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Diversity of primary CL textures in quartz from

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Contrib Mineral Petrol (2013) 166:12531268
DOI 10.1007/s00410-013-0923-0
ORIGINAL PAPER
Diversity of primary CL textures in quartz from porphyry
environments: implication for origin of quartz eyes
O. V. Vasyukova V. S. Kamenetsky
K. Goemann P. Davidson
Received: 31 January 2013 / Accepted: 9 July 2013 / Published online: 23 July 2013
 Springer-Verlag Berlin Heidelberg 2013
Abstract Porphyry-style mineralization is related to the
intrusion and crystallization of small stocks, which can be
of different compositions (from intermediate to felsic) and
can intrude into different host rocks (from magmatic to
sedimentary). We used cathodoluminescence and electron
probe microanalysis to study the internal textures of more
than 300 quartz eyes from six porphyry deposits, Panguna
(Papua New Guinea), Far Southeast porphyry (Philippines),
Batu Hijau (Indonesia), Antapaccay (Peru), Rio Blanco
(Chile) and Climax (USA). Significant diversity of the
internal textures in quartz eyes was revealed, sometimes
even within a single sample. Quartz grains with Ti-rich
cores surrounded by Ti-poor mantles were found next to the
grains showing the opposite Ti distribution or only slight Ti
fluctuations.We propose that diversity of the internal pat-
terns in quartz eyes can actually reflect in situ crystallization
history, and that prolonged crystallization after magma
emplacement under conditions of continuous cooling can
account for the observed features of internal textures. For-
mation of quartz eyes begins at high temperatures with
crystallization of high titanium Quartz 1, which as the melt
Communicated by C. Ballhaus.
O. V. Vasyukova (&)
V. S. Kamenetsky
P. Davidson
ARC Centre of Excellence in Ore Deposits and School of Earth
Sciences, University of Tasmania, Hobart, TAS 7001, Australia
e-mail: olgav@utas.edu.au; olga.vasyukova@mcgill.ca
Present Address:
O. V. Vasyukova
Earth and Planetary Sciences, McGill University,
Montreal H3A 0E8, Canada
K. Goemann
Central Science Laboratory, University of Tasmania,
Hobart 7001, Australia
becomes more and more evolved and cooler, is overgrown
by low Ti Quartz 2. Subsequent fluid exsolution brings
about dramatic change in the melt composition: OH2,
alkalis and other Cl-complexed elements partition into the
fluid phase, whereas Ti stays in the melt, contributing to a
rapid increase in Ti activity. Separation of the fluid and its
further cooling causes disequilibrium in the system, and the
Quartz 2 becomes partially resorbed. Exsolution of the fluid
gradually builds up the pressure until it exceeds the yield
strength of the host rocks and they then fracture. This
pressure release most likely triggers crystallization of
Quartz 3, which is higher in Ti than Quartz 2 because Ti
activity in the melt is higher and pressure of crystallization
is lower. As a result of the reaction between the exsolved
fluid and quartz a new phase, a so called heavy fluid forms.
From this phase Quartz 4 crystallizes. This phase has
extremely high metal-carrying capacity, and may give a rise
to mineralizing fluids. Finally, on the brink of the subsolidus
stage, groundmass quartz crystallizes. Prolonged crystalli-
zation under conditions of continuous cooling accounts
better for the diversity of CL textures than crystallization in
different parts of a deep magma chamber. It is also in a
better agreement with the existing model for formation of
porphyry-style deposits.
Keywords Cathodoluminescence
Quartz eyes

