Mineralogical Magazine (2021), 85, 639–664

doi:10.1180/mgm.2021.72

Review Article

Mineralogy and mineral chemistry of quartz: A review

Jens Götze1* , Yuanming Pan2 and Axel Müller3,4
1
Institute of Mineralogy, TU Bergakademie Freiberg, Brennhausgasse 14, 09599 Freiberg, Germany; 2Department of Geological Sciences, University of
Saskatchewan, Saskatoon, Saskatchewan S7N 5E2, Canada; 3Natural History Museum, University of Oslo, P.O. Box 1172, Blindern, 0318 Oslo, Norway; and 4Natural
History Museum, Cromwell Road, London SW7 5BD, UK

Abstract
Quartz (trigonal, low-temperature α-quartz) is the most important polymorph of the silica (SiO2) group and one of the purest minerals
in the Earth crust. The mineralogy and mineral chemistry of quartz are determined mainly by its defect structure. Certain point defects,
dislocations and micro-inclusions can be incorporated into quartz during crystallisation under various thermodynamic conditions and
by secondary processes such as alteration, irradiation, diagenesis or metamorphism. The resulting real structure is a fingerprint of the
specific physicochemical environment of quartz formation and also determines the quality and applications of SiO2 raw materials. Point
defects in quartz can be related to imperfections associated with silicon or oxygen vacancies (intrinsic defects), to different types of dis-
placed atoms, and/or to the incorporation of foreign ions in lattice sites and interstitial positions (extrinsic defects). Due to mismatch in
charges and ionic radii only a limited number of ions can substitute for Si4+ in the crystal lattice or can be incorporated in interstitial
positions. Therefore, most impurity elements in quartz are present at concentrations below 1 ppm. The structural incorporation in a
regular Si4+ lattice site has been proven for Al3+, Ga3+, Fe3+, B3+, Ge4+, Ti4+, P5+ and H+, of which Al3+ is by far the most common
and typically the most abundant. Unambiguous detection and characterisation of defect structures in quartz are a technical challenge
and can only be successfully realised by a combination of advanced analytical methods such as electron paramagnetic resonance
(EPR) spectroscopy, cathodoluminescence (CL) microscopy and spectroscopy as well as spatially resolved trace-element analysis such
as laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) and secondary-ion mass spectrometry (SIMS). The pre-
sent paper presents a review of the state-of-the-art knowledge concerning the mineralogy and mineral-chemistry of quartz and illustrates
important geological implications of the properties of quartz.

Keywords: quartz, mineral chemistry, real structure, point defects, trace elements, electron paramagnetic resonance (EPR),
cathodoluminescenece (CL)
(Received 25 June 2021; accepted 22 September 2021; Accepted Manuscript published online: 28 September 2021; Associate Editor:
Martin Lee)

Introduction is defined as quartz containing less than 50 ppm of impurity ele-

ments, specifically < 30 ppm Al, < 10 ppm Ti, < 8 ppm Na and K,
The SiO2 system is very complex. Though it has a simple chemical
< 5 ppm Li and Ca, < 3 ppm Fe, < 2 ppm P and < 1 ppm B
formula, SiO2, at least 15 modifications or polymorphs are
(Harben, 2002; Müller et al., 2012). The type of impurities
known, i.e. mineral phases with the same stoichiometric compos-
controlling the quality of high-purity quartz strongly influences
ition but different crystal structures. Quartz is the most important
the processing and potential use of the raw materials. Therefore,
silica polymorph in nature, and occurs as a common
exploration for high-purity quartz deposits requires a thorough
constituent of magmatic, metamorphic and sedimentary rocks.
knowledge of the factors influencing the petrological and chem-
In addition, quartz represents an economically important silica
ical properties of quartz. Several studies have shown that granitic
raw material. Both single crystals and polycrystalline quartz
pegmatites provide potentially the best sources of high-purity
material are used in industry, for example, as high-purity quartz
quartz (Larsen, 2000; Müller et al., 2007, 2012, 2015).
crystals or sands, refractory materials, or as an ore for silicon
The mineralogy and mineral chemistry of quartz are deter-
metal. For certain highly advanced applications, synthetic quartz
mined mainly by its defect structure. Certain point defects, dislo-
crystals or SiO2 materials are necessary due to increasing quality
cations, planar defects and micro-inclusions of fluids/melts and
requirements not being easily met by silica raw materials (Götze
minerals can be incorporated into quartz during crystallisation
and Möckel, 2012; Müller et al., 2012, 2015).
under diverse thermodynamic conditions and by secondary pro-
The growing worldwide consumption of a wide range of high-
cesses, such as alteration, irradiation, diagenesis or metamorph-
technology applications means there is an increasing demand for
ism (Götze, 2009). The resulting real structure is not only a
high-quality natural quartz raw materials. Such high-purity quartz
fingerprint of the specific physicochemical environment of quartz
formation and secondary processes, but also determines the qual-
*Author for correspondence: Jens Götze, Email: [email protected] ity of SiO2 raw materials. Therefore, quartz represents an import-
Cite this article: Götze J., Pan Y. and Müller A. (2021) Mineralogy and mineral chemistry
of quartz: A review. Mineralogical Magazine 85, 639–664. https://doi.org/10.1180/
ant industrial raw material, and also serves as an important
mgm.2021.72 mineralogical and geochemical indicator for geological and ore-
© The Author(s), 2021. Published by Cambridge University Press on behalf of The Mineralogical Society of Great Britain and Ireland

https://doi.org/10.1180/mgm.2021.72 Published online by Cambridge University Press

 640 Jens Götze et al.

forming processes (e.g. Götze and Möckel, 2012 and references

therein).
Quartz is one of the purest minerals, nevertheless minor impur-
ities and defects have potentially significant importance and infor-
mation, particularly regarding the mineral genesis. However, the
detection and characterisation of such defects is generally a tech-
nical challenge and can only be successfully accomplished by a
combination of advanced analytical methods, such as electron
paramagnetic resonance (EPR) spectroscopy, cathodolumines-
cence (CL) microscopy and spectroscopy, synchrotron X-ray
absorption spectroscopy (XAS) together with spatially resolved
trace-element analysis such as laser ablation inductively coupled
plasma mass spectrometry (LA-ICP-MS) and secondary-ion
mass spectrometry (SIMS). Trace-element analysis provides gen-
eral information about the types of impurities in quartz and
their quantitative abundance. Information about the homogeneity
or heterogeneity of quartz grains/crystals and the possible spatial
distribution of defects can be obtained from CL measurements.
Finally, EPR and XAS measurements yield additional information
about the structural incorporation of trace elements and other
structural defects not related to impurities, and are increasingly
Fig. 1. Projection of morphologically right-handed α-quartz atomic positions onto
complemented by theoretical data from first-principles the (0001) plane perpendicular to the c-axis, showing the EPR coordinate system
calculations. In addition, other spectroscopic techniques such as (xyz), crystallographic axes a1, a2 and a3, and z∥c; the central c-axis large channel
synchrotron XAS and Mössbauer spectroscopy, which have is seen to be surrounded by six c-axis small channels; LS denotes left-handed helices.
lower sensitivities than EPR techniques, have contributed useful
information about the structural states of iron in quartz. In
many cases, microscopic techniques (polarising microscopy, scan- character of alpha-quartz. The silicon atom in the quartz structure
ning electron microscopy (SEM), transmission electron micros- resides on a two-fold axis, whereas all oxygen atoms are at general
copy (TEM), micro-Raman spectroscopy, or microbeam positions (Le Page et al., 1980; Kihara, 1990; Baur, 2009). Each
synchrotron X-ray fluorescence and XAS can complement the SiO4 tetrahedron has two long and two short Si–O bonds at
investigations. 1.613(2) Å and 1.603(2) Å, respectively, in quartz measured at
This paper presents a review of the state-of-the-art knowledge 291 K and ambient pressure (Baur, 2009). Le Page et al. (1980)
concerning the mineralogy and mineral chemistry of quartz and noted that the two Si–O bond distances are 1.611(1) Å and
the importance for better understanding of certain geological 1.606(1) Å at 94 K, and they do not change in the temperature
processes, together with improvements in technical processing range from 94 K to 298 K, however the Si–O–Si angle increases
of silica raw materials. from 142.69(4)° to 143.65(5)°. In the EPR literature, the SiO4
tetrahedron in the quartz structure is typically represented by
the notation [SiO4]0 to emphasise its overall neutrality, whereas
The mineralogy of quartz substitutional groups such as [GeO4]0 and [AlO4]–, together
Quartz is a mineral with the chemical formula SiO2, which exists with their associated paramagnetic centres [GeO4]– and [AlO4]0
in two modifications in nature. The most common and most are denoted accordingly (Weil, 1984; Mashkovtsev and Pan,
important modification is trigonal, low-temperature alpha-quartz, 2013; Alessi et al., 2014).
which is stable under surface conditions. At atmospheric pressure, Several chemical and physical properties of quartz such as
alpha-quartz transforms at ca. 573°C into hexagonal, high- trace element and isotopic composition, luminescence behaviour,
temperature beta-quartz. This transformation is reversible and is micro-inclusion inventory or colour are strongly dependent on
accompanied by a change of the density from 2.65 to 2.51 g/cm3. the specific P–T–x conditions of its formation. These varying
The process also occurs, vice versa, during crystallisation from a properties result in the development of numerous varieties, i.e.
melt or high-grade metamorphism during which the hexagonal colour varieties such as amethyst, smoky quartz and rose quartz,
high-temperature beta-quartz forms and subsequently transforms or certain growth phenomena such as fibre and sceptre quartz, or
during cooling into the trigonal low-temperature modification. microcrystalline quartz varieties such as chalcedony and quartzine
The structural changes during this transformation typically result (Rykart, 1995; Blankenburg et al., 1994; Götze, 2009).
in the formation of defects or twinning (Blankenburg et al., 1994).
The crystal structure of alpha-quartz consists of a three-
Point defects in quartz
dimensional network of [SiO4]4–-tetrahedra, which are all linked
via the oxygen atoms and are arranged in helical chains along Zero-dimensional point defects in quartz can be related to the
the c-axis forming structural channels (Fig. 1). The left-handed incorporation of foreign ions in lattice sites and interstitial posi-
or right-handed helices in the quartz structure correspond to tions, to different types of displaced atoms, and/or to defects asso-
morphologically right and left crystals, respectively (Donnay ciated with silicon or oxygen vacancies (e.g. Weil, 1984, 1993;
and Le Page, 1978; Glazer, 2018), which can be distinguished Stevens Kalceff, 2009; Nilges et al., 2008, 2009; Pan et al., 2009;
by the relative position of the trapezohedron face x to the positive Mashkovtsev and Pan, 2012a, 2012b; Mashkovtsev et al., 2013a;
main rhombohedron face r. The c-axis in the trigonal symmetry is Alessi et al., 2014; Mashkovtsev and Pan, 2014). The latter
identical with the optical axis and results in the optical uniaxial represent pure lattice defects and can be generated without the

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 Mineralogical Magazine 641

incorporation of impurity ions into the quartz lattice. Point

defects can serve as the starting locations for more extended
defects such as dislocations or planar defects (McLaren et al.,
1983, 1989; Lin et al., 1994; McConnell et al., 1995).
According to their electronic structure, point defects can be
classified into diamagnetic and paramagnetic types and investiga-
tions are mainly recognised using EPR spectroscopy in combin-
ation with other spectroscopic methods (e.g. luminescence
spectroscopy, UV-Vis-IR absorption spectroscopy, synchrotron
XAS, Mössbauer spectroscopy) and trace-element analysis. Most
of the paramagnetic centres in quartz are metastable, i.e. they
are sensitive to irradiation and temperature treatment. However,
some stable centres have also been detected, which can be formed
by the incorporation of paramagnetic ions such as H+/0, Ag2+/0,
Li0, Cu2+/0 or Ni+, mainly in interstitial positions (Laman and
Weil, 1977; Davis and Weil, 1978; Isoya et al., 1983; Weil, Fig. 2. Representative powder EPR spectrum of a high-purity quartz from Kyshtym
(Russia) containing 4.2 ppm Al (Götze et al., 2017) measured at a microwave fre-
1993). Even these paramagnetic ions in quartz are mostly not
quency (ν) of
9.39 GHz and temperature of 85 K, showing the [AlO4]0 centre. Also
intrinsic and are either incorporated by electron diffusion or con- shown for comparison is the simulated spectrum of this centre using spin
verted from diamagnetic precursors via irradiation. Indeed, most Hamiltonian parameters from Walsby et al. (2003). Insert is a room-temperature spec-
point defects in quartz are diamagnetic, but can be converted to trum of the same sample containing <0.41 ppm Fe (i.e. the detection limit of
paramagnetic ones recognisable by EPR analysis, by various phys- LA-ICP-MS), showing a rhombic Fe3+ centre at the effective g =
4.28.

ical and chemical treatments (e.g. natural and artificial irradiation;

Weil, 1984; Pan and Nilges, 2014). 1984). Nuttall and Weil (1981c) also reported the triplet-state
The EPR techniques, with superior sensitivity unmatched by (S = 1) centre [AlO4]+ in quartz measured at
35 K after X-ray
any other structural methods, have identified a large number of irradiation at 77 K (Table S1), which contains two electron
paramagnetic defects (and their diamagnetic precursors) in quartz holes, one at each of two symmetry-related oxygen atoms bonded
(Supplementary Tables S1 and S2, see details below). In particu- to an aluminium substituting for silicon and apparently formed
lar, the common detection and analysis of diagnostic hyperfine or from the diamagnetic [AlO4/M+]0 precursors as well.
superhyperfine structures of paramagnetic defects, which arise
from interactions with non-zero-spin nuclei, not only aid Gemanium
in their unambiguous identification, but also typically provide
definitive information about their geometric and electronic con- Although the abundance of germanium in nature is low, the iso-
figurations. For example, 29Si hyperfine structures, which is the valent substitution of Ge4+ for Si4+ is common. The resulting dia-
only stable isotope of silicon with a non-zero nuclear spin (I = magnetic [GeO4]0 defect in quartz can be transformed by ionising
1/2) and a natural isotope abundance of 4.7%, are often detected radiation at <100 K into two paramagnetic [GeO4]– centres
by EPR. However, analysis of 17O hyperfine structures, which is (Table S1), which are distinguished by the orbital of the unpaired
the only stable isotope of oxygen with a non-zero nuclear spin spin lying along the different O–Ge–O bisectors of the GeO4
(I = 5/2) and an exceedingly low abundance of 0.04%, generally tetrahedron (Mackey, 1963; Isoya et al., 1978; McEachern et al.,
requires artificially 17O-enriched quartz samples (McEachern 1992; McEachern and Weil, 1994). On warming above 150 K or
and Weil, 1994; Mashkovtsev et al., 2013). irradiation at room temperature, the [GeO4]– centres can capture
M+ ions (Li+, Na+ and Ag+) released from associated [AlO4/M+]0
centres and form the [GeO4/M+]0 centres (Table S1; Mackey,
Aluminium 1963; Weil, 1971; Weil, 1984; Rakov et al., 1985; Dickson et al.,
Aluminium is the prevailing impurity in quartz. The [AlO4]0 1991; McEachern et al., 1992; McEachern and Weil, 1994;
centre (Fig. 2) was first described in smoky quartz by Griffiths Claridge et al., 2008).
et al. (1954). This paramagnetic centre is the most In addition, multiply-compensated germanium electron cen-
common trace-element defect in quartz, which is caused by sub- tres such as [GeHLi2] and [GeH–H+1 H+2 ] have been reported.
stitution of Si4+ by Al3+ with an electron hole localised at one of They are interpreted to derive from the diamagnetic [GeO4/
the four nearest O2– ions. The precursor state for this paramag- M1M2] precursors, containing a divalent Ge2+ ion and two mono-
netic centre is the diamagnetic [AlO4/M+]0 defect with an adja- valent charge compensators (M = Li+, H+, Na+), by capturing a
cent charge compensating cation (M+ = H+, Li+, Na+) at an paramagnetic atomic hydrogen during irradiation (Weil, 1971;
interstitial position in the c-axis channel (Botis et al., 2009). Laman and Weil, 1978; Weil, 1984).
These diamagnetic defects have been confirmed by the low-
temperature EPR characterisation of the paramagnetic [AlO4/
Iron
M+]+ centres in quartz irradiated and measured at 77 K
(Table S1; Mackey, 1963; Mackey et al., 1970; Nuttall et al., Iron can be incorporated into quartz in three different valence
1981a,b; Dickson and Weil, 1990; Walsby et al., 2003; Botis and states (Fe2+, Fe3+ and Fe4+; Cox, 1976, 1977; Cohen, 1985;
Pan, 2009, 2011). The paramagnetic [AlO4/M+]+ centres are Cressey et al., 1993; Weil, 1994; Schofield et al., 1995;
known to convert to the [AlO4]0 centre upon warming to room Dedushenko et al., 2004; Di Benedetto et al., 2009; SivaRamaiah
temperature (Cohen, 1956; Nuttall and Weil, 1981a; Walsby et al., 2011; SivaRamaiah and Pan, 2012), in addition colloidal
et al., 2003). The optically active [AlO4]0 centre is responsible clusters of metallic iron have also been reported to occur in quartz
for the colour of smoky quartz (O’Brien, 1955; Meyer et al., (Daniels and Morton, 1981; SivaRamaiah and Pan, 2012). EPR

