitating Al entry into quartz.
 Quartz chemistry of rare-metal granites 343

of 4001000 C at 1.0 GPa. The temperature dependence of

Ti in quartz explains its higher content in the early quartz
generations and its systematic decline in the later quartz gen-
erations, which reects the decline in the quartz crystallisa-
tion temperature.
The Li values in quartz in both granite systems are remark-
ably high for igneous quartz. Reported values for igneous
and pegmatitic quartz are commonly in the range of
525 lg g 1 Li, and more rarely up to 40 lg g 1 (e.g.,
Larsen et al., 2004; Jacamon & Larsen, in review). Gotze
et al. (2005) found values of 56166 lg g 1 Li in quartz
Fig. 2. Correlation between contents of Al and (Li + K) in quartz in Li-rich pegmatites from Namibia. Schron et al. (1988)
expressed in atoms per formula unit (apfu). About 2=3 of Al atoms is found up to 108 lg g 1 Li in pegmatite quartz from
compensated with (Li + K) in Katerina; only in the more Muiane, Mozambique. However, up to 10 000 lg g 1 Li
aluminous Podles system. were detected in hydrothermal quartz (Perny et al., 1992).
Like K, Li shows a linear correlation with Al, because Li+
serves as a charge compensator for Al3+ substitution. The
Table 5. Chemical composition of typical early and late granites linear correlation is even stronger if the sum of the Li and
from studied localities. Major elements were determined with wet K concentrations is plotted against Al (Fig. 2). The strong
chemistry at laboratories CGS Praha and trace elements with correlation supports the general assumption that Al3+ substi-
solution ICP-MS at ACME laboratories Vancouver. tution for Si4+ is charge-compensated by coupled substitu-
tion of monovalent cations, such as Li+, K+, Na+, and H+
Katerina Podles (e.g., Dennen, 1966).
1st stage 2nd stage 1st stage 2nd stage One of the aims of the study is to test if the high P2O5 con-
Sample 3097 4602 3386 3397 tent of the Podles granites is reected in the quartz chemis-
try. So far, elevated P concentrations were detected in
SiO2 74.16 75.73 71.29 72.28
TiO2 0.02 0.02 0.06 0.03 K-feldspar and topaz from the Podles granites (Breiter
Al2O3 13.19 12.83 14.98 15.29 et al., 2002; Breiter & Kronz, 2004). K-feldspars are the
Fe2O3 0.61 0.26 0.22 0.26 major hosts of P in peraluminous, highly fractionated gran-
FeO 0.63 0.66 0.71 0.55 ites (e.g., London, 1992). The ionic radii of Si4+and P5+ are
MnO 0.054 0.042 0.017 0.023 almost similar, being 0.40 A and 0.38 A, respectively, for
MgO 0.03 0.02 0.03 0.02 6-fold coordination (e.g., Lide, 1998), which theoretically
CaO 0.46 0.28 0.43 0.27
Li2O 0.10 0.13 0.16 0.28
allows P5+ to enter the Si4+ site despite the different oxida-
Na2O 4.04 4.43 3.23 4.15 tion state. Huttenlocher (1935) and Beck (1949) showed that
K2 O 4.58 4.06 5.93 4.27 berlinite (AlPO4) and its polymorphs are isostructural with
P2O5 0.02 0.01 0.48 0.72 quartz, tridymite and cristobalite. The coupled substitution
H2O+ 0.77 n.d. 0.85 0.90 of Al3+ + P5+ = Si4+ + Si4+, known as berlinite substitution
F 0.597 0.456 1.04 1.48 from feldspars (e.g., Simpson, 1977) has not been proved
H2 O 0.14 0.05 0.16 0.13 for natural quartz. However, Maschmeyer & Lehmann
Total 99.16 99.61 99.18 100.06
(1983) suggested that all P present in the quartz lattice is
ASI 1.06 1.05 1.19 1.28 associated with Al, which is in agreement with estimates
Be 6 19 n.d. n.d. of the equilibrium distribution based purely on a Coulomb
Cs 25 60 147 134
attraction between Al3+ and P5+ on sites of Si4+. Rusk
Ga 35 36 33 48
Hf 10.8 12.5 1.2 2.4 et al. (2006) reported what are probably the highest P values
Nb 79 64 22 56 from magmatic quartz found so far 478 lg g 1 from
Rb 1066 1178 1467 1841 quartz monzonite at Bute, Montana. Also in this case, the
Sn 40 24 20 16 content of P is positively correlated with the content of Al
Sr 8.5 3.3 30 58 (Al in range 25335 lg g 1). Rusk et al. (2006) does not
Ta 14 13 10 33 report whole-rock phosphorus data, but the Bute monzonite
Th 45 31 5 5
U 14 13 19 12
is generally not P-enriched, containing only 0.10.2 wt.%
W 54 13 30 53 P2O5 (Miller, 1978). Phosphorus values of pegmatite quartz
Y 157 74 6 2 published by Larsen et al. (2004) range from 923 lg g 1,
Zr 124 100 30 29 showing a weak correlation with Al. However, in both cases
n.d. not determined. the P values are presumably too high due to the application
of a single-standard calibration for concentration calculation
of the LA-ICP-MS data (Muller et al., 2008).
Wark & Watson (2006) proved the temperature depen- PQ6 is the only quartz generation that systematically con-
dence of Ti4+ Si4+ substitution in the presence of rutile tains elevated P concentrations in the range of 710 lg g 1.
and established a geothermometer for the temperature range In all other populations, the P-content exceeds 3.5 lg g 1
344 K. Breiter, A. Muller
only in individual points. The association of the elevated P
and high Al in PQ6 suggests that Al3+ and P5+ form a com-
bination centre (berlinite substitution) as assumed by Masch-
meyer & Lehmann (1983).