Porphyry deposits
Introduction
The interest in cathodoluminescence (CL) of quartz has
increased dramatically over the last two decades, due to the
fact that CL provides unique information that cannot be
obtained by other analytical methods. Cathodoluminescence
123
1254
is electron beam induced photon emission caused by lattice
imperfections and impurities; it reveals primary zonation
and secondary textures (e.g. alteration halos along grain
boundaries, healed microcracks etc.) that may be optically
invisible. The intensity of CL depends on the type of
chemical bond, lattice defects (vacancies), and impurity
elements, which can be revealed by complementary
microanalytical methods.
There are a few review papers which generalize the
types of CL in quartz from different environments (Gotze
2009; Gotze et al. 2004, 2001; Muller et al. 2010a, b; Rusk
et al. 2008; Stevens-Kalceff 2009; Stevens-Kalceff and
Phillips 1995; Wark et al. 2007; Wiebe et al. 2007). It was
shown that in porphyry environments quartz phenocrysts
exhibit contrasting CL patterns, often with low-Ti, CL-dark
cores and high-Ti, CL-bright rims (Wiebe et al. 2007).
Such patterns are currently assigned to multi-cycle crys-
tallization, when every cycle includes a period of resorp-
tion and regrowth. Such conditions may accompany multi-
stage magma ascent (Muller et al. 2005) or are associated
with magma rejuvenation (Shane et al. 2008; Wark et al.
2007; Wiebe et al. 2007). The other typical feature for
quartz phenocrysts in porphyry environments is the
extreme diversity of CL patterns even within a single thin
section (Wiebe et al. 2007). Unfortunately, there is cur-
rently no consensus as to what causes such diversity.
It is generally assumed that quartz phenocrysts in por-
phyry stocks crystallized in a deep magma chamber and
then were brought to the location of emplacement. In this
case CL diversity could be related to the mixing of crystals
crystallized in different parts of the magma chamber. On
the other hand, phenocryst content in intrusive rocks is
typically higher than in related extrusive rocks. This means
that at least some of the phenocrysts could crystallize after
magma emplacement. For example, it has been shown
(Vasyukova et al. 2013) that CL-dark cores may crystallize
after magma emplacement from extremely evolved melts
enriched in OH2, Al, Li just before fluid exsolution,
whereas CL-bright rims may crystallize after fluid exso-
lution, i.e. during the magmatic-hydrothermal transition.
Therefore, quartz crystals in porphyry environments may
crystallize during the late magmatic stage or even during
the magmatic-hydrothermal transition. Such late crystalli-
zation was suggested for vermicular quartz eyes from the
Empire Mine in Idaho (Chang and Meinert 2004) and the
Bajo de la Alumbrera porphyry Cu-Au deposit (Harris et al.
2004). These late conditions are significantly different from
those of crystallization of normal quartz phenocrysts in
volcanic rocks and may be related to a mineralization
process, and therefore, they are important to understand.
The term quartz eyes is used herein to describe these
quartz crystals, since it is both descriptive, and emphasizes
that their origin is yet to be established.
123
Contrib Mineral Petrol (2013) 166:12531268
We performed scanning electron microscopy (SEM)-CL
mapping of quartz combined with electron microprobe
microanalysis for Ti; 363 quartz crystals were mapped. As
a result of the study a new explanation for diversity of
internal textures within quartz eyes is derived and a new
general model for crystallization of quartz eyes in porphyry
environments is suggested.
Samples and localities
Quartz eyes from six world-class porphyry deposits were
studied: Panguna (Papua New Guinea, PNG), Far South-
east porphyry (Philippines), Batu Hijau (Indonesia),
Antapaccay (Peru), Rio Blanco (Chile) and Climax (USA).
Brief descriptions of the samples and deposits are in the
Table 1. The choice of samples allowed comparison of
quartz eyes from deposits of different age, rock types and
mineralization. The total of 363 quartz grains were studied
(See Table 1). Almost no alteration was observed in the
samples, only minor patchy sericite alteration of the
groundmass and Fe staining. In some cases there was minor
sericite alteration to some feldspar crystals along fractures.
All samples (except for two samples from Climax granites,
USA) show porphyritic textures; phenocryst content in the
studied samples varies from 30 to 60 vol% (Table 1).
Methods and techniques
Backscattered electron (BSE) images were acquired for
every sample. Quartz grains were then chosen and CL
imaging of the individual quartz grains were performed
using a Cameca SX100 electron microprobe (EPMA,
Central Science Laboratory, University of Tasmania)
equipped with a Cameca CL detector. During the first runs,
CL images were captured parallel to BSE images, which
allowed direct comparison of the two different image sig-
nals. Some of the CL images were collected on an FEI
Quanta 600 environmental scanning electron microscope
(Central Science Laboratory, University of Tasmania)
equipped with a Gatan PanaCLF CL detector. Imaging was
carried out on polished and carbon coated samples at an
accelerating voltage of 20 kV and beam current of 20 nA
(SX100) and around 3 nA (Quanta 600).
Microthermometry was performed on a Linkam TS1500
heating stage, using an Olympus model BX 60 optical
microscope fitted with a CCD camera. The heating stage
allowed heating of samples at any predetermined rate up to
700 C. The accuracy was 5 C.
For trace elements analysis in quartz, the same Cameca
SX100 EPMA was used at an accelerating voltage of
15 kV, a beam current of 200 nA, a beam diameter of
Contrib Mineral Petrol (2013) 166:12531268
Table 1 Brief description of the studied deposits and samples
Ore deposit Age, Ma Minera- Number of
(locality) lisation samples
type studied
Panguna (PNG) 3.44.5 Cu 2 19
Far Southeast porphyry 1.4 Cu-Au 1 20
(Philippines)
Batu Hijau (Indonesia) 3.75.9 Cu-Au 3 47
Antapaccay (Peru) 32.541.5 Cu-Au 3 40
Rio Blanco (Chile) 3.95.3 Cu-Mo 10
Climax (USA) 18.033.0 Mo 5 49
5 lm, and counting times of 300 s on the peak and 150 s on
two background positions. No significant changes of peak
or background intensities during the measurement could be
observed, and comparative measurements at shorter acqui-
sition times, lower beam current and higher beam diameter
of quartz areas with higher trace element contents yielded
similar results. Spectrosil 1000 (Saint-Gobain), a fused
silica material with certified contents of \20 ppb for Al
and \10 ppb for other trace elements, was used to deter-
mine blank corrections. Where possible, three EPMA spots
were positioned next to each other in bands with similar
panchromatic CL intensity to improve counting statistics. Ti
was calibrated on rutile (Astimex Scientific Ltd, Toronto)
and ideal quartz composition of 100 % SiO2 was assumed
for the matrix correction using the PAP algorithm. The
detection limits for Ti were 1014 ppm (99 % confidence).
Al and Zn were measured at the same conditions using
corundum and gahnite (McGuire et al. 1992) for calibration,
respectively. The detection limits were 1011 ppm for Al
and 9293 ppm for Zn.
Laser Ablation Inductively Coupled Plasma Mass
Spectrometry (LA-ICP-MS) was performed at CODES,
University of Tasmania, with a New Wave 213 nm solid-
state laser microprobe coupled to an Agilent 4,500 quad-
rupole ICP-MS. The beam diameter ranged from 35 to
100 lm, with the laser repetition rate 510 Hz and laser
beam energy 33.5 J/cm2. The analysis time for each
spectrum was 100 s, including a 30 s measurement of
background (laser off) and 70 s with laser on. The stan-
dards (NIST612 and BCR-2) were analyzed twice every
90 min to account for the instrument drift, with a 100 lm
beam at 10 Hz. The following isotopes were analyzed:
1255
Number of Rock Average phenocryst and quartz eye
quartz eyes compositions composition
studied
Diorites Plagioclase feldspar (40 %, 0.54 mm) and
biotite phenocrysts (5 %, 0.52 mm) and
quartz eyes (5 %, 0.52 mm)
Quartz diorite Plagioclase feldspar (35 %, 0.53 mm) and
quartz eyes (710 %, 0.52 mm)
Tonalites Plagioclase feldspar (40 %, 0.54 mm),
hornblende (2 %, 0.53 mm) and quartz
eyes (25 %, 0.54 mm)
Tonalites Plagioclase feldspar (30 %; 0.27 mm),
hornblende (4 %; 0.12.4 mm) and quartz
eyes (25 %; 0.23 mm)
188 Granites and Feldspar (2040 %, 0.55 mm) and biotite
granodiorites (2 %, 0.11 mm) phenocrysts and quartz
eyes (210 %, 0.58 mm)
Granites Feldspar (250 %, 0.54 mm), biotite
(4 %, 0.52 mm) and quartz eyes
(225 %, 0.54 mm)
7
Li, 24Mg, 27Al, 49Ti, 55Mn, 57Fe, 69Ga, 70Ge, 85Rb, 88Sr,
208
Pb. Only Al, Ti and Fe were found to be consistently
above detection limits. Unfortunately, the quartz host
always cracked at the initiation of ablation when impacted
by the laser beam, which caused formation of large craters
even when a small beam size was used. This precluded
representative quantitative analytical results on trace ele-
ments. As a result, EPMA was used as the principal method
for this study due to its superior spatial resolution and non-
destructive character.
Correlation of Al and Ti with the total CL emission
(panchromatic CL)
To investigate the relationship between trace element dis-
tribution and CL patterns, hyperspectral CL mapping was
performed on selected samples in addition to panchromatic
CL imaging and trace element mapping. The results of the
hyperspectral mapping were published in Vasyukova et al.
(2013). To avoid repetition we will only summarize the
major conclusions here.
Three major contributions for the CL emission were
found: the peaks centered at 1.93, 2.05 and 2.72 eV.
1.93 and 2.72 eV peaks were found the most signifi-
cant; their intensities typically dominate the total CL
emission.
Al and Ti are the major trace element impurities which
influence CL emission in the studied case. Their
distribution accounts for the intensity of each of the
peaks: Al shows an inverse correlation to 1.93 eV
123
1256 Contrib Mineral Petrol (2013) 166:12531268