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 642 Jens Götze et al.

studies have established at least six distinct Fe3+ centres substitut- [O3AlO–PO3] centre is responsible for radiation-induced rose col-
ing for Si, as either the charge uncompensated [FeO4]– centre or ouration of quartz.
charge-compensated [FeO4/M+]0 centres (M+ = Li+, H+, Na+, The aforementioned examples illustrate that there typically
Table S1; Scala and Hutton, 1976; Mombourqette et al., 1986, exists a close relation between point defects and the different col-
1989; Halliburton et al., 1989; Minge et al., 1989, 1990; Weil, ours of quartz (Lehmann, 1978; Rossman, 1994). Although sev-
1984, 1994). The larger ionic radius of Fe3+ (0.64 Å) compared eral allochromatic colours in quartz such as green, blue and red
to Si4+ (0.42 Å), means that the tetrahedra will be distorted. are caused by micro-inclusions of impurities (e.g. dickite, rutile,
Therefore, the structural incorporation of Fe3+ is only possible hematite, goethite, celadonite and dumortierite), idiochromatic
in marginal parts of the quartz crystals or in fissures (Götze colours are mainly generated by chromophores (Rossman, 1994;
and Plötze, 1997). Higher amounts of iron can cause lattice Yang et al., 2007; Scholz et al., 2012). This group consists of
defects promoting the formation of highly disordered areas such ions of 3d elements (e.g. synthetic blue quartz: Co2+, green
as in the case of amethyst (Mineeva et al., 1991). chrysoprase: Ni2+) or paramagnetic centres, which can be acti-
The [FeO4/M+]0 centres can be converted to the [FeO4]– cen- vated by irradiation (Lehmann, 1978; Meyer et al., 1984).
tre by irradiation (Hutton and Troup, 1966; Stegger and However, the discussion concerning the origin of colours in
Lehmann, 1989). This process also results in the conversion of quartz is very complex and partly controversial and will not be
Fe3+ to Fe4+ accompanied by the formation of the typical ameth- made here in detail. A thorough review about the origin of colours
yst colour (Fig. 3; Lehmann and Moore, 1966; Stegger and in quartz is given by Rossman (1994).
Lehmann, 1989; Dedushenko et al., 2004; Di Benedetto et al., A number of point defects can be attributed to oxygen and sili-
2009). However, details concerning the Fe4+ site and its local con vacancies or oxygen excess. Oxygen-excess centres in quartz
environment have not been determined unequivocally (Cox, include the peroxy linkage (≡Si–O–O–Si≡) and the peroxy rad-
1976, 1977; Dedushenko et al., 2004; Di Benedetto et al., 2009). ical (≡Si–O–O), an oxygen associated hole centre consisting of
Similarily, very little is known about the local structural environ- an O–2 ion bound to a single silicon on three oxygen atoms
ment of Fe2+ in quartz (Cressey et al., 1993; Schofield et al., 1995; (Friebele et al., 1979). In addition, hydrogen excess from the
Di Benedetto et al., 2009), because the magnetic properties of Fe2+ H2O crystallisation medium can also result in the formation of
with oxygen neighbours preclude its EPR observation at conven- OH– centres in quartz. This defect consists of a proton bound
tional X-band frequencies (Weil, 1994). on a regular O2– ion of the SiO4 tetrahedron (Weil, 1984,
1993). In addition, the EPR detection of two H-trapped hole cen-
tres ([H4O4]+ and [H3O4]0) (Table S1) has been used to suggest
Titanium the presence of the neutral diamagnetic precursor with four
hydrogen atoms located at the tetrahedral Si site (i.e. the
Titanium is a typical trace impurity in quartz and isovalently
[H4O4]0 or hydrogarnet defect; Nuttall and Weil, 1980; Lin
substitutes as Ti4+ for Si4+ in the SiO4 tetrahedra. The Ti4+ in
et al., 1994; Lees et al., 2003; Jollands et al., 2020). Similarly,
the diamagnetic [TiO4]0 centre can be transformed to the para-
the EPR detection of the [HLi2O4]0) centre in gamma-ray-irra-
magnetic [TiO4]– centre during irradiation at low temperatures
diated quartz suggests the presence of analogous diamagnetic
(Table S1; Bershov, 1970; Isoya and Weil, 1979; Weil, 1984;
precursors [HLi3O4]0 or [H2Li2O4]0 (Table S1; Lees et al., 2003).
Bailey et al., 1992; Bailey and Weil, 1992a,b). This [TiO4]– centre
is unstable above 120 K and, similar to the [GeO4]– centres, can
capture diffusing M+ ions (H+, Li+, Na+) to form charge compen- The group of oxygen-vacancy electron centres
sated [TiO4/M+]0 centres (Table S1; Wright et al., 1963;
The group of oxygen-vacancy electron centres (OVEC) involves
Rinneberg and Weil, 1972; Weil, 1984; Matyash et al., 1987;
an oxygen vacancy (≡Si–Si≡) and can be divided into the E′
Isoya et al., 1988; Bailey and Weil, 1991, 1992).
and E′′ types, denoting one and two unpaired electrons (S = 1/2
There is an ongoing discussion about the role of substitutional
and 1), respectively (Table S2). The E′ (the •Si≡O moiety) centres
Ti as an origin for the rose colour in quartz (Wright et al., 1963).
are the most frequent defects in quartz apart from Al centres and
Smith et al. (1978) suggested that the colour originates from a
can occur in different stages depending on thermal stability and
charge transfer between substitutional Ti4+ and interstitial Fe2+.
sensibility to irradiation (Griscom, 1985). The most common
Investigations by Lehmann and Bambauer (1973) and Cohen
E′ 1 centre can be formed by various irradiations involving alpha
and Makar (1985) showed that additional Ti3+ at interstitial struc-
particles, electron beams, neutrons, gamma- and X-rays, and
tural channel sites is responsible for the rose colouration.
has been used as palaeo-dosimeters and geochronometers due
However, further studies have shown that nano-inclusions of
to its high thermal stability (> 550°C) (Moiseev, 1985; Toyoda,
dumortierite can also produce the colour in massive rose quartz
2011, 2016). In addition, the E′ 1 centre in nature, induced by
(Goreva et al., 2001; Ma et al., 2002).
diverse radiation sources from U/Th-bearing rocks/fluids to
potassic alteration, can be used as an indicator for the formation
of uranium deposits when the dominant source of radiation is
Phosphorus
uranium (Pan et al., 2006; Botis et al., 2006, 2008; Cerin et al.,
Phosphorus as a trace element has been shown to substitute 2017). X-ray or fast-electron irradiation of Ge-doped quartz at
for Si4+ in the quartz structure as EPR has detected several room temperature yielded at least three Ge analogues of E′ cen-
radiation-induced [PO4]0 centres (Table S1). In particular, tres, including the Ge E′ 1 centre stable up to 700 K, the Ge E′ 2
Mashmeyer and Lehmann (1983) reported the [O3AlO–PO3] cen- centre with a hydrogen impurity stable up to 500 K, and another
tre with a hole trapped on the bridging oxygen atom between sub- Ge(IV) centre unstable at room temperature (Fig. 4; Feigl and
stitutional Al and P atoms in quartz, providing unambiguous Anderson, 1970; Mashkovtsev et al., 2013).
evidence for the coupled substitution: P5+ + Al3+ = 2 Si4+. In add- Understanding of the E′ 1 and Ge E′ 1 centres in quartz has
ition, Maschmeyer and Lehmann (1983) suggested that the evolved with increasingly complete EPR data and sophisticated

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 Mineralogical Magazine 643

Fig. 3. Representative single-crystal EPR spectrum of a natural amethyst measured

with B∥y and at 294 K. Letters S and I mark lines belonging to the S1 ([FeO4/Li]0;
Fig. 4. Representative single-crystal EPR spectrum of an electron-irradiated,
Han and Choh, 1989; Halliburton et al., 1989) and I centres, respectively. Note that 17
O-enriched quartz (JC324) measured, after annealing at 573 K, with B‖c, room tem-
the so-called interstitial (I) centre is actually [FeO4]– with substitutional Fe ions at
perature and X-band frequency (
9.3 GHz; modified from Mahskovtsev et al., 2013),
the Si sites (Mombouquette et al., 1986). Also present are the broad signal at g =
showing three 17O hyperfine sextets and one 73Ge hyperfine line of the Ge E′ 1 centre.
4.28 and the E′ 1 centre (modified from SivaRamaiah et al., 2011).
Insert shows the 3D spin density of the Ge E′ 1 centre calculated from the tri-vacancy
with an Al impurity model.

first-principles calculations (Fig. 4; Li and Pan, 2012; Mashkovtsev

et al., 2013). The tri-vacancy model with an Al impurity, which
best reproduces all available EPR data, involves the removal of
one Si and two O atoms as well as the presence of a neighbouring
Al impurity atom (Fig. 4; Li and Pan, 2012; Mashkovtsev et al.,
2013). Other well-characterised E′ centres in quartz include the
E′ 4 and E′ 11,16 centres (Table S2; Perlson and Weil, 2008;
Mashkovtsev and Pan, 2012a, 2016, 2018; Mashkovtsev et al.,
2019). The former contains a proton near the oxygen vacancy,
wheras the latter with diagnostic 27Al superhyperfine structures pro-
vide experimental proof for the hypothesis that Al impurity plays an
important role in the formation of E′ centres (Jani et al., 1983;
Mashkovtsev and Pan, 2018; Mashkovtsev et al., 2019). In addition,
various E′′ centres arising from interactions between two neigh-
bouring E′ centres have been discovered and characterised with
the triplet-state model in recent years (Table S2; Mashkovtsev
et al., 2007; Mashkovtsev and Pan, 2011, 2012a, 2012b, 2014).
A family of silicon-vacancy hole centres is represented by dif-
ferent localisations of the unpaired electron on one, two or three
oxygen atoms of the tetrahedra with silicon vacancies, which have
been denoted as the O–, O2–, O3– 2 or O
3–
type radicals (Fig. 5;
Fig. 5. Representative single-crystal EPR spectrum of an electron-irradiated quartz
Table S2; Mashkovtsev et al., 1978; Botis et al., 2005; Nilges
measured at W-band frequency (
94 GHz), B^c =
140°, T = 110 K and a microwave
et al., 2008, 2009; Pan et al., 2008, 2009; Mashkovtsev and Pan, power of 0.2 mW, illustrating three silicon-vacancy hole centres (H′ 1, H′ 4(I) and H′ 5)
2013; Alessi et al., 2014). By analogy to the notation for oxygen- (modified from Nilges et al., 2009). Note that the H′ 1 (alias #1) centre has six main
vacancy electron centres, Mashkovtsev and Pan (2013) relabelled lines corresponding to six magnetically inequivalent sites and that 29Si hyperfine
the silicon-vacancy hole centres as H′ 1 to H′ 7 (Table S2). The O– satellites are marked on four main lines. Also note that the two remaining main
lines at
3330 mT have irregular line shapes due to an incompletely resolved 27Al
centres with a hole trapped in a single nonbonding 2p orbital (i.e. superhyperfine structure (Nilges et al., 2009). The H′ 4(I) centre is characterised by a
the non-bridging oxygen hole centres or NBOHC; ≡Si–O) are well-resolved 27Al superhyperfine structure.
very common defects in almost all quartz types, which can be
detected by CL spectroscopy (Stevens Kalceff, 2009). However,
the majority of the O– centres in quartz are those associated (agate, chalcedony) and in some hydrothermal quartz formed
with impurity ions such as Al3+ described above (Table S1) and with high growth rates. In contrast, pegmatite quartz, in general,
are not linked with any silicon vacancy. has a remarkably low abundance of defects associated with oxy-
Several studies showed that defects associated with oxygen and gen or silicon vacancies indicating growth of quartz from a parent
silicon vacancies are most frequent in quartz crystallised at rela- melt/fluid under more or less constant physicochemical condi-
tively low temperature (< 250°C) from amorphous silica precur- tions (Götze et al., 2004, 2005).
sors due to rapid cooling (Götze et al., 1999, 2015a, 2020). Moreover, partial dissolution experiments demonstrated that
Therefore, these defects are common in microcrystalline quartz the silicon-vacancy hole centres in detrital quartz from the

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 644 Jens Götze et al.