The patterns and thus, behaviour of Be and Ge in quartz are
similar. Both elements are slightly more enriched in late-
stage quartz KQ5 and KQ6 from Katerina A-type melt. How-
ever, the most evolved KQ6 has lower average Be and Ge
than KQ5, probably due to escape of vapour, forming beryl
in ssures. In contrast, Be is very low in the Podles quartz
and Ge shows no clear trend. The Ge contents in the highly
fractionated granites studied reach enrichment comparable
with pegmatitic quartz as reported by Gotze et al. (2004)
and Larsen et al. (2004). Schron et al. (1988) suggested a
GeAlTi ternary diagram for distinguishing quartz from
rhyolites and granites (Fig. 3). Gotze et al. (2004) supple-
mented the diagram with a eld for compositions of
pegmatite quartz. The early quartz generations of both the
Podles and Katerina igneous systems (PQ1 and KQ1) plot
near the rhyolite eld, suggesting that the phenocrysts of
these granites are similar in composition to those commonly
found in rhyolites. During further evolution, the chemistry of
Katerina quartz KQ2KQ5 follows the eld of pegmatites,
while Podles quartz evolved between the proposed gran-
ite and pegmatite trends. Due to relative enrichment in
Al, the most fractionated quartz from Katerina (KQ6) has a
similar position between the proposed trends. Thus, the com-
positional elds for rhyolitic, granitic and pegmatitic quartz
are transitionally and not strictly separated, as suggested by
Schron et al. (1988) and Gotze et al. (2004).
The elevated B concentrations in the Podles quartz com-
pared to the Katerina quartz reect the presence of B in the
granite system. The Podles granite stock is surrounded by
an extensive halo of tourmalinization. Although the actual
WR content of B is low, we should assume that there are
Fig. 3. GeAlTi diagram of quartz according to Schron et al.
(1988) (elds of rhyolites and granites) and Gotze et al. (2004) (eld
of pegmatites). Note that the evolution of both the Podles and the
Katerina igneous systems starts near the eld of rhyolites and
continues to the eld of pegmatites.
much higher contents in the intruding magma. At the nal
stage, a hydrous borosilicate phase separated from the mag-
mas, escaped from the intrusion and precipitated as dissem-
inated tourmaline in the phyllitic host rocks.
The high Fe and Mn in the pegmatitic PQ3 are explained
here by the marked change of the oxidation stage of the
quartz-forming uid. Meteoric uids with oxidized Fe and
Mn interacted and mingled with the residual magmatic u-
ids in the cupola of the Podles granite stock. The marginal
stockscheider precipitated from this uid mixture causing
the unusually high Fe and Mn in quartz. Similar features
have been observed in quartz in the epithermal Asachinskoe
gold deposit in Kamchatka (Takahashi et al., 2008).
7. Summary and outlook
This study demonstrates the applicability of the trace-ele-
ment signature of igneous quartz for discrimination of differ-
ent granitic suites as well as for more objective interpretation
of individual evolutionary stages (magma pulses) within
each suite. The contents of the chemical elements deter-
mined are, with the exception of P, Ca, Na, and Mn, well
above the limits of detection of the LA-ICP-MS.
The most common trace element in igneous quartz is Al
(in the range of 1001200 lg g 1) followed by Ti, Li,
and K (usually in the range of 10100 lg g 1). Contents
of B, Be, Ge, Fe, Mn, and P are generally < 10 lg g 1.
Contents of all analysed elements tend to be enriched during
fractionation; only Ti decreases. Mixing of the magmatic
uids with oxidizing meteoric uids caused occasional
increases in Fe and Mn.
With fractionation of granitic melt, independent of its alu-
minosity, the content of Ti in quartz decreases systematically
and Al increases. The Ti vs. Al diagram is the most tting
indicator of evolution (fractionation) of the melt from which
the quartz crystallised. Nevertheless, there is no simple cor-
relation between Ti and Al contents (or activity) in the melt
and crystallising quartz. The entry of 5070 % of the Al into
the quartz lattice is compensated by the entry of monovalent
cations Li+ and K+, probably partially also by H+-ions.
The berlinite substitution (Al3+ + P5+ = Si4+ + Si4+) is
important for P-incorporation in quartz lattice, but in com-
parison with other silica minerals (feldspar, topaz, and gar-
net) is quantitatively strongly limited. There is no simple
correlation between the P-content in the whole-rock and in
the magmatic quartz.
The major differences in chemical composition of both
granitic systems are well correlated with the trace-element
spectrum of appropriate quartz populations:
The older quartz populations from Podles are more
enriched in Al, and the younger quartz populations from
Podles are enriched in P and B, which corresponds to the
higher peraluminosity and the P- and B-enrichment of the
Podles granite system.
The younger quartz from Katerina is more enriched in Be
and Ge, while the Katerina granite system is enriched in
Be (whole-rock data on Ge are not available).
 Quartz chemistry of rare-metal granites
Acknowledgements: This article is a contribution to IGCP
Project 510 A-type granites and related rocks through time.
This is IGCP-510 publication No. 45. The investigation was
supported by the Geological Institute of the Czech Academy
of Science v.v.i. (project No. 9212) and by the Geological
Survey of Norway. Financial support for KB from the Czech
IGCP committee is highly appreciated. We greatly appreciate
the critical comments and language improvement of R. Boyd.
Our thanks go also to Carlos Villaseca Gonzalez and one
anonymous reviewer for comments and suggestions that
helped us to improve the manuscript.
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Received 30 May 2008
Modied version received 18 September 2008
Accepted 27 October 2008