emission, whereas Ti positively correlates with 2.72 eV Results

emission. There was no correlation found between Fe
and CL intensity in the studied samples. Primary quartz
2.72 eV maps can be transformed into Ti distribution maps
(the calibration curve displays an R2 value of a 0.9631). The studied samples contain between 2 and 25 vol% of
quartz eyes ranging in size from 0.2 to 8 mm (Table 1).
Since Al appears to quench 1.93 eV emission (Vas-
The typical size of quartz eyes is 12 mm. Their shapes
yukova et al. 2013), the 2.72 eV emission should become
vary significantly within a single thin section: euhedral
more pronounced in samples (or zones) with high Al
crystals are found next to subhedral or anhedral ones
content, and therefore the total CL emission should depend
(Fig. 2). Quartz eyes are often embayed; some embay-
mainly on the 2.72 eV peak, i.e. on the Ti concentration.
ments are short (Fig. 2a), others are long and sinuous and
However, we found that even in zones with low Al content
extend deep into the core of the grain (Fig. 2d, e). Different
showing higher 1.93 eV emission (see the arrow in
styles of embayment are found in grains within a single
Fig. 1c), the total CL emission still reflects 2.72 eV emis-
thin section (Fig. 2). The quartz grains often cluster toge-
sion rather than 1.93 eV (see the arrow in Fig. 1a).
ther, with clusters consisting of two to five or more quartz
Therefore, in spite of the fact that Al is a common trace
grains. When examined optically in crossed polars, several
element in quartz (Gotze 2009; Muller et al. 2005; Rusk
distinct optical orientations are often observed. Quartz
et al. 2008; Wiebe et al. 2007), and its concentration in
grains within a single cluster in most cases show identical
some samples can be significant, its influence on the total
CL zoning (Fig. 2c).
CL emission (panchromatic CL) appears to be negligible in
our samples. For the samples that were not studied by
Types of CL patterns
hyperspectral mapping, we compared Al and Fe concen-
trations and total CL intensities. No correlation was found,
Although different deposits represent different magma
which indirectly indicates that in those samples the total
chemistry, ages and type of mineralization (see Table 1),
CL intensity is also determined by Ti impurity. Thus, we
the studied samples show similar types of internal textures
will discuss textural features revealed by panchromatic CL
revealed by CL mapping. Four major types of CL patterns
only in relation to the respective Ti concentration.
were observed in this study (Fig. 3a).
A detailed discussion of the major contributors for CL
emission and the type and quality of CL spectra can be Quartz grains with Pattern 1 show CL-dark cores
found in Vasyukova et al. (2013). The paper presented here overgrown by a bright mantle. CL-dark cores are
focuses on two general features of CL textures in quartz always rounded, rarely display oscillatory zoning, and
eyes from porphyry environments: the diversity of CL sometimes show sector zoning (Figs. 2c, 3b). CL-bright
patterns even within a single thin section, and their origin. rims often show oscillatory zoning (Figs. 2c, d, 3b);

Fig. 1 Correlation between the panchromatic CL map (a, e) and 2.72 eV (b, f), 1.93 (c, g), 2.05 (d, h) emission maps in two quartz eyes from
Rio Blanco. An arrow in c points to the area with high 1.93 eV intensity (low Al), which is not pronounced in the panchromatic CL map (a)