Athabasca Basin (Canada) are concentrated preferentially along (Ramseyer et al., 1988; Götze et al., 2001a). The visible lumines-
the grain margins. This observation is consistent with the limited cence colours of quartz in most igneous and metamorphic rocks
penetration distances of alpha particles emitted from the decay of and in some authigenic quartz depend on the relative intensities
the uranium series present in palaeo-uranium-bearing fluids, pro- of these two dominant emission bands (Fig. 6).
viding the best linkage with mineralisation processes in uranium
deposits (e.g. tracing the conduits of uranium-bearing fluids and
Blue emission band at
450 nm (2.75 eV)
constraining the sources of uranium; Pan et al., 2006; Hu et al.,
2008; Cerin et al., 2017). The
450 nm (2.75 eV) blue emission band (Fig. 6c) is related to
In addition, abundant data exist on the health effects of quartz. oxygen deficiency centres (ODC) and is similar in amorphous
This varies widely in emphasis from particle sizes/morphologies to and crystalline SiO2 (Skuja, 1998). Recombination of the so-called
surface properties and structural states. Long-term exposures to self-trapped exciton (STE) involves an irradiation-induced elec-
quartz and other silica forms (e.g. cristobalite and amorphous sil- tron hole pair (oxygen Frenkel pair) consisting of an oxygen
ica) are known to cause serious and potentially life-threatening dis- vacancy and a peroxy linkage (Stevens Kalceff and Phillips,
eases such as silicosis, fibrosis and lung cancer (Goldsmith, 1994). 1995). The blue emission at ca. 450 nm is probably the most com-
Of particular interest are the identification of various defects such mon CL emission in natural quartz and can be detected in almost
as the peroxy and superoxide radicals and NBOHC on the surfaces all quartz types.
of, and in, bulk quartz and their effects on toxicity and carcinogenic In addition to the evidenced activation of the 450 nm band by
activity (Fubini et al., 1990; Giordano et al., 2007; Di Benedetto a structural defect, several studies reported a strong correlation
et al., 2019, 2021). For example, Fubini et al. (1990) proposed between the intensity of luminescence and the concentration of
the presence of these radicals on quartz surfaces or chemical func- Ti in quartz, with the brightest CL corresponding to the highest
tionalities as a possible mechanism for fibrogenecity via their reac- Ti concentrations (e.g. Müller et al., 2002, 2003; Van den
tions with macrophage oxygen metabolites, triggering the Kerkhof et al., 2004; Rusk et al., 2008; Leeman et al., 2012;
abnormal production of fibroblast stimulating factors and ultim- Drivenes et al., 2016). Up to now there has been no serious spec-
ately silicosis. However, a comprehensive synthesis of the volumin- troscopic evidence that Ti is responsible for the activation of the
ous literature on the health effects of quartz is beyond the scope of blue emission in quartz. However, recent systematic studies of
this review in which the emphasis is on geological contexts. Ti-rich natural quartz from igneous rocks, as well as synthetic
quartz from Ti-diffusion experiments could prove that Ti might
also be responsible for the activation of the 450 nm luminescence
Cathodoluminescence properties of quartz
emission band (unpublished data – compare with Fig. 22).
Cathodoluminescence (CL) is a powerful method, which enables
the visualisation of the defect structure of minerals and reveals
Red emission band at 620–650 nm
visually internal features caused by the varying spatial distribution
of point defects that are not discernible by other analytical meth- The red emission band at 620–650 nm (1.95–1.9 eV; Fig. 6c) is
ods (Götze, 2012a; Götze et al., 2013; Götze and Hanchar, 2018). attributed to the recombination of electrons in the non-bridging
In general, quartz and other SiO2 modifications (including oxygen band-gap state with holes in the valence-band edge
amorphous silica) show similar main luminescence emission (Siegel and Marrone, 1981; Stevens-Kalceff, 2009). A number of
bands. This is due to the fact that short-range order structural different precursors of this NBOHC has been proposed such as
defects are caused mainly by silicon–oxygen and silicon–silicon strained silicon–oxygen bonds, hydrogen or sodium impurities,
interactions rather than by interactions between oxygen atoms or peroxy linkages (Stevens-Kalceff and Phillips, 1995). The
(Walker, 1985). However, the band positions of the CL emissions formation of the NBOHC from these different defects causes
can vary depending on the specific structure of the SiO2 poly- variations of the band position. It is assumed that the 620 nm
morph and experimental conditions (e.g. Walker, 1985; Luff (1.95 eV) component is characteristic for hydroxyl precursors
and Townsend, 1990; Remond et al., 1992). (:Si–OH), which are common in hydrothermal and authigenic
The CL emissions for quartz are mostly weak but variable and quartz as well as silicified wood (Stevens-Kalceff et al., 2000).
the relation of specific luminescence emission bands to different The CL emission at 1.9 eV (650 nm) commonly increases dur-
defect centres causes a diversity of CL characteristics and visible ing electron irradiation due to the formation of NBOHC from dif-
CL colours, both in natural and synthetic quartz, depending on ferent precursors. A high state of lattice damage can be attained in
the processes of mineral formation or alteration (Table 1). radiation-damaged quartz. The creation of NBOHC defects by
Therefore, knowledge about the origin of different lumines- bond breaking due to the α-particles was observed in both natural
cence centres can help to reconstruct geological processes and radiation-damaged quartz samples and in radiation experiments
to reveal different growth generations (Fig. 6). However, the inter- (e.g. Komuro et al., 2002; Krickl et al., 2008). In natural quartz,
pretation of the origin of CL emission bands in quartz is difficult such lattice damage causes halos around U- and Th-bearing
due to a lack of stringent quantitative correlations between the accessory minerals or migration tracks of U-bearing fluids
intensities of CL bands and the concentrations of specific defects (Fig. 7), which cannot be detected by conventional microscopic
or trace elements. techniques (e.g. Owen, 1988; Ramseyer et al., 1988; Meunier
In general, structural defects are much more important than et al., 1990; Götze et al., 2001a ; Botis et al., 2005; Cerin et al.,
trace elements as CL activators in quartz. Although correlations 2017).
between CL zoning and several trace elements have been observed
(e.g. Watt et al., 1997; Müller et al., 2003; Rusk et al., 2006, 2008;
Yellow emission band at 570 nm (2.15 eV)
Leeman et al., 2012), the origin of the CL is related mostly to
intrinsic lattice defects. The most common CL emission bands Another defect-related CL emission in quartz is a broad yellow
in natural quartz are bands with maxima at 450 and 650 nm emission band centred at 570 nm (2.15 eV) that was first observed

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 Mineralogical Magazine 645

Table 1. Main emission bands in CL spectra of quartz and suggested activators (modified after Götze, 2012a).

Emission Suggested activator References

175 nm (7.3 eV) Intrinsic emission of pure SiO2 Entzian and Ahlgrimm (1983)
290 nm (4.28 eV) Oxygen vacancy Jones and Embree (1976); Stevens-Kalceff (2009)
330–340 nm (3.75–3.6 eV) Oxygen vacancy Rink et al. (1993)
[AlO4/Li+] centre Demars et al. (1996)
[TiO4/Li+] centre Plötze and Wolf (1996)
380–390 nm (3.2–3.1 eV) [AlO4/M+] centre; M+ = Li+, Na+, H+ Alonso et al. (1983)
[H3O4]0 hole centre Gorton et al. (1996); Yang and McKeever (1990)
450–460 nm (2.8–2.7 eV) ODC / E′ 1 centre with self-trapped exciton (STE) Stevens-Kalceff and Phillips (1995)
Substitutional Ti Stevens-Kalceff (2009)
500 nm (2.45 eV) Interstitial impurity cations Ramseyer and Mullis (1990)
(Li+, Na+, H+) Perny et al. (1992); Götze et al. (2005)
500–600 nm (2.45–2.06 eV) Uranyl ion (UO2+2 ) Gorobets and Rogozine (2002)
Multiple lines Götze et al. (2015a)
570 nm (2.15 eV) Self-trapped exciton (STE) (strong disorder and oxygen deficiency) Götze et al. (2015b)
620–650 nm (1.95–1.9 eV) Non-bridging oxygen hole centre (NBOHC) with several precursors Siegel and Marrone (1981); Stevens-Kalceff and Phillips (1995)
705 nm (1.65 eV) Substitutional Fe3+ Pott and McNicol (1971); Gorobets and Rogozine (2002)
1280 nm (0.97 eV) Interstitial molecular oxygen Stevens-Kalceff (2009)

Fig. 6. Photomicrographs of quartz in transmitted light (crossed polars – a) and CL (b) in a rhyolite from Kemmlitz (Saxony, Germany); different quartz generations
are distinguishable by different CL colours: (1) primary quartz phenocryst with blue CL, (2) reddish volcanic quartz of a second generation, (3) secondary micro-
crystalline quartz of hydrothermal origin with yellow CL. (c) The volcanic quartz exhibits two main emission bands at 450 and 620 nm with varying intensity ratios,
whereas the hydrothermal quartz has a main emission at 570 nm and a subordinate shoulder at 620 nm; the circles in (b) mark the positions of spectral CL
analyses.

by Rink et al. (1993) in natural quartz of hydrothermal origin and the UV region with a maximum at ca. 385 nm (3.15 eV; Fig. 8)
Götze et al. (1999) in agates of acidic volcanic rocks and hydro- correlates well with the Al content and the concentration of para-
thermal vein quartz (Fig. 6c). Götze et al. (2015b) showed that magnetic [AlO4/M+] centres (Alonso et al., 1983; Luff and
the appearance of the 570 nm emission band can be attributed Townsend, 1990; Perny et al., 1992). The short-lived blue CL is
to high oxygen deficiency and local structural disorder in quartz. the typical feature of natural and synthetic hydrothermal quartz
The proposed luminescence centre model implies self-trapped (Ramseyer et al., 1988; Götze et al., 2001a, 2009). Because of
exciton (STE) emissions from strongly disordered regions in the sensitivity to electron irradiation, this emission has been
quartz. Additional geochemical data proved that quartz with yel- attributed to the recombination of a hole trapped adjacent to a
low CL occurs exclusively in a low-temperature hydrothermal substitutional, charge-compensated aluminium-alkali ion centre
environment (mostly <250°C) and is related to fast crystallisation (Stevens Kalceff and Phillips, 1995). The rapid attenuation of
in an environment with oxygen deficiency. the 385 nm emission under an electron beam results from the dis-
sociation and electromigration of the charge compensating
cations out of the interaction volume under the influence of the
Blue emission band at 385 nm (3.15 eV)
irradiation induced electrical field (Perny et al., 1992). However,
Trace-element activated CL in quartz is rare, but can be observed Gorton et al. (1996) found a reduced 390 nm band even in ultra-
for specific geological environments, in particular in hydro- pure synthetic quartz and suggested that the 3.15 eV emission is
thermal and pegmatite quartz. A blue emission at the edge of probably not completely related to Al.

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 646 Jens Götze et al.

Fig. 7. Photomicrographs in transmitted light (crossed polars, a) and CL (b) of drusy quartz from the Arrow U-deposit, Athabasca basin (Saskatchewan, Canada);
the CL image reveals a continuous yellow orange radiation rim around the crystal as well as radiation halos around radioactive inclusions (arrow). (c) The CL spectra
display strong development of the 650 nm emission band (NBOHC) due to radiation induced lattice damage; the circles in (b) mark the positions of spectral CL
analyses.

Fig. 8. Photomicrographs in transmitted light (crossed polars, a) and CL (b) of an Al-doped, synthetic hydrothermal quartz; CL reveals growth zones not visible in
transmitted light. (c) The CL image after 60 s of electron irradiation reveals the transient character of the CL, which turns from initial blue (b) to reddish-brown (c).
The related CL spectra (d) show a strong decrease of the blue emission band, whereas the red band increases due to the conversion of precursor centres (e.g.
silanol groups :Si–OH) into the NBOHC.

Blue green emission at
500 nm (2.45 eV), can be related to ionisation-enhanced diffusion of luminescence
centres as was proved by electro-diffusion experiments
Another trace-element related luminescence emission band in
(Ramseyer and Mullis, 1990). The short-lived CL can be restored
quartz is the short-lived blue-green CL (Fig. 9) at ca. 500 nm
by heating the quartz to 500°C for one day (Perny et al., 1992)
(2.45 eV), which can be related to the alkali-compensated
indicating an opposite mechanism to that of thermolumines-
trace-element centres in the quartz structure (Ramseyer and
cence. In contrast, gamma-irradiation causes a decrease in the
Mullis, 1990; Perny et al., 1992, Götze et al., 2005). Ramseyer
intensity of the short-lived blue-green CL and an increase in
and Mullis (1990) and Perny et al. (1992) performed CL measure-
smoky colouration (Ramseyer and Mullis, 1990). This can be
ments, microprobe analyses, temper and electro-diffusion experi-
explained by the conversion of [AlO4/M+]0 luminescence centres
ments and concluded that the CL can be related to the uptake of
into [AlO4]0 colour centres.
positively charged interstitial cations (H+, Na+, Li+) associated
with the substitution of Al for Si. Several studies showed that
the transient blue-green CL is a characteristic feature of pegmatite
Green luminescence at
500–600 nm
quartz and can also occur in hydrothermal and even in meta-
morphic quartz (Ramseyer and Mullis, 1990, Perny et al., 1992; A remarkable feature of some microcrystalline silica varieties as
Götze et al., 2001a, 2005; Sittner and Götze, 2018). Recent studies well as macrocrystalline quartz in agates is greenish luminescence
showed the predominance of Li+ as a charge-balancing cation for emitted in CL and under short-wave UV (<300 nm) excitation,
the 500 nm CL emission in pegmatite quartz (Sittner, 2019). which is uncommon in quartz of magmatic and metamorphic
The intensity of the blue-green CL falls off rapidly within 30 to rocks (Fig. 10). There have also been a few reports about
60 seconds during electron irradiation. This transient behaviour UV-excited green luminescence in opal and chert that have

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 Mineralogical Magazine 647

Fig. 9. Photomicrographs in transmitted light (crossed polars, a) and CL (b) of a pegmatite quartz from Heftetjern, Tørdal region (Norway); the sample exhibits the
characteristic transient blue-green CL; fluid trails are visible due to dark CL. (c) The CL spectra show a drastic drop of the CL intensity of the 500 nm emission band
during electron irradiation; the circle in (b) marks the position of spectral CL measurements.

Fig. 10. Photomicrographs in transmitted light (crossed polars, a) and CL (b) of a chalcedony sample from Kardzali, Bulgaria; microcrystalline quartz exhibits a
2 ) is responsible for the emission peak at
500 nm accompanied by several equidistant lines; there is an
bright green CL. (c) The CL spectra reveal that uranyl (UO2+
additional CL emission band at 650 nm due to the non-bridging oxygen hole centre (NBOHC). The circle in (b) marks the position of spectral CL analyses.

elevated uranium concentrations (Gaillou et al., 2008). The green the quartz lattice similar to other silicates such as feldspar miner-
luminescence is due to the electron transition from an excited to a als (Pott and McNicol, 1971; Gorobets and Rogojine, 2002). Some
ground state of the uranyl ion (UO2+ 2 ) and is shown by a typical red luminescing quartz was also found in metasomatically over-
emission line at
500 nm (2.45 eV) accompanied by several equi- printed granites from Khaldzan Buregte (Mongolia), where the
distant lines (Götze et al., 2015a; Fig. 10c). These are due to the ferric iron was probably mobilised during fenitisation processes
harmonic vibrations of oxygen atoms along the uranyl axis (Kempe et al., 1999). Because of the relatively large ionic radius
(Gorobets and Rogojine, 2002). Recent studies have revealed of Fe3+ its incorporation into the quartz lattice is limited and
that U is mainly incorporated in the form of a uranyl-silicate therefore, the 705 nm emission is rare. Its origin has to be further
complex in opal and microcrystalline quartz (Pan et al., 2021). verified by measurements of the luminescence lifetime and/or the
The mechanism of the uranyl luminescence is very effective and luminescence excitation spectra.
can be detected in SiO2 phases with U contents as low as 1 ppm.

Mineral chemistry of quartz

Red luminescence at 705 nm (1.65 eV)
Quartz is one of the purest minerals in the Earth’s crust in terms
A CL emission band in the red on the edge to the infrared around of chemical impurities expressed as trace-element contents. Due
705 nm (1.65 eV) was first reported from synthetic quartz crystals to limitations in charge and ionic radii only a limited number
(Pott and McNicol, 1971). It is assumed that this
705 nm emis- of ions can substitute for Si4+ in the crystal lattice or can be incor-
sion can be related to the substitutional incorporation of Fe3+ into porated in interstitial positions. Therefore, most elements are

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 648 Jens Götze et al.

present in quartz in concentrations below 1 ppm (Müller et al.,

2003, 2012; Götze, 2009). The structural incorporation in a regu-
lar Si4+ lattice position has been proven for Al3+, Ga3+, Fe3+, B3+,
Ge4+, Ti4+ and P5+ (e.g. Weil, 1984), in which Al is probably the
most common ion (up to a few 1000 ppm) because of its abun-
dance in the Earth’s crust and the similar ionic radii of Si4+
and Al3+. Mono- and divalent ions, primarily H+, Li+, Na+, K+,
Be+, Rb+ and Fe2+ may enter interstitial lattice positions in
small amounts and charge-compensate trivalent substitutional
ions, mainly Al3+ (Bambauer, 1961, Kats, 1962, Perny et al.,
1992, Stalder et al., 2017, Potrafke et al., 2019). For most other ele-
ments (e.g. Ca, Mg, Ba, Sr, REE, Mn, U and Th) capture by nano-
(< 100 nm) or micro-inclusions (0.1–1 μm) of fluids or minerals
is the most important mechanism (e.g. Gerler and Schnier, 1989;
Müller et al., 2003; Götze, 2009).

Aluminium
The structural incorporation of aluminium is evidenced by
numerous studies using EPR spectroscopy (Alonso et al., 1983).
The substitution of Si4+ by Al3+ is mostly accompanied by charge
compensating cations in interstitial positions. Combined studies
by EPR, CL, spatially resolved trace-element analyses and SIMS
mapping have revealed that Li+ seems to be the dominant charge
compensating ion in igneous and pegmatite quartz (Götze et al.,
2005; Beurlen et al., 2011; Sittner, 2019), whereas H+ plays an
additional significant role in hydrothermal quartz and authigenic
quartz in sedimentary/diagenetic environments (Bambauer, 1961;
Miyoshi et al., 2005; Müller and Koch-Müller, 2009; Jourdan
et al., 2009; Götte et al., 2011; Lehmann et al., 2011; Götte,
2016; Stalder et al., 2017; Fig. 11). The preferred incorporation
of H+ in interstitial structural positions in natural and synthetic
hydrothermal quartz can be explained by its input from the
mineralising aqueous fluids (Bambauer et al., 1962; Stenina,
2004). Further possible mechanisms of structural incorporation
of Al3+ are the coupled substitution with a pentavalent ion or
the charge compensation by electron defects on vacancies.
The concentration of Al in quartz in magmatic systems seems
to be mainly controlled by the aluminium saturation index of the
melt rather than by the temperature (Jacomon and Larsen, 2009;
Breiter et al., 2013, 2020). Accordingly, the Al concentration in
quartz increases during melt evolution from metaluminous to
peraluminous compositions. In hydrothermal systems, factors
such as temperature, growth rate and Al concentration in the
aqueous solution influence the Al content in quartz. It was
shown that changes in pH have strong effects on Al solubility
and the aqueous Al concentration, and thus cause variations of
the Al concentration in hydrothermal quartz (e.g. Perny et al.,
1992; Rusk et al., 2008; Müller et al., 2010; Luo et al., 2020).
The incorporation of Al into SiO4 tetrahedra is limited by the
ionic radius of the Al3+ ion (0.54 Å), which can occur both in
fourfold and sixfold coordination with oxygen. Therefore, high
amounts of Al substitution in quartz result in a distortion of
the tetrahedra and destroy the perfection of the crystal lattice.
Nevertheless, previous EPR studies of [AlO4]0 centres in chalced-
ony and the macrocrystalline quartz in agates have revealed
abnormal high concentrations of structural Al in these SiO2 Fig. 11. Element correlation for Al vs. Li (ppma = atoms per 106 atoms Si) in quartz of
different origin: (a) pegmatite quartz from Norway; (b) pegmatite quartz from differ-
phases (Götze et al., 2001b). There are strong indications that ent deposits in Norway and Namibia; (c) hydrothermal quartz from the Ural region,
the formation of some hydrothermal quartz and/or agate proceeds Russia. The pegmatite quartz shows almost 1:1 ratios of Al to Li, whereas the hydro-
through several structural states of SiO2 with amorphous silica as thermal quartz is Li deficient (data from Götze et al., 2004, 2017; Sittner, 2019).

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 Mineralogical Magazine 649

the first solid phase (Dong et al., 1995, Götze et al., 2020). This
might result in areas or zones with a high degree of disorder
and large numbers of lattice defects (oxygen and silicon vacan-
cies), which enable the incorporation of high concentrations of
‘defect’ Al. Such a scenario could also explain the extreme high
concentrations of Al in neighbouring individual growth zones
or generations of hydrothermal quartz, which reflect abrupt
changes in the physicochemical conditions (open hydrothermal
system).

Titanium
In contrast to Al, titanium can be both incorporated as substitu-
tional ion for Si4+ and bound on mineral micro-inclusions such as
rutile or anatase. The geochemical compatibility of Ti and its rela-
tively large ionic radius (Ti4+ 0.61 Å) results in a preferred uptake
in early formed quartz at high temperatures and pressures.
Therefore, the highest Ti contents in quartz can be found in Fig. 12. Plot of Ti content in quartz measured by ICP-MS vs. concentration of struc-
quartz phenocrysts in volcanic rocks and early crystallised quartz tural Ti ([TiO4/Li+]0 centres) determined by EPR spectroscopy (concentrations were
determined as peak to base intensity under constant analytical settings according
grains in igneous rocks. In granitic melts, decrease in the Ti con- to Moiseev, 1985). Pegmatite quartz samples from the Rubicon Mine, Namibia (red
centrations in quartz can be observed during increasing fraction- circles) exhibit a linear correlation with zero intercept indicating a complete presence
ation and decreasing temperature (Larsen et al., 2004; Breiter and of Ti as structural substituent for Si; quartz samples from Norway (blue squares) are
Müller, 2009). The lowest Ti concentrations in quartz were mea- mostly far away from the correlation and show higher Ti contents; in these samples
micro-inclusions of rutile were detected (data from Götze et al., 2004).
sured in quartz crystallised from aqueous solutions at relatively
low temperatures (Blankenburg et al., 1994; Müller et al., 2003).
Using the temperature dependence of Ti uptake in quartz,
Germanium contents in quartz from magmatic and meta-
Wark and Watson (2006) created a Ti-in-quartz geothermometer
morphic rocks are mostly in the range between 0.5 and 1.5 ppm
based on the Ti concentration in quartz. Subsequently, Huang
(Walenczak, 1969; Blankenburg et al., 1994). In most hydrothermal
and Audétat (2012) discovered, in addition, that Ti incorporation
quartz, the Ge content is similar. Only some hydrothermal quartz
in quartz is slightly controlled by the crystallisation pressure, and
veins in paragenesis with metalliferous deposits show elevated Ge
modified the geothermometer to a Ti-in-quartz geothermoba-
contents up to several ppm (Blankenburg et al., 1994; Müller
rometer. The geothermobarometer is, however, very sensitive to
et al., 2018; Breiter et al., 2020). Concentrations of >1.5 ppm up
the Ti saturation of the melt in which the quartz crystallises
to 23 ppm Ge were measured in quartz crystallised from fractio-
and thus has to be applied with caution.
nated granitic and pegmatitic magmas (Götze et al., 2004; Beurlen
The limitations in structural compatibility of Ti frequently
et al., 2011; Breiter et al., 2014). Extraordinary Ge concentrations
cause exsolution phenomena at lower temperatures, such as the
of partially > 90 ppm were found in micro- and macrocrystalline
formation of TiO2 micro-inclusions (rutile, anatase) in quartz
quartz of agates, which exceeded the average concentration of the
crystals. Ti4+ is commonly sixfold coordinated by oxygen because
Earth’s crust and also the Ge content in the surrounding host
of its ionic radius. The substitution of fourfold coordinated Ti4+
rocks (Götze et al., 2016, 2020).
for Si4+ in the tetrahedral position is only possible at elevated tem-
peratures. Therefore, a straight correlation between bulk Ti con-
tents in quartz and structural Ti measured by EPR spectroscopy
Phosphorus
is often missing (Fig. 12). However, it should also be considered
that Ti can be incorporated as a diamagnetic [TiO4]0 centre Phosphorus can substitute as P5+ with an ionic radius of 0.38 Å
that cannot be detected by EPR spectroscopy. for Si4+ in the quartz structure. A coupled mechanism 2 Si4+ ↔
P5+ + M3+ (M3+ = Al3+, B3+) is assumed for the structural incorp-
oration with Al3+ as the most frequent charge compensator, con-
Germanium
firmed by the paramagnetic [O3AlOPO3]+ centre (Maschmeyer
Germanium shows a similar geochemical behaviour compared to Si, and Lehmann, 1983). However, P is generally not considered in
in addition Ge4+ has a similar ionic radius (0.53 Å). Therefore, Ge4+ analytical measurements. Therefore, a specified procedure for
can substitute isovalently for Si4+ in the SiO4 tetrahedra. However, the precise determination of P in quartz was developed by
Ge belongs to the group of elements occurring in low concentra- Müller et al. (2008).
tions in the Earth’s crust (Clark value 1.4 ppm) mostly resulting The absolute concentration of P in quartz is mostly low and
in low concentrations in quartz. Germanium does not partition rarely exceeds several ppm (e.g. Larsen et al., 2004; Müller
into any particular mineral phase and is therefore enriched in et al., 2003, 2012; Beurlen, 2011; Breiter et al., 2013, 2020;
residual melts or fluids. In particular the presence of halogens Sittner, 2019). The concentration of P is typically buffered by
(e.g. fluorides) in the crystallisation medium favours the develop- the presence of fractionating mineral phases that particularly
ment of durable and volatile compounds (Walenczak, 1969). incorporate it at the expense of the residual melt and quartz.
Thermodynamic considerations suggest that the transport and accu- Therefore its distribution in quartz seems to be erratic (Beurlen
mulation of Ge as the GeF4 complex during chemical transport et al., 2011). Nevertheless, it seems to be slightly enriched during
reactions could probably explain elevated Ge concentrations in the differentiation of granitic and pegmatitic systems in late crys-
quartz in specific geological environments (Götze et al., 2012). tallisation phases (Larsen et al., 2004).

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 650 Jens Götze et al.

Iron the charge compensation of Al rather than the concentration in

4+ fluid inclusions (Götze et al., 2004). Hence, the uptake of Li in
Iron can be incorporated structurally by substituting for Si in
the quartz lattice seems to be mostly limited by the amount of sub-
the tetrahedra or in interstitial sites. However, the ionic radii of
stitutional Al (Müller and Koch-Müller, 2003). The availability of
Fe2+ (0.78 Å) and Fe3+ (0.65 Å) are much larger than that of
Li at time of quartz crystallization is thereby also controlled by
Si4+. Therefore, the incorporation is limited and mostly occurs
the crystallization order of Li minerals and quartz in granites and
in marginal parts or damaged areas of quartz crystals (Mineeva
granitic pegmatites.
et al., 1991; Götze and Plötze, 1997). Therefore, elevated contents
Although Na and K were also proven to be potential charge
of Fe in quartz can mostly be related to micro-inclusions of
compensators (e.g. Heaney and Davis, 1995; Botis et al., 2009;
Fe-bearing minerals (e.g. hematite, goethite) or nano-clusters of
Luo et al., 2020), these ions are more commonly hosted by micro-
amorphous Fe-compounds.
inclusions of minerals and fluids or accumulated along micro-
fissures (e.g. Günther et al., 1998, Müller et al., 2003; Götze
Boron et al., 2004, 2017; Sittner, 2019; Ladenburger et al., 2020). For
instance, K is commonly associated with Al in quartz of granitic
Boron mostly occurs in low concentrations (< 1 ppm) in quartz igneous rocks and pegmatites as nano-inclusions of K-feldspar or
(Blankenburg et al., 1994). Elevated contents of > 10 ppm B sheet silicates (e.g. Zolensky et al., 1988; Jacamon, 2006; Jacamon
have been measured in quartz of pegmatites (e.g. Götze et al., and Larsen, 2009; Seifert et al., 2011). Müller et al. (2012), for
2004; Beurlen et al., 2011; Müller et al., 2012), and remarkably instance, suggested a formation of micro-inclusions with musco-
high concentrations of up to 46 ppm were detected in quartz of vite composition due to accumulation of Al and K during deform-
agates from different locations (Götze et al., 2020). Similar to ation processes. However, the majority of K, Na, Rb, Cs, Ca, Mg
Ge, a preferred transport of boron as a volatile BF3 complex dur- and Sr seems to be bound preferentially to fluid inclusions.
ing chemical transport reactions could be responsible for the In general, the trace amounts of most alkali and alkali earth
accumulation of B in quartz, if halogens were available in the par- elements in quartz show parallel trends because of their similar
ticipating fluids (Götze et al., 2012). geochemical behaviour (Figs 14, 15). The data indicate that the
The existence of nano-inclusions of tourmaline has been dis- majority of elements is bound preferentially to micro-inclusions.
cussed as a possible reason for high B contents in pegmatite Chemical investigations of inclusion fluids in quartz revealed
quartz (Müller et al., 2012). However, quartz commonly lacks that those inclusions play a major role in hosting alkali and alkali
such impurities and a structural incorporation of boron must be earth elements (e.g. Rossman et al., 1987; Gerler, 1990; Gerler and
assumed by analogy with other silicates (Grew and Hinthorne, Schnier, 1998; Günther et al., 1998; Götze et al., 2004;
1983). Because of the small ionic radius of the B3+ ion (0.27 Å), Ladenburger et al., 2020). For instance, Bottrell et al. (1988)
the formation of planar BO3-groups in minerals is commonly reported evidence for the presence of Na, K, Mg and Ca in
favoured (Jolland et al., 2020), however the incorporation as fluid inclusions of different quartz samples.
BO4 tetrahedra is also possible. Therefore, a coupled substitution
of B3+ with pentavalent ions (P5+) in two neighbouring MO4
tetrahedra or in combination with charge-balancing cations and Rare earth elements
electron defects, respectively, has to be considered. Rare earth elements (REE) generally have very low concentrations
in quartz. Therefore, their absolute abundance is not
Gallium typically determined. However, REE distribution patterns are
commonly used for the reconstruction of mineral forming pro-
Gallium occurs at very low concentrations in natural quartz cesses and thus, the distribution of REE in quartz can provide use-
(< 0.1 ppm) and is, thus, rarely detected. Walenczak (1969) was ful information about the geological environment of quartz
probably the first who reported Ga concentrations of igneous, formation (Monecke et al., 2000, 2002; compare with Fig. 20).
metamorphic and hydrothermal quartz. In most of the quartz Because of their crystal-chemical properties, REE cannot be
investigated, Ga showed concentrations between 0.02 and 0.4 incorporated into the quartz crystal structure. It is assumed that
ppm and amethyst had generally high Ga up to 25 ppm. Recent REE in quartz are hosted preferentially in fluid inclusions.
publications, applying in situ micro-beam techniques with very Rossman et al. (1987), Ghazi et al. (1993) and McCandless
low detection limits for trace-element determination, have not et al. (1997) reported a correlation of REE together with Rb
confirmed such high Ga contents in natural quartz, and only chal- and Sr with fluid-inclusion water indicating that these elements
cedony and macrocrystalline quartz of agates had Ga contents of are mostly contained in the inclusion fluids. These results were
1–2 ppm (Götze et al., 2015a). Müller et al. (2021) has shown, confirmed by Götze et al. (2004) for pegmatite quartz, who
however that Al and Ga concentrations in quartz correlate found a correlation of REE contents in quartz with the absolute
(Fig. 13). amount of inclusion fluid (Fig. 16). On the basis of these consid-
erations, REE may provide important fingerprints concerning the
composition of mineral forming fluids.
Alkali and alkali earth elements
Alkali and alkali earth elements can occur in elevated concentra-
Antimony
tions (up to >100 ppm) in quartz. In principle, cations such as
Li+, Na+ or K+ can be incorporated in interstitial positions (Botis Antimony is another trace element in quartz that can probably be
et al., 2009), where Li+ is the most common charge-compensating related to a supply by mineralising fluids. Although the concen-
ion. The lithophile character of Li probably favours its partition tration of Sb in most quartz of igneous, volcanic and meta-
into silicate melts and quartz rather than in aqueous fluids. morphic rocks is far below 1 ppm (Blankenburg et al., 1994),
Therefore, it prefers the incorporation into structural channels for Rusk et al. (2011) found detectable Sb contents in quartz of