123
Contrib Mineral Petrol (2013) 166:12531268
Fig. 2 Diversity of shapes and CL patterns within a single thin
section, sample DC-DP-1 (Rio Blanco). a, ceuhedral, b, d
subhedral, eanhedral crystals, fposition of ae relative to each
other shown in (f). aPattern 3 (oscillatory zoning), bPattern 4:
CL-bright euhedral core, CL-dark mantle and CL-bright rim, ce
oscillatory layers close to a core are often brighter than
outer rim zones (Fig. 2c). Grains with Pattern 1 CL are
often heavily embayed (Fig. 2d, e); embayments are
deep and sinuous, and CL layers are always adapted to
the shape of embayments. A relationship between
quartz eye shapes and their CL patterns is observed: the
higher CL-dark/CL-bright ratio in a grain the more
irregular shape it show with deeper embayments
(Fig. 2). Transitions between CL-dark cores and CL-
bright rims are always sharp.
Pattern 2 grains display CL-bright cores with a CL-
darker mantle. Unlike dark cores (Pattern 1), bright
cores often show crystallographic shapes (Fig. 3b);
only in a few cases were they found resorbed. Cores are
overgrown by CL-darker quartz, often showing oscil-
latory zoning (Fig. 3b). Embayments in Type 2 grains
are common; unlike embayments in Pattern 1 quartz,
they are short with smooth edges, but also have
adjacent layers adapted to them. Transitions between
CL-bright cores and CL-darker rims are always sharp.
Pattern 3 grains show oscillatory zoning only (slight
fluctuations in CL intensity). Embayments in this type
1257
Pattern 1: CL-dark cores and CL-bright rims with different core/rim
proportions. Sector zoning is shown by black arrows in (c). Note that
different styles of embayments are observed (shown by white
arrows): short in a and deep and sinuous in (d) and (e). Scale bars
are 500 lm. aeCL images, fBSE image
of quartz are similar to those in Pattern 2 quartz: short
with smooth edges (Fig. 2a).
Pattern 4 grains display more complex CL patterns with
CL-bright cores, CL-darker mantles and CL-bright rims
(Figs. 2b, 3b). CL-bright cores are resorbed in some cases
and show crystallographic shapes in others (Fig. 3b). In
contrast CL-dark mantles are always rounded. Grains
with Patterns 4 CL are less frequently observed than
grains with the other three patterns. Transitions between
CL-bright core and CL-dark mantle are sharp in some
samples and gradual in others. Transitions between CL-
dark mantle and CL-bright rims are always sharp
(Figs. 2b, 3b). Embayments in this type of quartz grains
are mostly short with smooth edges, although in rare
cases deep sinuous embayments are observed; CL layers
are always adapted to the shape of an embayment.
In most cases all of the described CL pattern types can
be observed within a single thin section. There is no clear
distribution pattern for different types of CL zoning: within
different thin sections of the same sample different distri-
bution can be observed.
123
1258
Fig. 3 Diversity of CL patterns
within a single thin section.
aa sketch showing observed
CL patterns, 1, 2, 3a and 3b are
different quartz types according
to Ti content; ban example of
the diversity of CL patterns
within a single thin section.
Sample CA6, Rio Blanco.
14Types of CL patterns
shown in (a). Central image is
BSE, the others are CL images.
The dotted arrow points to
sector zoning. Scale bar is 1 cm
Variations in Ti content within a thin section
Different deposits represent different magma chemistry,
ages and type of mineralization (see Table 1). Therefore, it
was not surprising that samples from different deposits
showed different Ti content in primary quartz (Table 2).
For example sample 09229700 from Antapaccay have Ti
content from 30 to 90 ppm, whereas quartz eyes from Batu
Hijau show Ti concentrations from 58 to 166259 ppm.
Due to such significant differences, a direct comparison of
absolute concentrations is not possible. Therefore, we can
either study the Ti content within samples of a single
deposit, or use qualitative data on Ti distribution to com-
pare samples from different deposits.
Regarding the Ti content, four types of quartz can be
distinguished as representing different internal zones
(Fig. 3a; Table 2). The first type, Quartz 1, shows the
highest Ti concentrations and forms CL-bright cores in
Pattern 4 grains. Quartz 2 shows the lowest Ti concentra-
tions and comprises Cl-dark cores in Pattern 1 and CL-dark
mantles in Pattern 4 grains (Fig. 3a; Table 2). Quartz 2
often displays sector zoning, which is controlled by slight
123
Contrib Mineral Petrol (2013) 166:12531268
variations in Ti (the details on Ti distribution in sector
zoning can be found in Vasyukova et al. 2013).
Quartz 3 is high in Ti, but usually not as high as Quartz
1 (Table 2), and comprises Pattern 2 and 3 grains and rims
in Patterns 1 and 4 (Fig. 3a). In many cases the CL-brighter
inner rim zones (Quartz 3a) can be distinguished from
slightly darker in CL Quartz 3b outer zone (Fig. 3a), which
show slightly lower Ti content (Table 2). In some cases,
though, Quartz 3 is homogeneous (Table 2).
Quartz 4 shows very distinctive features compared to the
other quartz types, i.e. its extreme CL intensity, which is
correlated with unusually high Ti (Fig. 4d; Table 2). Such
quartz was extremely rare, and therefore is not shown in
typical CL patterns. Quartz 4 also displays micro-inclu-
sions, which can be observed in transmitted light (Fig. 4d).
Titanium in groundmass quartz varies over a wide range
reaching concentrations twice as high as in quartz eyes
(Table 2).
An example of Ti distribution in quartz of different CL
patterns within a single deposit is shown in Fig. 4. Four
quartz eyes from three samples from Rio Blanco are shown
in the figure. The quartz eye in Fig. 4a (sample CA6)
Contrib Mineral Petrol (2013) 166:12531268
Table 2 Ti concentrations in different quartz generations
Locality Sample Quartz 1 Quartz 2
Climax 109647 bdl-44
109644 65143 3245
Rio Blanco DC-DLP-1 1947
DC-DP-1 1847
CA6 5866 2137
Batu Hijau SBD69 5880
SRD-02
Antapaccay 09229700 3090
SEP P13 113 3753
Panguna 109607 5078
bdl below detection limits
represents Pattern 4 quartz, in which Quartz 1 forms CL-
bright core and has 5866 ppm Ti, Quartz 2 comprises CL-
dark mantle and shows the lowest Ti content2137 ppm,
and Quartz 3 forms CL-bright rim, where Ti increases
abruptly to 4858 ppm. The quartz eye in Fig. 4b (sample
DC-DP-1) represents Pattern 3 comprised by Quartz 3,
which shows 3957 ppm Ti. Figure 4c shows quartz eye
with typical Pattern 1 (sample DC-DP-1), in which Quartz
2 forms the CL-dark core and shows the minimum
Tifrom 21 to 47 ppm, Quartz 3a comprises the inner rim,
where CL intensity is the highest, and contains 5565 ppm
Ti. Quartz 3b forms the outer rim, which is slightly
CL-darker, and shows lower Ti content, i.e. 47 ppm.
Another Pattern 1 grain (sample DC-DLP-1, Fig. 4d)
shows similar Ti distribution in Quartz 2 (1947 ppm) and
Quartz 3 (4569 ppm) as well as rare example of Quartz 4,
where Ti reaches 287 ppm.
Secondary quartz and fluid inclusions
Secondary quartz is CL-darkest, and shows the lowest Ti
content (always below detection limit, see Table 2). Sec-
ondary quartz is always associated with fluid inclusions
(Fig. 5a, b). Fluid inclusions exposed to the surface have a
halo of secondary quartz around it, and all the halos are
connected by fractures (healed with the same CL-dark
quartz, Fig. 5c, d). Since all of the exposed inclusions
showed an association with secondary quartz and were
texturally related to fractures, the same correlation was
assumed for inclusions under the surface.
In some cases inclusion halos contained several gener-
ations of secondary quartz (Fig. 5d). In rare cases fluid
inclusions were localized within the transition between the
core and the rim (Fig. 5g, h). Unfortunately, such inclu-
sions were too small for microthermometry. Inclusions
which were located in an intersection of healed fractures
are often vapor-rich (Fig. 5e, f).
1259
Quartz 3a Quartz 3b Quartz 4 Groundmass Secondary
quartz quartz
4562 3251
4569 5159 147287
6072 3951 bdl
4858 49 bdl
166259
76225 12289 bdl
bdl-109 bdl
181 149179
70122 77
Inclusions are usually 525 lm in diameter, and show
significant diversity in compositions: from vapor-rich to
two-phase fluid with variable volume fraction and multi-
phase crystal-rich inclusions (with a shrinkage bubble). All
the described types can be found in the same trails
(Fig. 5e). Microthermometry was performed for fluid
inclusions from two samples from two deposits (Rio
Blanco and Batu Hijau). As it can be assumed from the
diversity of vapor/liquid/solid volume fractions, the ranges
of homogenization temperatures are also wide, i.e. from
430 C to higher than 600 C in sample G1 from Rio
Blanco and from 340 C to higher than 600 C in sample
(SBD69) from Batu Hijau.
Some of the studied quartz eyes contain inclusions of
sulfides, which are also associated with secondary CL-dark
quartz (healed fractures crossing the grain, Fig. 6).
Although such CL-dark quartz is secondary it does not
extend outside the quartz. Figure 6 displays an example of
a quartz grain with sulfide grains (sphalerite) along a
healed fracture. Titanium concentrations in this secondary
quartz are below the detection limit (Fig. 6), Al is enriched
in narrow areas close to the sulfide blebs and along tiny
fractures, whereas Zn shows extremely high concentrations
(up to 5,691 ppm) and strong affiliation to the secondary
quartz, increasing diffusively from the edges of healed
fractures towards the sphalerite grains.
Discussion
Our data showed that diversity of CL patterns within a
single thin section is a typical feature for all studied sam-
ples. Diversity on such a small scale is usually assigned to
crystallization within different parts of a magma chamber
and following mixing during magma emplacement (Agangi
et al. 2011; Muller et al. 2005, 2010b). However, the total
phenocryst content in porphyry stocks is generally very
123
1260 Contrib Mineral Petrol (2013) 166:12531268