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 Mineralogical Magazine 651

Fig. 13. Aluminium vs. Ga in pegmatite quartz of different origin

(data from Müller et al., 2021; NYZ = Nb/Y/F-pegmatite, LCT = Li/
Cs/Ta-pegmatite according to Černỳ and Ercit, 2005).

epithermal ore deposits. Antimony was measured at concentra- incorporated into quartz as uranyl ions (UO2+ 2 ), which are bound
tions from <5 to
120 ppm and concentrations fluctuated dra- to the silica surface (Götze et al., 2015a). The presence of uranyl
matically among quartz generations and growth zones. ions can be confirmed easily by its characteristic green luminescence
Similarly, Monnier et al. (2021) found highest Sb contents (up (compare Fig. 10). Recent data confirmed the binding mechanism of
to 200 ppm) in quartz from stibnite-bearing veins, considerably uranyl silicate complexes in microcrystalline SiO2 and suggested a
higher than the values measured in quartz unrelated to Sb min- new mechanism of uranium deposition (Fig. 17b; Pan et al.,
eralisation (mainly ≤ 1 ppm). The lack of a consistent relationship 2021). This model involves uranyl co-precipitation during silicifica-
between Sb and other trace elements in quartz lead to the conclu- tion without the putative reduction process and provided new
sion that Sb incorporation in quartz is probably controlled by the aspects concerning the formation of uranium deposits.
content of Sb in the mineralising fluid (Rusk et al., 2011; Pacák
et al., 2019; Li et al., 2020; Monnier et al., 2021). Therefore, the
Sb content in quartz might be used as a potential indicator for tra- OH
cing Sb deposits.
In addition to water contained in fluid or melt inclusions, quartz may
incorporate different amounts of OH point defects in its structure
(e.g. Kats, 1962; Bambauer et al., 1962; Chakraborty and Lehmann,
Niobium, tantalum, uranium and thorium
1976; Stalder, 2021). The specific OH defects can be distinguished
For a number of elements the nature of incorporation into quartz and quantified by Infrared (IR) spectroscopy based on their charac-
is very difficult to determine. In particular these are elements that teristic absorption bands. The most common type is the Al–OH
are present in extremely low concentrations and sometimes below defect followed by the Li–OH defect, whereas B–OH and hydro-
the detection limit of some trace-element analytical methods (e.g. garnet defects (4H) are less common. Systematic investigations of
U, Th, Nb and Ta). It can be assumed that the ions are either too OH contents in different quartz types revealed that the incorporation
large to substitute for the small Si4+ ion in the quartz lattice or of OH defects depends on the specific conditions of formation, but
that they are not soluble in the mineralising fluids that accumulate shows no correlation with the amount of molecular water incorpor-
in fluid inclusions. This can be observed for the immobile ele- ation (Baron et al., 2015; Jaeger et al., 2019; Stalder, 2021).
ments niobium and tantalum in quartz of Nb–Ta mineralisation, Quartz from granitic systems may show large variations in OH
where the extreme low concentrations of these trace elements in content with average values of ca. 20 wt. ppm (Stalder, 2021). It
associated quartz do not reflect the mineralisation and, therefore, has been shown that Variscan samples with 20–35 wt. ppm OH
cannot be used as petrogenetic indicators (Götze et al., 2004). contents have much higher values than Proterozoic samples
Uranium and thorium are two elements that are typically present from Scandinavia with
3 wt. ppm (Müller and Koch-Müller,
in very low concentrations in quartz. Quartz from magmatic, meta- 2009; Stalder et al., 2017; Potrafke et al., 2020). Granitic pegma-
morphic rocks and pegmatites has U and Th contents at sub-ppm tites contain average OH contents of ca. 20 wt. ppm (Müller
levels (e.g. Gerler, 1990; Blankenburg et al., 1994; Götze et al., 2004; and Koch-Müller, 2009). OH contents of up to 13 wt. ppm (aver-
Götze, 2009). These characteristic low concentrations in quartz can age of 6 wt. ppm) were determined for quartz from felsic volcanic
be explained by the fact that the crystal-chemical properties of U rocks. Individual phenocrysts can show strong zoning with a
and Th (in particular ion sizes) prevent a substitutional incorpor- decrease in OH from core to rim (Tollan et al., 2019; Jollands
ation into the quartz structure. The correlation of the U and Th con- et al., 2020). Hydrothermal quartz crystals are also heterogeneous
centrations (Fig. 17a) indicates that traces of both elements are with respect to the OH content (0–225 wt. ppm) with the highest
situated on interstitial places in the lattice or bound on submicro- concentrations in the crystal centre (Kats, 1962; Chakraborty and
scopic mineral inclusions (e.g. on grain boundaries). Lehmann, 1976). The lowest OH contents (mostly <5 wt. ppm)
Unusually high U concentrations of up to >70 ppm were were measured in quartz from metamorphic rocks (Müller and
detected in some microcrystalline quartz and even in macrocrystal- Koch-Müller, 2009; Stalder et al., 2017).
line quartz of agates from different worldwide occurrences (Götze A thorough review about OH defects in quartz has been given
et al., 2009, 2015a). Results of CL spectroscopy indicate that U is recently by Stalder (2021).

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 652 Jens Götze et al.

Fig. 15. Contents of alkali and alkali earth elements in quartz: (a) Na vs. Mg; (b) Rb
vs. Sr; (c) Ba vs. Mg (red symbols) and Ba vs. Sr (blue symbols). All log plots show
Fig. 14. Contents of alkali elements in quartz: (a) K vs. Na; (b) Rb vs. Na (red symbols) similar trends with varying absolute concentrations (Mg > Sr); note that pegmatite
and Rb vs. K (blue symbols); (c) Rb vs. Cs. All log plots show positive trends and simi- quartz mostly contains < 0.1 ppm Sr and hydrothermal quartz > 0.1 ppm Sr (circles
lar absolute concentrations of K and Na with nearly 1:1 ratio (circles = hydrothermal = hydrothermal quartz, rhombs = pegmatite quartz; data from Götze et al. 2004,
quartz, rhombs = pegmatite quartz; data from Götze et al. 2004, 2017). 2017).

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 Mineralogical Magazine 653

and rhyolites, and established the Ti ‒ Al/10 – 10Ge ternary dis-

crimination diagram, which is still used widely. Most recently
Breiter et al. (2020) proposed that this diagram does not only
enable the discrimination between pegmatitic and granitic quartz,
but also permits, to some extent, discrimination between common
and rare-metal, and between S- and A-type granites (Fig. 18).
A steady increase in the Ge/Al values in quartz during the
transition from magmatic to hydrothermal stages related to rare
metal mineralised systems was reported by Müller et al. (2018)
and Breiter et al. (2020). In the case of the Zinnwald/Cinovec
Sn–W–Li greisen-type deposit the value of Ge/Al = 0.008 is a dis-
criminator between magmatic and hydrothermal quartz (Müller
et al., 2018). In the case of the Panasqueira W deposit, the
value of Ge/Al = 0.01 was found to discriminate most of the mag-
matic quartz from hydrothermal quartz (Breiter et al., 2020).
Breiter and Müller (2009) also detected decreasing Ti content
Fig. 16 Bulk REE content in pegmatite quartz plotted vs. absolute amount of inclu- in granitic quartz with increasing fractionation. In contrast, Al
sion fluid in the quartz samples; the correlation trend indicates the preferred accu- contents in quartz increased from the early to the late population
mulation of REE in fluid inclusions; the scatter can be explained by variations of independent of the peraluminosity of the melt, resulting in a
their absolute concentrations in the fluid (data from Götze et al., 2004). negative correlation between the Al and Ti contents.
Accordingly, the Ti vs. Al diagram seems to be the most valuable
indicator for the evolution of the melt from which the quartz crys-
Geological implications of quartz properties
tallised (Müller et al., 2002, 2003, 2017; Breiter and Müller, 2009;
Depending on the specific conditions of formation, quartz can Jacamon and Larsen, 2009; Breiter et al., 2012; Peterková and
develop characteristic chemical, physical and morphological prop- Dolejš, 2019). These general trends were also found in quartz
erties (indicator properties), which range from the atomic scale from plutons of different geochemical character (Breiter et al.,
(point defects) up to macroscopic appearance and 2013; Hong et al., 2019). The Ge/Ti vs. Al/Ti plot shows a positive
crystal morphology. Knowledge about such characteristic features correlation reflecting the fractionation trend of granitic melts
is indispensable for the recognition of any relationships between (Breiter et al., 2020).
quartz genesis, its specific properties and possible industrial The trace-element composition of quartz from hydrothermal
applications. environments also provides information about primary crystal-
lisation conditions, the mineralisation regime in hydrothermal
ore deposits as well as about processes of secondary hydrothermal
Trace elements in quartz as petrogenetic indicators
overprint in different types of host rocks (e.g. Monecke et al.,
The trace-element distribution in quartz from different rock types 2002; Rusk et al., 2008, 2012; Jourdan et al., 2009; Luo et al.,
can provide useful information about the formation history of 2020). For instance, Jourdan et al. (2009) reported Al and Li con-
these rocks, as they are highly sensitive to crystallisation and frac- centrations of more than several hundreds of ppm for distinct
tionation processes. For instance, trace elements in granites and growth zones within hydrothermal quartz crystals formed at tem-
granitic pegmatites reflect the evolution of the melt and can there- peratures of about 300°C or less. These quartz crystals also dis-
fore be used as petrogenetic indicators. Elements such as K, Fe played patterns of cyclic growth under CL. In contrast, quartz
and Ti are geochemically compatible and therefore have the high- crystals formed at temperatures closer to 400°C and without vis-
est concentrations in early formed quartz. In contrast, P, Ge, Rb ible cyclic growth have low concentrations of Al, Li and other
and Li are relatively incompatible resulting in elevated concentra- trace elements.
tions in quartz that formed in more evolved granitic melts and/or Such variations were also reported in different quartz genera-
residual fluids (Schrön et al., 1982, 1988; Larsen et al., 2004; tions of ore mineralisation (Rusk et al., 2006, 2008, 2011; Luo
Beurlen et al., 2011; Monnier et al., 2018; Müller et al., 2017; et al., 2020). The variations of trace elements such as Ti, Al, Li,
Breiter et al., 2020). K or Na might be related to variations in the pressure and tem-
Larsen et al. (2004) suggested the Ge/Ti ratio is robust during perature regime, but can also result from fluctuations of the pH
sub-solidus processes in igneous systems and concluded that it and composition of the mineralising solutions or crystallisation
represents a strong index for the evolution of melt differentiation rate rather than changes in temperature. Rusk (2012) investigated
in granitic igneous rocks, and has potential as an igneous quartz from almost 30 hydrothermal ore deposits including
geothermometer (Jacomon and Larsen, 2009). The Ge/Ti ratio porphyry-type (Cu–Mo–Au) deposits, orogenic Au deposits,
is a reliable melt fractionation index as Ti in quartz is a function and epithermal deposits and concluded that each of these ore
of magma temperature and Ti melt saturation and, thus, decreases types can be distinguished from one another on the basis of Al
with melt differentiation, whereas Ge increases with the melt frac- and Ti concentrations alone. The temperature dependence of Ti
tionation degree. A similar behaviour was proposed for the Ge/Fe incorporation was used to establish an Al versus Ti discrimination
ratio in quartz (Schrön, 1982, 1988). However, as noted above diagram of quartz based on the observation that the Ti content,
most of the detected elevated contents of Fe in quartz are related and to the same extent the Al content, vary systematically
to micro-inclusions of Fe-bearing minerals. Thus, the ratio should among these ore deposit types (Fig. 19).
not be used for genetic interpretations. Most porphyry-type quartz contains 1–200 ppm Ti and 50–
Schrön et al. (1988) noticed that elevated Ge concentrations 500 ppm Al showing a linear correlation with an Al/Ti ratio
are found in pegmatitic quartz compared to quartz from granites between 1 and 10. In contrast, quartz from epithermal ore

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 654 Jens Götze et al.

Fig. 17 (a) Th vs. U concentrations in quartz samples from different parent rocks and localities (data from Götze et al., 2004, 2017; circles = hydrothermal quartz,
rhombs = pegmatite quartz); (b) model of the uranyl–silicate complex in microcrystalline SiO2 with neighbouring SiO4 tetrahedra and uranyl polyhedra (modified
after Pan et al., 2021).

Fig. 19. Log plot of Ti vs. Al contents in quartz for the discrimination of hydrothermal
quartz originating from epithermal, orogenic Au and porphyry type deposits (modi-
fied after Rusk, 2012).
Fig. 18. Triangle for discrimination of S-type granites, A-type granites and pegmatites
(modified after Breiter et al., 2020); the arrows indicate evolution trends during
magma fractionation.
light, middle and heavy REE indicate the source of the silica-
bearing fluids and the influence of the complexation of the REE
deposits always contains < 3 ppm Ti with a wide scatter of Al during transport (Lipin and McKay, 1986). Moreover, negative
between 20 and 4000 ppm (Al/Ti ratios 100–10,000), whereas and positive anomalies of Ce and Eu can reflect adopted proper-
quartz from orogenic Au deposits mostly has 100–1000 ppm Al ties from the mineralising fluids and/or variations in redox con-
and 1–10 ppm Ti (Al/Ti ratio 10–100; Rusk, 2012). These system- ditions resulting in a change of the valence state of the ions
atic variations in trace-element concentration reflect the different (Fig. 20).
physical and chemical conditions during quartz formation. The hydrothermal quartz samples in Fig. 20a represent differ-
Concentrations of REE in quartz can also be used as valuable ent hydrothermal systems and accordingly display characteristic
indicators for geological and/or geochemical processes, as they REE distribution patterns. The chondrite-normalised REE distri-
can reflect the evolution of mineralising fluid and melt composi- bution pattern of the hydrothermal quartz from the
tions. Thus, REE distribution patterns contain important infor- Trans-Atlantic Geotraverse (TAG) mound in the Mid-Atlantic
mation concerning the primary conditions of quartz formation Ridge (Fig. 20a) is bell-shaped with no significant Ce or Eu anom-
and also information about secondary effects (Fig. 20). The gen- aly. This REE distribution can be related to the origin and evolu-
eral shape of the REE distribution and the relationships between tion of the fluids within the hydrothermal system that is related to

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 Mineralogical Magazine 655

Fig. 20. Chondrite-normalised REE distribution patterns of quartz from different geological environments: (a) hydrothermal quartz from the TAG mound
(Mid-Atlantic Ridge), high-purity quartz (HPQ) from Vjazovka (Ural region, Russia) and from the gold deposit Muruntau/Myutenbai (Uzbekistan); (b) pegmatite
quartz from Hittero (Norway) and macrocrystalline (agateqtz) as well as chalcedony (agatechal ) of an agate from Hohenstein-Ernstthal (Saxony, Germany) both
showing positive Ce-anomalies, negative Eu-anomalies and tetrad effects; (c) metamorphic quartz from the Middle Erzgebirge (Germany) and overprinted
counterpart from the area of tin mineralisation; (data from Monecke et al., 2000, 2002; Götze et al., 2004, 2016, 2017).