Fig. 4 Distribution of Ti in
quartz showing different types
of CL patterns from two Rio
Blanco samples. aPattern 4,
bPattern 3, cPattern 1,
dPattern 1 ? Quartz 4
(extremely high in Ti). The
dashed rectangle is the area
shown in the inset. All are CL
images except for the inset in
(d), which is optical image
(transmitted light). Scale bars
are: 500 lm in (a) and 200 lm
in (bd)

high (from 30 up to 60 vol% in this study). Magmas with
such a high degree of crystallinity cannot be fully mobile.
According to Cloos (2001), only magma with up to about
25 vol% of phenocrysts is fully mobile; in such magma
convective flow is possible as well as crystal settling or
floating. If the phenocryst content is higher than 25 vol%
(up to 50 vol%), limited mobility is implied and only
porous flow of residual melt is possible (Cloos 2001).
Finally, if phenocryst content is more than 50 vol%, then
any magma movement is unlikely and only diffusion in
static residual melt occurs (Cloos 2001). We therefore
assume that the porphyry magmas had significantly lower
phenocryst content before emplacement than what is
observed now, and at least some phenocrysts crystallized
after magma emplacement. Since quartz is the last phe-
nocrystic phase to crystallize in intermediate magmas (as
the level of silica saturation required for crystallization is
usually reached late), quartz eyes rather than feldspar

123
Contrib Mineral Petrol (2013) 166:12531268 1261

Fig. 5 Relationships between

secondary CL-dark quartz and
fluid inclusions. Fluid inclusion
trails (a) are correlated with
secondary quartz (b); exposed
inclusions are shown with
arrows in (c) and in white in (d);
they have halos of secondary
quartz, and are connected by
healed fractures (d). Many
inclusions are located on
intersections of healed fractures
(e, f). Dashed arrows in (e) and
(f) point to the same inclusions.
In some cases fluid inclusions
are localized within the
transition between the core and
the rim (g and h), where
inclusions trails are shown with
arrows. a, e and hoptical
images, b, d, f and gCL
images, csecondary electron
image

phenocrysts crystallized after emplacement. In this case,
mixing of phenocrysts within a deep magma chamber
cannot be responsible for the observed diversity of quartz
eyes.
MacLellan and Trembath (1991) showed that develop-
ment of different shapes of quartz crystals can occur in situ
during prolonged crystallization within evolving melts. The
authors observed several quartz morphologies within run
products of experiments on crystallization of quartz from
haplogranodiorite melt at 597850 C and 1 kbar.
Depending on the initial degree of undercooling and
duration of the experiments, they observed quartz as

123
1262
Fig. 6 Sphalerite blebs associated with CL-dark quartz, sample
092-29700, Antapacay. aquartz eye with sphalerite blebs distrib-
uted along a fracture. b, c are closeup views of the area marked with
the rectangle in (a). a and b are BSE images, c is Cl image. dtrace
euhedral hexagonal dipyramids, skeletal crystals, anhedral
crystals, granophyric intergrowths, micropoikilitic quartz,
and as a component of spherulites. They concluded that
several quartz morphologies can form in a single envi-
ronment under conditions of continuous non-equilibrium
cooling, and that the sequences of the formation depend on
cooling rates. Our data showed that quartz with different
morphologies also have different CL patterns (Fig. 2), and
therefore we suggest that diversity of CL patterns can
similarly indicate conditions of continuous non-equilibrium
cooling.
The diversity of CL patterns in the quartz eyes in our
study can partly be explained by the fact that the surface of
the thin sections prepared for CL imaging intersects grains
randomly (i.e. not necessarily through a grain center). For
123
Contrib Mineral Petrol (2013) 166:12531268
element (Ti, Al and Zn) concentrations in points shown in b, etrace
element (Ti, Al and Zn) maps for the same area, points are the same
as in (b) and in the table (d). The width of the field of view in b, c and
e is 600 lm
example, as shown in Fig. 7 if cut along line marked
level 1 a quartz grain would show Pattern 3, whereas cut
along levels 2, 3 or 4 grains will display Patterns 2, 1, and 4
respectively. On the other hand, observed CL patterns can
also represent fully exposed (i.e. cut through the center of
grains) quartz eyes. The following model for the formation
of quartz eyes accounts for both options.
A model for the in situ formation of quartz eyes
during prolonged crystallization of porphyries
Stage I: crystallization of Quartz 1
As previously discussed, prior to emplacement porphyry
magma contains less phenocrysts than observed upon
Contrib Mineral Petrol (2013) 166:12531268
Fig. 7 A sketch showing the CL pattern type from which all types of
the observed patterns can be derived (14) by cutting it at different
levels. The sketch also show different types of embayments formed at
different stages. See text for more details
complete crystallization. At this stage magmas of inter-
mediate composition (andesitic) contain no quartz pheno-
crysts or they are scarce. For most samples it is likely that
the beginning of quartz crystallization takes place after
magma emplacement, when saturation of silica in the melt
has been achieved due to fractional crystallization. At this
point Quartz 1 crystallizes; it is Tirich because of the high
temperature of crystallization and characterized by CL of
high intensity (Stage I, Fig. 8). Rough estimates of the
crystallization temperatures were made with TitaniQ geo-
thermometer (Wark and Watson 2006). In fact, the geo-
thermometer provides high precision (5 C) only if Ti
activity is known and provided that other parameters (e.g.
pressure or magma composition) did not change. In our
case, however, due to a number of uncertainties, such as
unknown activity of titanium and unknown pressure, high
precision was not possible. It is generally assumed that Ti
activity values lower than 0.5 are rare in silicic magmas
(Wiebe et al. 2007); at the same time higher than 0.5
activities yield unrealistically low temperatures for some of
the samples. Therefore aTiO2 = 0.5 was used for calcula-
tions. Temperature estimates indicate that Quartz 1 could
crystallize at around 780891 C in Climax, 765782 C in
Rio Blanco and around 856 C in South East Porphyry
(Table 3).
1263
Stage II: crystallization of Quartz 2
Upon continuous crystallization and cooling the residual
melt becomes more enriched in silica and incompatible
elements such as water and alkali elements. It is also likely
that at this stage magma mobility is limited (2550 vol%
phenocryst content), but interstitial melt still can migrate
and form pods of fluid-rich melt within the crystal mush.
From this highly evolved melt Quartz 2 crystallizes either
as overgrowth on earlier Quartz 1 or forming new centers
of crystallization (Stage II, Fig. 8). Quartz 2 exhibits
extremely low Ti concentrations (Table 2), in most cases
too low to imply their origin from a deep magmatic
chamber. Temperature estimations (at Ti activity 0.5)
showed that Quartz 2 could crystallize at around 585
732 C in Climax, 638740 C in Rio Blanco, 653807 C
in Batu Hijau, 712754 C in SEP and 747804 C in
Panguna (Table 3).
Crystallization from a highly evolved melt is also con-
sistent with our earlier data (Vasyukova et al. 2013)
showing that those Ti-low cores often display elevated
concentrations of Al, Li and OH. Quartz 2 also displays
sector zoning (Figs. 2, 3), a feature characteristic for non-
equilibrium growth within fluids or fluid-rich melts. It is
unlikely that hydrothermal conditions apply here, therefore
sector zoning in Quartz 2 may indicate crystallization from
a fluid-rich melt, which is in a good agreement with our
other data. Clustering is also common at this stage and
multiple grain clusters can form.
Stage III: resorption of Quartz 2 and formation
of heavy fluid
As a result of prolonged crystallization of anhydrous
minerals under continuous cooling, a second boiling will
inevitably occur (Burnham 1979). Exsolution of fluid leads
to a dramatic change in the melt composition: OH2 as well
as Li and other chlorine-complexed elements partition into
the fluid, whereas Ti stays in the melt, leading to a corre-
sponding increase in Ti activity within the residual melt.
This exsolution as well as further cooling of the system
brings about disequilibrium between the fluid, the melt and
quartz eyes, which may have caused partial resorption of
the latter. Within pods of residual melt, concentration of
the exsolved fluid would be higher; bubbles could coalesce
to larger size and, if they are attached to Quartz 2 crystals
they are likely to cause formation of deep sinuous
embayments (Figs. 7, 8). Such a mechanism for formation
of deep sinuous embayments was also proposed by Chang
(2004).
Due to the reaction of the exsolved fluid with quartz a
new silica-rich liquid phase can form (Stage 3, Fig. 8).
Such reaction will be especially pronounced in systems
123
1264 Contrib Mineral Petrol (2013) 166:12531268