an actively forming sulfide deposit (Monecke et al., 1999). In con- Another common feature in sedimentary and diagenetic envir-
trast, the high-purity quartz from Vjazovka (Ural region, Russia) onments is secondary quartz neomorphism as quartz overgrowth
and the quartz from the hydrothermal gold deposit show typical cements in sandstones or isolated euhedral quartz crystals in vari-
crustal signatures with a smooth chondrite-normalised REE pat- ous sedimentary host rock. Authigenic quartz cements play a
tern with decreasing REE concentrations from La to Lu. The major role in controlling the hydraulic properties and quality of
negative Ce- and positive Eu-anomalies, result from the evolution reservoir sandstones (McBride, 1989). The combination of
of the hydrothermal fluids in the deposits and their interactions trace-element studies with other analytical methods (e.g. CL,
with the surrounding wall rocks. fluid inclusion and isotope studies) can provide important infor-
Unusual REE fractionation and the development of tetrad mation about timing of quartz cementation and the burial history
effects (Fig. 20b) can be related to fluid immiscibility and prefer- of sandstones or concerning temperature and salinity of fluids
ential partitioning of the REE between the vapour and coexisting during precipitation (e.g. Burley et al., 1989; Kelly et al., 2007;
liquid (Monecke et al., 2007). Tetrad effects were observed both in Lehmann et al., 2011).
quartz of pegmatites (Götze et al., 2004) and quartz of agates in Moreover, some investigations have used complex geochemical
acidic volcanic rocks (Götze et al., 2016) and probably reflect the and mineralogical studies for the reconstruction of silica sources
participation of volatiles during SiO2 accumulation and crystallisa- and diagenetic conditions during the formation of euhedral authi-
tion. The marked increase of heavy REE indicates the complexation genic quartz crystals in soil, limestones and carbonates, sulfate
of REE by fluorine or carbonate complexes (Wood, 1990). and salt deposits as well as bituminous coal and lignite (e.g.
The hydrothermal overprint of crystalline host rocks in the Füchtbauer, 1961; Grimm, 1962; Fabricius, 1987; Richter, 1971;
vicinity of ore deposits can also result in a change of the REE dis- Friedman and Shukla, 1980; Ruppert et al., 1985; Soong and
tribution pattern. An example from quartz in unaltered meta- Blattner, 1986; Götze, 2012b). The resulting mineralogical and
morphic host rocks located distal to the alteration halo within a geochemical characteristics show that the authigenic quartz
tin deposit is shown in Fig. 20c. The hydrothermally overprinted from the various sedimentary environments differs clearly from
quartz shows REE signatures that deviate significantly from the quartz of crystalline rocks and a distinction between quartz
unaltered equivalent. These differences are interpreted to result from different sedimentary environments is possible.
from the interaction of the pre-existing quartz with the hydrother-
mal fluids (Monecke et al., 2004).
Interpretation of CL and trace-element data
Several studies have shown that the trace-element composition
of quartz can be used to fingerprint the source of detrital quartz In general, quartz commonly shows growth zoning in CL, reflect-
grains in clastic sediments (Götze and Zimmerle, 2000). Quartz ing either variations of the composition of the crystallisation
can retain chemical signatures of the source rocks because of its medium (melt or fluid) or changing physicochemical conditions
common occurrence and relative mechanical and chemical stabil- (temperature, Eh, pH). Therefore, combined CL and trace-
ity during sedimentary processes. These geochemical signatures element studies have significant potential for the reconstruction
can be used to reveal the origin and provenance of individual of crystallisation sequences in magmatic and hydrothermal sys-
quartz grains within sediments. Differences in the distribution tems (e.g. Kempe et al., 1999; Landtwing and Pettke, 2005;
of selected trace elements and/or trace-element ratios may be Müller et al., 2005, 2010; Jourdan et al., 2009; Götte et al.,
related to inherent characteristics of the source and can be used 2011; Audétat, 2013; Mao et al., 2017; Wertich et al., 2018;
as discriminating tools (e.g. Dennen, 1967; Hallbauer, 1992; Wang et al., 2019; Luo et al., 2020; Lan et al., 2021).
Götze and Lewis, 1994; Müller and Knies, 2013; Ackerson et al., Although a correlation of the CL response and the concentra-
2015; Stalder et al., 2019). tion of trace elements has been noted by several authors (e.g. Watt

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 656 Jens Götze et al.

et al., 1997; Müller et al., 2003; Rusk et al., 2006, 2008, 2011; between Al-Li centres and the 395 nm emission band. They
Lehmann et al., 2011; Leeman et al., 2012), CL zoning (in particu- assumed that the conversion of [AlO4|Li+] centres to [AlO4]0 cen-
lar in panchromatic CL images) in quartz cannot be related solely tres by natural irradiation and/or the existence of intrinsic defects
to variations in the trace-element concentration. For instance, such as oxygen deficiency centres can affect the luminescence
Watt et al. (1997) analysed volcanic quartz phenocrysts and xeno- properties. Similar results were reported by Sittner (2019) for
crysts by ion microprobe (SIMS) and found higher Al contents in the CL of pegmatite quartz. The 500 nm emission band could
areas of bright CL emission, though they suggested that other fac- clearly be ascribed to structurally incorporated Li, but a clear
tors (e.g. the effect of growth rate on defect density) may also play quantitative correlation between Li concentration and intensity
a major role in controlling CL intensity. Several important aspects of the 500 nm emission band was missing. The incorporation
limit the possible correlation between the abundance of specific of other monovalent cations and the charge-compensation of
trace elements and visible CL colours or CL zoning. Al3+ by electron defects were discussed as possible explanations.
In summary, it must be emphasised that most of the CL emis- Another problem is the ongoing discussion about the role of Ti
sions in quartz are related to intrinsic lattice defects and not to as an activator of CL in quartz. Observations about correlations
trace elements. Therefore, a correlation of CL response to trace between the Ti content in quartz and the CL intensity resulted
elements is often very equivocal. Among the detectable trace ele- in the conclusion that the blue CL emission band at 450 nm
ments in quartz only a few of them act as activators for CL emis- might be activated by Ti (e.g. Müller et al., 2002, 2003; Van
sion (compare Table 1). Only Al, Ti and charge compensating den Kerkhof et al. 2004; Rusk et al., 2008; Drivenes et al.,
alkali ions in hydrothermal and pegmatite quartz sometimes 2016). First attempts have been made to quantify the Ti concen-
show relations to visible CL behaviour. Most of the inherited tration in quartz by using the intensity of the 450 nm emission
trace elements in quartz have no influence on the CL behaviour. band (Leeman et al., 2012). These assumptions are in sharp con-
To attempt to correlate the concentration of selected trace ele- trast to previous investigations, which have provided evidence by
ments with the visible CL is not reasonable. Spectral CL measure- spectroscopic methods that the blue 450 nm emission can be
ments are necessary and it is only possible to compare related to oxygen deficiency centres (ODC) (e.g. Stevens-Kalceff
trace-element variations with specific individual CL emission and Phillips, 1995; Skuja, 1998; Stevens-Kalceff, 2009).
bands. In most cases, the bulk CL emission consists of different Recent studies on quartz of different origin and containing dif-
emission bands and thus, represents a mixture of point defects ferent concentrations of Ti revealed that structural defects not
responsible for the CL signal. Therefore, correlative relations related to trace elements (self-trapped exciton – STE) and also
between the CL and single trace elements are very difficult or incorporation of Ti into the quartz structure can both activate a
impossible. In addition, the complexity of the luminescence pro- blue CL emission at the same position (450 nm, 2.75 eV; unpub-
cess and analytical conditions hamper a clear quantitative evalu- lished data). The STE-activated CL emission is unstable under the
ation of the CL spectra (Habermann, 2002; Götze, 2012a). electron beam and in particular detectable in quartz with low Ti
The example in Fig. 21 illustrates these complex relationships contents (e.g. high-purity hydrothermal quartz), whereas high Ti
and demonstrates possible misinterpretations. The hydrothermal concentrations (e.g. in quartz phenocrysts of rhyolites) result in a
quartz crystal exhibits marked zoning in panchromatic CL stable CL emission (Fig. 22). In conclusion, even in the case of Ti
(Fig. 21a), visible by variations in the intensity of the bulk (cumu- activation of the 450 nm luminescence emission in quartz, the
lative) CL signal (bright and dark zones). Local measurements of superposition with the STE emission at the same position
the Al content show the dark zones have the highest concentra- would prevent any serious quantitative evaluation of the CL sig-
tions (300 ppm) and the bright zones have low (<50 ppm) and nal. A reliable distinction of the two different CL emissions at
not detectable Al concentrations. Attempting to correlate the Al 450 nm is only possible by time-resolved CL spectroscopy com-
concentration with the panchromatic CL intensity would result bined with EPR spectroscopy and trace-element analysis of the
in the conclusion that Al correlates negatively with the CL inten- Ti concentration. This example emphasises that the correlation
sity (brightness). However, the corresponding true colour CL of CL and trace-element data has to be done with caution.
image (Fig. 21b) demonstrates that the dark zones exhibit blue
CL, whereas bright areas are dominated by yellow CL. Related
Conclusions
CL spectra of these zones (Fig. 21c) reveal that the dark areas
(transient blue CL) are caused by activation due to Al defects Quartz is one of the most common minerals in the Earth crust
([AlO4/M+] centres), whereas the bright areas (yellow CL) have and occurs ubiquitously in magmatic, metamorphic and sedi-
no relation to trace elements and are exclusively due to structural mentary rocks. This common occurrence makes it an important
defects (e.g. STE). In conclusion, the visible zoning in brightness pathfinder mineral for the reconstruction of geological processes
in panchromatic CL (Fig. 21a) is caused mainly by lattice defects and palaeoclimatic conditions as well as the exploration of min-
and is essentially not related to trace-element variations. This eral deposits and other natural resources.
interpretation was only possible by the application of CL Although quartz has a simple composition and represents a
spectroscopy. very pure mineral with low abundances of defects and impurities,
This example shows the essential problems with CL data, in it develops significant indicator properties depending on its for-
particular for the interpretation of panchromatic CL images. mation history and the influence of secondary processes.
Even the combination of CL spectroscopy with local Analytical techniques with low detection limits and/or high spa-
trace-element analysis never provides a quantitative relationship tial resolution can provide a wealth of data concerning the real
between trace elements and the intensity of specific emission structure and chemistry of natural and synthetic quartz. The ana-
bands. For instance, Götte et al. (2011) demonstrated the corres- lytical combination of CL microscopy and spectroscopy, EPR
pondence of Li abundances with [AlO4|Li+]– defects and the tran- spectroscopy, as well as spatially resolved trace-element analysis
sient CL emission at 395 nm in hydrothermal quartz, however has been demonstrated to characterise the type and abundance
they found inconsistencies with a simple causal relationship of structural defects and trace elements in quartz, and permit

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 Mineralogical Magazine 657

Fig. 21 Photomicrographs of intensely zoned hydrothermal quartz from Chemnitz (Saxony, Germany) in panchromatic CL (a) and true colour optical microscopy–
cathodluminescence image (b); the dark luminescent zones in panchromatic CL (blue CL zones in b) have elevated Al concentrations up to 300 ppm, whereas the
bright zones in panchromatic CL (yellow in b) have mostly low (< 50 ppm) or no detectable Al contents; Ti concentrations are generally < 10 ppm. (c) The spectra
reveal that the blue CL (1) is caused by the incorporation of structural Al ([AlO4/M+] centre), the yellow CL (2) is related mainly to structural defects (e.g. STE) and
not to trace elements; the circles in (a) mark the positions of spectral CL analyses.

Fig. 22. CL emission spectra of (a) a quartz phenocryst in the Leisnig porphyry (Saxony, Germany) and (b) high-purity quartz from Kuznechikhinsk (Ural, Russia).
Both quartz samples exhibit a blue CL (see insets) with a dominant emission band at 450 nm. The blue CL emission band of the Ti-rich quartz phenocryst (up to
80 ppm Ti and paramagnetic [TiO4/M+]– centres) is stable during electron irradiation and can probably be related to the activation by substitutional Ti. In contrast,
the intensity of the STE-activated 450 nm emission band of the HPQ quartz (4.52 ppm Ti, no detectable Ti-centres) shows a strong decrease due to electron
bombardment.

reconstruction of processes responsible for their formation and genetic information. Cathodoluminescence can help to visualise
secondary effects. Each of these analytical techniques can provide the real structure of quartz and to relate internal textures to pos-
specific information about the point defects and trace-element sible formation processes.
uptake in quartz. However, interpretation of analytical data might be limited by
It has been shown that quartz from different geological settings the ability of quartz to regenerate during secondary alteration pro-
might have different trace-element composition related to the dif- cesses occurring under metamorphic or hydrothermal conditions.
ferent supply and mechanisms of incorporation of certain ele- Therefore, primary genetic information concerning the real struc-
ments. Therefore, trace elements in quartz are important ture or trace-element composition might be obliterated during
petrogenetic indicators in geosciences. In addition, intrinsic quartz alteration or regeneration (Kempe et al., 2012). In these
types of point defects detected by EPR can provide valuable cases care has to be taken when interpreting the genetic

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 658 Jens Götze et al.

information encoded. Distinction of features related to primary Botis S.M., Pan Y., Bonli T., Xu Y., Zhang A., Nokhrin S. and Sopuck V. (2006)
growth or secondary alteration of quartz is not simple and Natural radiation-induced damage in quartz. II. Distribution and implica-
requires application of complementary analytical techniques. tions for uranium mineralization in the Athabasca Basin, Saskatchewan,
Canada. The Canadian Mineralogist, 44, 1387–1402.
Acknowledgements. We are grateful for analytical help and productive dis- Botis S.M., Pan Y., Nokhrin S. and Nilges M.J. (2008) Natural radiation induced
cussions from Jonathan Sittner, Axel Renno and Ulf Kempe (Freiberg, damage in quartz. III. A new ozonide radical in drusy quartz from the
Germany), Rudolf Mashkovtsev (Novosibirsk, Russia) as well as Marion Athabasca basin, Saskatchewan. The Canadian Mineralogist, 46, 125–138.
Stevens-Kalceff (Sidney, Australia). We acknowledge comprehensive reviews Bottrell S.H., Yardley B. and Buckley F. (1988) A modified crush-leach method
by Rune B. Larsen, K. Breiter and an anonymous reviewer, which improved for the analysis of fluid inclusion electrolytes. Bulletin de Minéralogy, 111,
the quality of the manuscript significantly. 279–290.
Breiter K. and Müller A. (2009) Evolution of rare-metal granitic magmas
Supplementary material. To view supplementary material for this article, documented by quartz chemistry. European Journal of Mineralogy, 21,
please visit https://doi.org/10.1180/mgm.2021.72 335–346.
Breiter K., Svojtka M., Ackerman L. and Švecová K. (2012) Trace element com-
position of quartz from the Variscan Teplice caldera (Krušné Hory/
References Erzgebirge Mts., Czech Republic/Germany): insights into the volcano-
Ackerson M.R., Tailby N.D. and Watson E.B. (2015) Trace elements in quartz plutonic complex evolution. Chemical Geology, 326–327, 36–50.
shed light on sediment provenance. Geochemistry, Geophysics, Geosystems, Breiter K., Ackerman L., Svojtka M. and Müller A. (2013) Behavior of trace
16, 1894–1904. elements in quartz from plutons of different geochemical signature: A
Alessi A., Agnello S., Buscarino G., Pan Y. and Mashkovtsev R.I. (2014) EPR case study from the Bohemian Massif, Czech Republic. Lithos, 175–176,
on radiation-induced defects in SiO2. Pp. 255–298 in: Applications of EPR 54–67.
in Radiation Research (A. Lund and M. Shiotani, editors). Springer, Berlin. Breiter K., Ackerman L., Ďurišová J., Svojtka M. and Novák M. (2014) Trace
Alonso P.J., Halliburton L.E., Kohnke E.E. and Bossoli R.B. (1983) X-ray element composition of quartz from different types of pegmatites: a case
induced luminescence in crystalline SiO2. Journal of Applied Physics, 54, study from the Moldanubian Zone of the Bohemian Massif (Czech
5369–5375. Republic). Mineralogical Magazine, 78, 703–722.
Audétat A. (2013) Origin of Ti-rich rims in quartz phenocrysts from the Breiter K., Ďurišová J. and Dosbaba M. (2020) Chemical signature of quartz
Upper Bandelier Tuff and the Tunnel Spring Tuff, southwestern USA. from S- and A-type rare-metal granites – A summary. Ore Geology
Chemical Geology, 360–361, 99–104. Reviews, 125, 103674.
Bailey P. and Weil J.A. (1991) EPR study of the [SiO4/Li]0 center in alpha- Burley S.D., Mullis J. and Matter A. (1989) Timing diagenesis in the Tartan
quartz. Journal of the Chemical Society-Faraday Transactions, 87, 3143– Reservoir (UK North Sea): constraints from combined cathodolumines-
3146. cence microscopy and fluid inclusion studies. Marine Petrology and
Bailey P. and Weil J.A. (1992a) EPR of [TiO4/Li]B0 and related centers in Geology, 6, 98‒120.
X-irradiated alpha-quartz. Journal of Physics and Chemistry of Solids, 53, Cerin D., Götze J. and Pan Y. (2017) Radiation induced damage in quartz at
601–610. the Arrow uranium deposit, southwestern Athabasca Basin, Saskatchewan.
Bailey P. and Weil J.A. (1992b) The EPR spectral parameters and dynamic The Canadian Mineralogist, 55, 457–472.
properties of the center [TiO4/Na]0A in X-irradiated alpha-quartz. Journal Černỳ P. and Ercit T.S. (2005) The classification of granitic pegmatites revis-
of Physics and Chemistry of Solids, 53, 309–318. ited. The Canadian Mineralogist, 43, 2005–2006.
Bailey P., Pawlik T., Sothe H., Spaeth J.-M. and Weil J.A. (1992) [TiO4]– in Chakraborty D. and Lehmann G. (1976) Distribution of OH in synthetic and
α-quartz studied by low-temperature electron paramagnetic resonance. natural quartz crystals, Journal of Solid State Chemistry, 17, 305–31.
Journal of Physics Condensed Matters, 4, 4063–4073. Claridge R.F., Kryliouk O.M., Weil J.A. and Williams J.A. (2008) Paramagnetic
Bambauer H.U. (1961) Spurenelemente und γ-Farbzentren in Quarzen aus Ge-Li centres in alpha quartz revisited: The DLi ([GeO4/Li ]0D centre.
Zerrklüften der Schweizer Alpen. Schweizerische Mineralogische Canadian Journal of Physics, 86, 1303–1311.
Petrographische Mitteilungen, 41, 335–367. Cohen A.J. (1956) Color centers in alpha-quartz. Part I. Smoky quartz. Journal
Bambauer H.U., Brunner G.O. and Laves F. (1962) Wasserstoff-Gehalte in of Chemistry and Physics, 25, 908–914.
Quarzen aus Zerrklüften der Schweizer Alpen. Schweizerische Cohen A.J. (1985) Amethyst color in quartz, the result of radiation protection
Mineralogische Petrographische Mitteilungen, 42, 221–236. involving iron. American Mineralogist, 70, 1180–1185.
Baron M.A., Stalder R., Konzett J. and Hauzenberger C.A. (2015) Formation Cohen A.J. and Makar L.N. (1985) Dynamic biaxial absorption spectra of Ti3+
conditions of quartz recorded by OH-point defects – experimental and ana- and Fe2+ in a natural rose quartz crystal. Mineralogical Magazine, 49, 709–715.
lytical approach. Physics and Chemistry of Minerals, 42, 53–62. Cox R.T. (1976) ESR of an S = 2 centre in amethyst quartz and its possible
Baur W.H. (2009) In search of the crystal structure of low quartz. Zeitschrift identification as the d4 ion Fe4+. Journal of Physics C, Solid State Physics,
für Kristallographie, 224, 580–592. 9, 3355–3361.
Bershov L.V. (1970) Isomorphism of titanium in natural minerals. Izvestya Cox R.T. (1977) Optical absorption of the d4 ion Fe4+ in pleochroic amethyst
Akademii Nauk SSSR, Seria Geologizna, 12, 47–54 [in Russian]. quartz. Journal of Physics C, Solid State Physics, 10, 4631–4643.
Beurlen H., Müller A., Silva D. and Da Silva M.R.R. (2011) Petrogenetic sig- Cressey G., Henderson C.M.B. and Van der Laan G. (1993) Use of L-edge
nificance of LA–ICP–MS trace-element data on quartz from the X-ray absorption spectroscopy to characterize multiple valence states of
Borborema pegmatite province, Northeast Brazil. Mineralogical Magazine, 3d transition metals; a new probe for mineralogical and geochemical
75, 2703–2719. research. Physics and Chemistry of Minerals, 20, 111–119.
Blankenburg H.-J., Götze J. and Schulz H. (1994) Quarzrohstoffe. Deutscher Daniels M.E. and Morton I.P. (1981) The thermal conductivity and magnetiza-
Verlag für Grundstoffindustrie, Leipzig-Stuttgart, Germany, 296 pp. tion of iron-doped quartz crystals. Physica, 108B, 867–868.
Botis S.M. and Pan Y. (2009) First-principles calculations on the [AlO4/M+]0 Davis P.H. and Weil J.A. (1978) Silver atom center in alpha-quartz. Journal of
(M = H,Li,Na,K) defects in quartz and crystal-chemical controls on the the Physics and Chemistry of Solids, 39, 775–80.
uptake of Al. Mineralogical Magazine, 73, 537–550. Dedushenko S.K., Makhina I.B., Marin A.A., Mukhanov V.A. and Perfiliev
Botis S.M. and Pan Y. (2011) Modeling of [AlO4/Li+]+ paramagnetic defects in Y.D. (2004) What oxidation state of iron determines the amethyst colour?
α-quartz. Canadian Journal of Physics, 89, 809–816. Hyperfine Interaction, 156(157), 417–422.
Botis S.M., Nokhrin S.M., Pan Y., Xu Y. and Bonli T. (2005) Natural Demars C., Pagel M., Deloule E. and Blanc P. (1996) Cathodoluminescence of
radiation-induced damage in quartz. I. Correlations between cathodolumin- quartz from sandstones: Interpretation of the UV range by determination of
escence colors and paramagnetic defects. The Canadian Mineralogist, 43, trace element distributions and fluid-inclusion P-T-X properties in authi-
1565–1580. genic quartz. American Mineralogist, 81, 891–901.

https://doi.org/10.1180/mgm.2021.72 Published online by Cambridge University Press

 Mineralogical Magazine 659

Dennen W.H. (1967) Trace elements in quartz as indicators of provenance. (P.J. Heaney, C.T. Prewitt, and G.V. Gibbs, editors). Reviews in
Geological Society of America Bulletin, 78, 125–130. Mineralogy, Vol. 29. Mineralogical Society of America, Washington DC.
Di Benedetto F., D’Acapito F., Fornaciai G., Montegrossi G., Pardi L., Tesi S. Goreva J.S., Ma C. and Rossman G.R. (2001) Fibrous nanoinclusions in mas-
and Romanelli M. (2009) Fe K-edge XAS study of amethyst. Physics and sive rose quartz: The origin of rose coloration. American Mineralogist, 86,
Chemistry of Minerals, 37, 283–289. 466–472.
Di Benedetto F., Giaccherini A., Montegrossi G., Pardi L.A., Zoleo A., Gorobets B.S. and Rogozine A.A. (2002) Luminescent Spectra of Minerals. RPC
Capolupo F., Innocenti M., Lepore G.O., d’Acapito F., Capacci F., Poli C., VIMS, Moscow, Russia.
Iaia T.E., Buccianti A. and Romanelli M. (2019) Chemical variability of arti- Gorton N.T., Walker G. and Burley S.D. (1996) Experimental analysis of the
ficial stone powders in relation to their health effects. Scientific Reports, 9, composite blue CL emission in quartz. Journal of Luminescence, 72–74,
6531. 669–671.
Di Benedetto F., Giaccherini A., Romanelli M. et al. (2021) A study of radicals Götte T. (2016) Trace element composition of authigenic quartz in sandstones
in industrial raw cristobalite powders. Physics and Chemistry of Minerals, and its correlation with fluid–rock interaction during diagenesis. Pp. 435 in:
48, 9. Reservoir Quality of Clastic and Carbonate Rocks: Analysis, Modelling and
Dickson R.S. and Weil J.A. (1990) The magnetic properties of the oxygen-hole Prediction. (P.J. Armitage, A.R. Butcher, J.M. Churchill, A.E. Csoma,
aluminum centres in crystalline SiO2. IV. [AlO4/Na+]+. Canadian Journal of C. Hollis, R.H. Lander, J.E. Omma, and R.H. Worden, editors.)
Physics, 68, 630–642. Geological Society Special Publications, London, Great Britain.
Dickson R.S., Weil J.A. and Davis P.H. (1991) The paramagnetic germanium Götte T., Pettke T., Ramseyer K., Koch-Müller M. and Mullis J. (2011)
sodium impurity centers [GeO4/Na]0A and [GeO4/Na]0C in alpha-quartz. Cathodoluminescence properties and trace element signature of hydrother-
Canadian Journal of Physics, 69, 761–779. mal quartz: A fingerprint of growth dynamics. American Mineralogist, 96,
Dong G., Morrison G. and Jaireth S. (1995) Quartz textures in epithermal 802–813.
veins, Queensland – Classification, origin, and implication. Economic Götze J. (2009) Chemistry, textures and physical properties of quartz – geo-
Geology, 90, 1841–1856. logical interpretation and technical application. Mineralogical Magazine,
Donnay J.D.H. and Le Page Y. (1978) The vicissitudes of the low-quartz crystal 73, 645–671.
setting or the pitfalls of enantiomorphism. Acta Crystallographica, A34, Götze J. (2012a) Application of cathodoluminescence (CL) microscopy and
584–594. spectroscopy in geosciences. Microscopy and Microanalysis, 18, 1270–1284.
Drivenes K., Larsen R.B., Müller A. and Sørensen B.E. (2016) Crystallization Götze J. (2012b) Mineralogy, Geochemistry and cathodoluminescence of
and uplift path of late Variscan granites evidenced by quartz chemistry authigenic quartz from different sedimentary rocks. Pp. 287–306 in:
and fluid inclusions: Example from the Land’s End granite, SW England. Quartz: Deposits, Mineralogy and Analytics. (J. Götze and R. Möckel, edi-
Lithos, 252–253, 57–75. tors). Springer Geology, Heidelberg-New York-Dordrecht-London.
Entzian W. and Ahlgrimm C. (1983) Comparative studies about the cathodo- Götze J. and Hanchar J. (2018) Atlas of Cathodoluminescence (CL)
luminescence of SiO2. Wissenschaftliche Zeitschrift Universität Rostock, Microtextures. GAC Miscellaneous Publication No. 10. Geological
Naturwissenschaftliche Reihe 32, 27–29 [in German]. Association of Canada, St. John’s, Newfoundland and Labrador, Canada.
Fabricius J. (1987) Natural Na-K-Mg-Cl solutions and solid derivatives Götze J. and Lewis R. (1994) Distribution of REE and trace elements in size
trapped in euhedral quartz from Danish Zechstein salt. Chemical Geology, and mineral fractions of high purity quartz sands. Chemical Geology, 114,
61, 95‒112. 43–57.
Feigl F.J. and Anderson J.H. (1970) Defects in crystalline quartz: electron para- Götze J. and Möckel R. (editors) (2012) Quartz: Deposits, Mineralogy and
magnetic resonance of E’ vacancy centers associated with germanium Analytics. Springer Geology, Heidelberg-New York-Dordrecht-London.
impurities. Journal of Physics and Chemistry of Solids, 31, 575–596. Götze J. and Plötze M. (1997) Investigation of trace-element distribution in
Friebele E.J., Griscom D.L., Stapelbroek M. and Weeks R.A. (1979) detrital quartz by Electron Paramagnetic Resonance (EPR). European
Fundamental defect centers in glass: the peroxy radical in irradiated, high- Journal of Mineralogy, 9, 529–537.
purity, fused silica. Physical Review Letters, 42, 1346–1348. Götze J. and Zimmerle W. (2000) Quartz and silica as guide to provenance in
Friedman G.M. and Shukla V. (1980) Significance of authigenic quartz euhe- sediments and sedimentary rocks. Contributions to Sedimentary Petrology,
dra after sulphates; example from the Lockport formation (Middle Silurian) 21, 91 p.
from New York. Journal of Sedimentary Research, 50, 1299‒1304. Götze J., Plötze M., Fuchs H. and Habermann D. (1999) Defect structure and
Fubini B., Giamello E., Volante M. and Bolis V. (1990) Chemical functional- luminescence behaviour of agate – results of electron paramagnetic reson-
ities at the silica surface determining its reactivity when inhaled. Formation ance (EPR) and cathodoluminescence (CL) studies. Mineralogical
and reactivity of surface radicals. Toxicology and Health, 6, 571–598. Magazine, 63, 149–163.
Füchtbauer H. (1961) Zur Quarzneubildung in Erdöllagerstätten. Erdöl und Götze J., Plötze M. and Habermann D. (2001a) Cathodoluminescence (CL) of
Kohle, 14, 169‒173. quartz: origin, spectral characteristics and practical applications. Mineralogy
Gaillou E., Delaunay A., Rondeau B., Bouhnik-le-Coz M., Fritsch E., Cornen and Petrology, 71, 225–250.
G. and Monnier C. (2008) The geochemistry of gem opals as evidence of Götze J., Plötze M., Tichomirowa M., Fuchs H. and Pilot J. (2001b)
their origin. Ore Geology Reviews, 34, 113–126. Aluminium in quartz as indicator for the temperature of formation of
Gerler J. (1990) Geochemische Untersuchungen an hydrothermalen, agate. Mineralogical Magazine, 65, 400–406.
metamorphen, granitischen und pegmatitischen Quarzen und deren Götze J., Plötze M., Graupner T., Hallbauer D.K. and Bray C. (2004) Trace
Flüssigkeitseinschlüssen. PhD thesis, University Göttingen, Germany. element incorporation into quartz: a combined study by ICP-MS, electron
Gerler J. and Schnier C. (1989) Neutron activation analysis of liquid inclusions spin resonance, cathodoluminescence, capillary ion analysis and gas chro-
exemplified by a quartz sample from the Ramsbeck Mine, F.R.G. Nuclear matography. Geochimica et Cosmochimica Acta, 68, 3741–3759.
Geophysics, 3, 41–48. Götze J., Plötze M. and Trautmann T. (2005) Structure and luminescence
Ghazi A.M., Vanko D.A., Roedder E. and Seeley R.C. (1993) Determination of characteristics of quartz from pegmatites. American Mineralogist, 90, 13–21.
rare earth elements in fluid inclusions by inductively coupled plasma-mass Götze J., Möckel R., Kempe U., Kapitonov I. and Vennemann T. (2009) Origin
spectrometry (ICP-MS). Geochimica et Cosmochimica Acta, 57, 4513–4516. and characteristics of agates in sedimentary rocks from the Dryhead area,
Giordano L., Sushko P.V., Pacchioni G. and Shluger A.L. (2007) Optical and Montana/USA. Mineralogical Magazine, 73, 673–690.
EPR properties of point defects at a crystalline silica surface: ab initio Götze J., Schrön W., Möckel R. and Heide K. (2012) The role of fluids in the
embedded-cluster calculations. Physical Reviews B, 75, 24109–24119. formation of agate. Geochemistry, 72, 283–286.
Glazer A.M. (2018) Confusion in the description of the quartz structure yet Götze J., Hanchar J., Schertl. H.-P., Neuser D.K. and Kempe U. (2013)
again. Journal of Applied Crystallography, 51, 915–918. Optical microscope-cathodoluminescence (OM–CL) imaging as a powerful
Goldsmith D.F. (1994) Health effects of silica dust exposure. Pp. 545–595 in: tool to reveal internal textures of minerals. Mineralogy and Petrology, 107,
Silica: Physical Behavior, Geochemistry, and Materials Applications 373–392.