Fig. 8 A sketch showing different stages of quartz crystallization. c

1silicate melt, 2silicate melt with exsolved fluid, 3heavy fluid,
4feldspar crystals. 58types of quartz: 5Quartz 1, 6Quartz 2,
7Quartz 3, 8Quartz 4, 9groundmass quartz. See the detailed
description in the text

where the fluid phase underwent immiscibility, i.e. where

separation of a brine-rich phase (alkali-rich) from a vapor-
rich phase (acid-rich) occurred. This process is commonly
known as high temperature hydrolysis and is considered to
be responsible for dissolution of quartz and formation of
the new liquid phase (Kotelnikova and Kotelnikov 2010a;
Veksler 2004). The fact that fluid phase underwent
immiscibility is consistent with our fluid inclusion data, i.e.
with diversity of vapor/liquid/solid volume fractions,
which indicates heterogeneous entrapment of the fluid.
Generally, heterogeneous entrapment of fluid is inferred in
many studies of fluid inclusions for porphyry environments
(Roedder 1984; Wilkinson 2001). Unfortunately, it is not
possible to use our fluid inclusion microthermometry data
for the reconstruction of PT conditions of quartz eyes
crystallization, since the association of inclusions with
secondary quartz of healed fractures indicates their sec-
ondary origin.
The formation of this silica- and water-rich phase is
consistent with other researches, in which it was called
heavy fluid (Kotelnikova and Kotelnikov 2010b),
hydrosilicate liquid (Smirnov et al. 2012) or silicother-
mal fluid (Wilkinson et al. 1996). This heavy fluid con-
tains more silica than any hydrothermal fluid and more
water than any silicate melt, so forms an intermediate
between hydrothermal fluids and conventional melts. In
experiments such phase was found to be stable in a wide
range of temperatures (250800 C), pressures (0.52.5
kbar and [15 kbar) and compositions (Kotelnikova and
Kotelnikov 2010b; Peretyazhko et al. 2010; Thomas and
Davidson 2008; Wilkinson et al. 1996). It also was found in
natural environments as formed after prolonged fractional
crystallization (Fulignati et al. 2011; Kamenetsky and
Kamenetsky 2010; Thomas and Davidson 2008; Veksler
2004).

Stage IV: crystallization of Quartz 3

At some stage the pressure built-up by fluid becomes

unsustainable for host rocks and they fracture. This point
can be a trigger for crystallization (pressure quenching) of
Quartz 3 as overgrowth on earlier Quartz 2, or as new
crystallization centers (Stage IV, Fig. 8). Since Ti stays in
the melt whereas volatiles and alkalis partition into the
fluid phase, the activity of Ti in the melt will dramatically
increase. Also, a decrease in pressure provides higher Ti

123
Contrib Mineral Petrol (2013) 166:12531268 1265

Table 3 Estimated crystallization temperatures

Locality Sample Quartz 1 T C Quartz 2 T C Quartz 3a T C Quartz 3b T C
at aTiO2 = 0.5 at aTiO2 = 0.5 at aTiO2 = 0.8 at aTiO2 = 0.8

Climax 109647 585732 683718 648696

109644 780891 695735
Rio Blanco DC-DLP-1 643740 683730 696712
DC-DP-1 638740 714735 668696
CA6 765782 653712 689710 692
Batu Hijau SBD69 765807 829a
SRD-02 741829a
Antapaccay 09229700 642762
SEP P13 856 712754 829a 829a
Panguna 109607 747804 732801 743
a
It was shown that above concentration of around 150 ppm, Ti not only substitutes Si but also occupies interstitial positions (Stevens-Kalceff
2009) or occurs in nanoinclusions. In this case, the TitaniQ thermometer is inapplicable for the total Ti concentration. The values marked * were
calculated for Ti = 150 ppm
bdl below detection limits

uptake (Thomas et al. 2010a), explaining why Quartz 3
(and especially Quartz 3a) shows significantly higher Ti
content compared to Quartz 2.
At this stage, crystallinity of the magma is rather high,
and growth impediments must be common. Growth
impediments are small crystals, which can hinder crystal
growth where they are attached to the surface; such
embayments are small and have CL layers adapted to them
(Fig. 2a shown by white arrows).
Temperature ranges estimated using TitaniQ thermom-
eter (Wark and Watson 2006) generally confirmed that
Quartz 3 could crystallize at about the same temperatures
as Quartz 2 if we assume an increase in aTiO2, from 0.5 to
0.8 (Table 3). Thus, crystallization of Quartz 3 in Climax
started at 683718 C and finished around 648696 C, in
Rio Blanco it started at 683735 C and continued until
668712 C. In Batu Hijau Quart 3 crystallized at around
741829 C, in Antapaccayat around 642762 C and in
SEPat around 829 C. The slightly higher temperatures
of crystallization of Quartz 3a compare to Quartz 3b may
reflect a decrease in pressure.
Stage V: crystallization of Quartz 4 and groundmass quartz
The heavy fluid is chemically aggressive, extremely mobile
and may easily migrate leaving no evidence of its exis-
tence; it forms when the fluid reacts with the melt and
crystals, therefore its composition can vary depending on
what it reacted with during its formation. Heavy fluid has
extremely high metal-carrying capacity (Peretyazhko et al.
2010; Thomas and Davidson 2008; Thomas et al. 2010b;
Wilkinson et al. 1996). For example, it was found that F,
Ta, Sn and Zn partition strongly into the heavy fluid so that
concentrations of Sn and Zn in the heavy fluid are 2050
times as high as those in aqueous fluid (Thomas et al.
2010b). Therefore, quartz crystallizing from the heavy fluid
would show high concentrations of metals (most likely as
microinclusions). An example of the quartz precipitated
from the heavy fluid can be secondary quartz within the
quartz eye from Antapaccay (Fig. 6), which shows extre-
mely high concentrations of Zn. We suggest that heavy
fluid can also carry high concentrations of Ti and Al;
therefore, quartz crystallized from this phase would likely
to show extremely high Al and Ti (as nano- or micro-sized
inclusions), which was observed in Quartz 4 (Fig. 4d).
Therefore, formation of Quartz 4 is likely to occur during
the Stage V; it precipitates from the heavy fluid and can
form both discrete crystals (or outer zones) and heal frac-
tures (Stage V, Fig. 8).
Groundmass quartz crystallizes just before the onset of
the subsolidus stage. Under such conditions the rates of
crystallization are very fast, whereas diffusion rates are
slow, which leads to formation of abundant crystallization
centers and high trace element content in crystallizing
quartz. It was shown that Ti uptake in quartz is not only
temperature but also pressure dependent (Thomas et al.
2010a), therefore, pulses of pressure release (during which
a network of fractures forms) can also contribute to high Ti
uptake during this very late crystallization (Stage V,
Fig. 8).
Comparison with other models
There are two other possible mechanisms for formation of
quartz grains with CL-dark cores and CL-bright rims. The
first one involves multi-stage magma ascent, when crystal
cores crystallized in deeper and drier environments,
become partly resorbed during uplift and finally crystallize

123
1266
at lower pressures (Muller et al. 2005, 2010b). This model
however is not consistent with our data on trace elements
within CL-dark cores, which showed that they crystallized
from more evolved melt than the CL-bright rims.
The second explanation invokes magma rejuvenation
when hotter mafic magma is injected into a partly crystal-
line porphyry pluton and causes an increase of temperature,
which leads to partial resorption of dark cores and crystal-
lization of CL-brighter rims (Wark et al. 2007; Wiebe et al.
2007). This model is also not in agreement with our data.
Firstly, an increase in temperature not followed by
quenching must cause diffusion of Ti within quartz, which
would result in a change of the character of all transitions
from sharp to diffusive. This is not the case; all transitions
are sharp. Moreover, considering that in porphyry condi-
tions no quenching can be assumed and that gradual cooling
is one of the main features of those environments, any
temperature increase would be temporary and gradual
decrease of Ti uptake in quartz must eventually occur. Thus,
crystallization of groundmass quartz takes place at lower
temperatures and therefore it should show less intense CL.
On the contrary, in the studied samples groundmass quartz
shows the brightest CL with the highest Ti content.
The origin for quartz eyes suggested here provides a
better explanation for all observed features. Extremely low
Ti content in Quartz 2 together with enrichment in OH2, Li
and Al (reported in Vasyukova et al. (2013)) and presence
of sector zoning are in a good agreement with their crys-
tallization from highly evolved fluid-rich melt just on the
brink of fluid exsolution. High Ti content (relatively to that
in the cores of quartz eyes) in Quartz 3 together with
extremely sharp transitions between cores and rims are
consistent with crystallization from the drier melt with
higher Ti activity, which formed after the onset of fluid
separation from the melt (no temperature increase is
involved). Pressure releases as a result of fracturing of host
rocks can further contribute to an increase in Ti uptake in
Quartz 3. Estimations of crystallization temperatures by
TitaniQ geothermometer made for different types of quartz
at different Ti activity generally confirm the possibility that
no temperature increase was involved (Table 3). Even the
different character of embayments can be explained by
prolonged crystallization under continuous cooling: deep
and sinuous embayments form due to attached fluid bub-
bles, whereas short embayments form due to growth
impediments as a result of an increase of magma crystal-
linity during later stages (Fig. 7).
Significance of this model for the formation
of porphyry deposits
The suggested origin of quartz eyes is also more consistent
with the existing model for formation of porphyry deposits
123
Contrib Mineral Petrol (2013) 166:12531268
(Burnham 1979). According to the model fluid exsolution
and its accumulation in the apical portions of a porphyry
body causes fracturing of roof rocks and the formation of a
3D network of fractures where ore minerals precipitate
(stockwork ore). The most common feature of many por-
phyry deposits are several generations of healed fractures
(veinlets), which stresses that several pulses of fluid-
releasing events likely took place. The presence of several
generations of secondary quartz is in a good agreement
with the model. Every such pulse is expected to start with
an accumulation of fluids in the apical portion, which
gradually builds up the pressure. Once the fluid pressure is
higher than the lithostatic pressure, fracturing occurs, fluid
escapes from the intrusion, and pressure is released
(Burnham 1979; Gustafson 1978; Sinclair 2007).
Such events in the apical part are reflected in the whole
pluton by sporadic drops in pressure accompanied by
pulses of fluid exsolution alternating with periods of
gradual pressure increase. Those multiple pulses are pre-
served in the CL textures observed in quartz eyes: the first
event of fluid exsolution, its accumulation, building up of
pressure and subsequent pressure release causes resorption
of CL-dark cores and subsequent crystallization of CL-
bright rims, respectively. Further pressure fluctuations
would cause oscillatory zoning within the CL-bright rims.
When the system is closed again, a new cycle can begin:
progressively CL-darker quartz will crystallize when
pressure is increasing and the residual melt becomes
slightly richer in incompatible elements. The sudden drop
of pressure (the beginning of a new cycle) will be recorded
by crystallization of a slightly brighter in CL quartz layer.
Conclusions
Our study of CL patterns in quartz eyes from six porphyry
deposits reveals significant diversity of their internal tex-
tures. Mechanisms suggested earlier that can explain such
diversity were found inconsistent with our data. We pro-
pose that quartz eyes in porphyry stocks primarily crys-
tallize in situ after magma emplacement. Early Quartz 1 is
Ti-high and crystallizes at relatively high temperatures.
Quartz 2 crystallizes later from the more evolved melt on
the brink of fluid exsolution; it shows low Ti content and
often displays sector zoning. Subsequent fluid exsolution
causes immediate change in melt chemistry: OH2, alkalis
and other Cl-complexed elements partition into the fluid
phase, whereas Ti stays in the melt, which brings about an
abrupt increase in Ti activity in the latter. During further
cooling the exsolved fluid reacts with both melt and CL-
dark Quartz 2 leading to resorption of the latter: where fluid
bubbles are attached to the quartz deep sinuous embay-
ments form; other quartz crystals become rounded.
Contrib Mineral Petrol (2013) 166:12531268
Accumulation of the fluid under the cupola builds up the
pressure, which at some point becomes unsustainable for
host rocks, and they fracture. This triggers crystallization
of Quartz 3, which is much higher in Ti content then
Quartz 2 (partially because the melt, from which it crys-
tallizes has higher Ti activity, and also due to pressure
release). When the fluid phase reacts with quartz, a new
fluid-like silica-rich phase can form, a so-called heavy
fluid. From this phase Quartz 4 crystallizes overgrowing
Quartz 3 or healing fractures.
Prolonged crystallization under continuous cooling
accounts better for diversity of CL textures than crystalli-
zation in different parts of deep magma chamber. Not only
it is more consistent with all CL features observed in this
study but it is also in a better agreement with the existing
model for formation of porphyry-style deposits.
Acknowledgments
This research was performed as a part of the PhD study
supported by a CODES Graduate Research Scholarship
(University of Tasmania, Grant No. 037923).
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