https://doi.org/10.1180/mgm.2021.72 Published online by Cambridge University Press

 660 Jens Götze et al.

Götze J., Gaft M. and Möckel R. (2015a) Uranium and uranyl luminescence in Jaeger D., Stalder R., Masago H. and Strasser M. (2019) OH defects in quartz
agate/chalcedony. Mineralogical Magazine, 79, 983–993. as a provenance tool: application to fluvial and deep marine sediments from
Götze J., Pan Y., Stevens-Kalceff M., Kempe U. and Müller A. (2015b) Origin SW Japan. Sedimentary Geology, 388, 66–80.
and significance of the yellow cathodoluminescence (CL) of quartz. Jani M.G., Bossoli R.B. and Halliburton L.E. (1983) Further characterization of
American Mineralogist, 100, 1469–1482. the E′ 1 center in crystalline SiO2. Physical Reviews B, 27, 2285–2293.
Götze J., Möckel R., Vennemann T. and Müller A. (2016) Origin and geo- Jollands M.C., Blanchard M. and Balan E. (2020) Structure and theoretical
chemistry of agates from Permian volcanic rocks of the Sub-Erzgebirge infrared spectra of OH defects in quartz. European Journal of Mineralogy,
basin (Saxony, Germany). Chemical Geology, 428, 77–91. 32, 311–323.
Götze J., Pan Y., Müller A., Kotova E.L. and Cerin D. (2017) Trace element Jones C.E. and Embree D. (1976) Correlations of the 4.77–4.28 eV lumines-
compositions and defect structures of high-purity quartz from the cence band in silicon dioxide with oxygen vacancy. Journal of Applied
Southern Ural region, Russia. Minerals, 7, 189. Physics, 47, 5365–5371.
Götze J., Möckel R. and Pan Y. (2020) Mineralogy, geochemistry and genesis of Jourdan A.-L., Vennemann T.W., Mullis J., Ramseyer K. and Spiers C.J. (2009)
agates – a review. Minerals, 10, 1037. Evidence of growth and sector zoning in hydrothermal quartz from Alpine
Grew E.S. and Hinthorne J.R. (1983) Boron in sillimanite. Science, 221, 547– veins. European Journal Mineralogy, 21, 219–231.
549. Kats A. (1962) Hydrogen in alpha quartz. Philips Research Reports, 17, 133–
Griffiths J.H.E., Owen J. and Ward I.M. (1954) Paramagnetic resonance in 279.
neutron-irradiated diamond and smoky quartz. Nature, 173, 439–442. Kelly J.L., Fu B., Kita N.T., Valley J.W. (2007) Optically continuous silcrete
Grimm W.-D. (1962) Idiomorphe Quarze als Leitmineralien für salinare quartz cements of the St. Peter sandstone: High precision oxygen isotope
Fazies. Erdöl und Kohle, 15, 880‒887. analysis by ion microprobe. Geochimica et Cosmochimica Acta, 71, 3812‒
Griscom D.L. (1985) Defect structure of glasses. Journal of Non-Crystalline 3832.
Solids, 73, 51–77. Kempe U., Götze J., Dandar S. and Habermann D. (1999) Magmatic and
Günther D., Audétat A., Frischknecht R. and Heinrich C.A. (1998) metasomatic processes during formation of the Nb-Zr-REE deposits from
Quantitative analysis of major, minor and trace elements in fluid inclusions Khaldzan Buregte (Mongolian Altai): indications from a combined
using laser ablation–inductively coupled plasma mass spectrometry. Journal CL-SEM study. Mineralogical Magazine, 63, 165–167.
of Analytical Atomic Spectrometry, 13, 263–270. Kempe U., Götze J., Enchbat D., Monecke T. and Poutivtsev M. (2012) Quartz
Habermann D. (2002) Quantitative cathodoluminescence (CL) spectroscopy of regeneration and its use as a repository of genetic information. Pp. 331–355
minerals: possibilities and limitations. Mineralogy and Petrology, 76, 247– in: Quartz: Deposits, Mineralogy and Analytics. (J. Götze and R. Möckel,
259. editors). Springer Geology, Heidelberg-New York-Dordrecht-London.
Hallbauer D.K. (1992) The use of selected trace elements in vein quartz and Kihara K. (1990) An X-ray study of the temperature dependence of the quartz
quartz pebbles in identifying processes of formation and source rocks. structure. European Journal of Mineralogy, 2, 63–77.
Proceedings Geological Society South Africa, Bloemfontein, 157–159. Komur, K., Horikawa Y. and Toyoda S. (2002) Development of radiation-
Halliburton L.E., Hantehzadeh M.R., Minge J., Mombourquette M.J. and Weil damage halos in low-quartz: cathodoluminescence measurement after
J.A. (1989) EPR study of Fe3+ in alpha quartz: a reexamination of the He+ ion implantation. Mineralogy and Petrology, 76, 261–266.
lithium-compensated center. Physical Reviews B, 40, 2076–2081. Krickl R., Nasdala L., Götze J., Grambole D. and Wirth R. (2008) Alteration of
Han C.S. and Choh S.H. (1989) EPR study of iron centers in natural amethyst. SiO2 caused by natural and artificial alpha-irradiation. European Journal of
Journal of the Korean Physical Society, 22, 241–252. Mineralogy, 20, 517–522.
Harben P.W. (2002) The Industrial Mineral Handbook – A Guide to Markets, Ladenburger S., Walter B.F., Marks M.A.W. and Markl G. (2020) Combining
Specifications and Prices, 4th Edition. Industrial Mineral Information. ion chromatography and total reflection X-ray fluorescence for detection of
Worcester Park, Surrey, UK 412 p. major, minor and trace elements in quartz-hosted fluid inclusions. Journal
Heaney P.J. and Davis A.M. (1995) Observation and origin of self-organized of Analytical Chemistry, 75, 1477–1485.
textures in agates. Science, 269, 1562–1565. Laman F.C. and Weil J.A. (1977) Silver-compensated germanium center in
Hong W., Cooke D.R., Zhang L., Fox N. and Thompson J. (2019) α-quartz. Journal of Physics and Chemistry of Solids, 38, 949–956.
Cathodoluminescence features, trace elements, and oxygen isotopes of quartz Laman F.C. and Weil J.A. (1978) A germanium tri-hytrogen center in alpha-
in unidirectional solidification textures from the Sn-mineralized Heemskirk quartz. Pp. 253–257 in: The Physics of SiO2 and its interfaces (S.T.
granite, western Tasmania. American Mineralogist, 104, 100–117. Pantelides, editor). Pergamon, New York, USA.
Hu B., Pan Y., Botis S., Rogers B., Kotzer T. and Yeo G. (2008) Lan Q., Lin J., Fu S. and Luo J. (2021) Cathodoluminescent textures and trace
Radiation-induced defects in drusy quartz, Athabasca Basin, Canada: A element signatures of hydrothermal quartz from the granite-related No. 302
new aid to exploration of uranium deposits. Economic Geology, 103, uranium deposit, South China: A reconnaissance study for their genetic sig-
1571–1580. nificances. Journal of Geochemical Exploration, 224, 106740. doi.org/10.
Huang R. and Audétat A. (2012) The titanium-in-quartz (TitaniQ) thermoba- 1016/j.gexplo.2021.106740.
rometer: A critical examination and re-calibration. Geochimica et Landtwing M. and Pettke T. (2005) Relationships between
Cosmochimica Acta, 84, 75–89. SEM-cathodoluminescence response and trace-element composition of
Hutton D.R. and Troup G.J. (1966) Paramagnetic resonance centres in ameth- hydrothermal vein quartz. American Mineralogist, 90, 122–131.
yst and citrine quartz. Nature, 211, 621. Larsen R.B., Polvé M. and Juve G. (2000) Granite pegmatite quartz from
Isoya J. and Weil J.A. (1979) Uncompensated titanium(3+) center in alpha- Evje-Iveland: trace-element chemistry and implications for the formation
quartz. Physica status solidi a, 52, K193–K196. of high-purity quartz. NGU Bulletin, 436, 57–59.
Isoya J., Weil J.A. and Claridge R.F.C. (1978) The dynamic interchange and Larsen R.B., Henderson I., Ihlen P.M. and Jacamon F. (2004) Distribution and
relation between germanium centers in alpha-quartz. The Journal of petrogenetic behaviour of trace elements in granitic pegmatite quartz from
Chemical Physics, 69, 4876–4884. South Norway. Contributions Mineralogy Petrology, 147, 615–628.
Isoya J., Weil J.A. and Davis P.H. (1983) EPR of atomic-hydrogen 1H and 2H Leeman W.P., McRae C.M., Wilson N.C., Torpy A., Lee C.-T.A., Student J.J.,
in α-quartz. Journal of Physics and Chemistry of Solids, 44, 335–343. Thomas J.B. and Vicenzi E.P. (2012) A study of cathodoluminescence
Isoya J., Tennant W.C. and Weil J.A. (1988) Electron-paramagnetic-res of the and trace element compositional zoning in natural quartz from volcanic
TiO4/Li center in crystalline quartz. Journal of Magnetic Resonance, 79, 90– rocks: Mapping titanium content in quartz. Microscopy and
98. Microanalysis, 18, 1322–1341.
Jacamon F. and Larsen R. (2009) Trace element evolution of quartz in the Lees N.S., Walsby C.J., Williams J.A.S., Weil J.A. and Claridge R.F.C. (2003)
charnockitic Kleivan granite, SW-Norway: the Ge/Ti ratio of quartz as an EPR of a hydrogen/double-lithium centre in α-quartz. Physics and
index of igneous differentiation. Lithos, 107, 281–291. Chemistry of Minerals, 30, 131–141.

https://doi.org/10.1180/mgm.2021.72 Published online by Cambridge University Press

 Mineralogical Magazine 661

Lehmann G. (1978) Farbe von Mineralien und ihre Ursachen. Fortschritte Mashkovtsev R.I., Shcherbakova M.Ya. and Solntsev V.P. (1978) EPR of radi-
Mineralogie, 56/2, 172–252. ation hole centers in α-quartz. Trudy Instituta Geologii i Geofyziki
Lehmann G. and Bambauer H.U. (1973) Quarzkristalle und ihre Farben. Akademii Nauk SSSR, Sib. Otd., 385, 78–86 [in Russian].
Angewandte Chemie, 85, 281–289. Mashkovtsev R.I., Howarth D.H. and Weil J.A. (2007) Biradical states of
Lehmann G. and Moore W.I. (1966) Optical and paramagnetic properties of oxygen-vacancy defects in α-quartz. Physical Reviews B, 76, 214114.
iron centers in quartz. Journal of Chemical Physics, 44, 1741–1745. Mashkovtsev R.I., Li Z., Mao M. and Pan Y. (2013) 73Ge, 17O and 29Si hyper-
Lehmann K., Pettke T. and Ramseyer K. (2011) Significance of trace elements fine interactions of the Ge E′ 1 center in crystalline SiO2. Journal of Magnetic
in syntaxial quartz cement, Haushi Group sandstones, Sultanate of Oman. Resonance, 233, 7–16.
Chemical Geology, 280, 47–57. Mashkovtsev R.I., Botis S.M., Nilges M.J. and Pan Y. (2019) Paramagnetic
Le Page Y., Calvert L.D. and Gabe E.J. (1980) Parameter variation in low- defects in neutron-irradiated α-quartz: Novel Al-associated E′ centers.
quartz between 94 and 298 K. Journal of Physics and Chemistry of Solids, EPL, 128, 54004.
41, 721–725. Matyash I.V., Brik A.B., Zayats A.P. and Masykin V.V. (1987)
Li Z. and Pan Y. (2012) First-principles calculations of the E′ 1 center in quartz: Radiospectroscopy of Quartz. Naukova Dumka, Kiev, USSR.
structural models, 29Si hyperfine parameters and association with Al impur- McBride E.F. (1989) Quartz cement in sandstones: a review. Earth Science
ity. Pp. 161–175 in: Quartz: Deposits, Mineralogy and Analytics. (J. Götze Reviews, 26, 69‒112.
and R. Möckel, editors). Springer Geology, Heidelberg-New York- McCandless T.E., Lajack D.J., Ruiz J. and Ghazi A.M. (1997) Trace element
Dordrecht-London. determination of single fluid inclusions in quartz by Laser Ablation
Li J., Hu R., Xiao J., Zhuo Y., Yan J. and Oyebamiji A. (2020) Genesis of gold ICP-MS. Geostandard Newsletter, 21, 279–287.
and antimony deposits in the Youjiang metallogenic province, SW China: McConnell J.D.C., Lin J.S. and Heine V. (1995) The solubility of [4H]Si defects
Evidence from in situ oxygen isotopic and trace element compositions of in α-quartz and their role in the formation of molecular water and related
quartz. Ore Geology Reviews, 116, 103257. weakening on heating. Physics and Chemistry of Minerals, 22, 357–366.
Lin J.S., Payne M.C., Heine V. and McConnell J.D.C. (1994) Ab initio calcula- McEachern R.J. and Weil J.A. (1994) 17O hyperfine interaction for the [GeO4]–I,
tions on (OH)4 defects in α-quartz. Physics and Chemistry of Minerals, 21, 0
II and [GeO4/Li]A,C centers in an enriched crystal of alpha-quartz. Physical
150–155. Review B, 49, 6698–6709.
Lipin B.R. and McKay G.A. (Editors)(1986) Geochemistry and Mineralogy of McEachern R.J., Weil J.A. and Sawyer B. (1992) Distortion and 17O hyperfine
Rare Earth Elements. Reviews in Mineralogy, 21. The Mineralogical interaction in the centres [GeO4]I,II in α-quartz. Solid State
Society of America, Washington DC, 349 pp. Communications, 81, 207–209.
Luff B.J. and Townsend P.D. (1990) Cathodoluminescence of synthetic quartz. McLaren A.C., Cook R.F., Hyde S.T. and Tobin R.C. (1983) The mechanisms
Journal Physics Condensed Matter, 2, 8089–8097. of the formation and growth of water bubbles and associated dislocation
Luo K., Zhou J.-X., Huang Z.-L., Caulfield J., Zhao J.-X., Feng Y.-X. and loops in synthetic quartz. Physics and Chemistry of Minerals, 9, 79–94.
Ouyang H. (2020) New insights into the evolution of McLaren A.C., Fitz Gerald J.D. and Gerretsen J. (1989) Dislocation nucleation
Mississippi-Valley-Type hydrothermal system: A case study of the and multiplication in synthetic quartz: relevance to water weakening.
Wusihe Pb-Zn deposit, south China, using quartz in-situ trace elements Physics and Chemistry of Minerals, 16, 465–482.
and sulfides in-situ S-Pb isotopes. American Mineralogist, 105, 35–51. Meunier J.D., Sellier E. and Pagel M. (1990) Radiation-damage rims in quartz
Ma C., Goreva J.S. and Rossman G.R. (2002) Fibrous nanoinclusions in mas- from uranium-bearing sandstones. Journal of Sedimentary Petrology, 60,
sive rose quartz: HRTEM and AEM investigations. American Mineralogist, 53–58.
87, 269–276. Meyer B.K., Lohse F., Spaeth J.M. and Weil J.A. (1984) Optically detected mag-
Mackey J.H. (1963) EPR study of impurity-related color centers in netic resonance of the [AlO4]0 centre in crystalline quartz. Journal of Physics
germanium-doped quartz. Journal of Chemical Physics, 39, 74–83. C: Solid State Physics, 17, L31–L36.
Mackey J.H., Boss J.W. and Wood D.E. (1970) EPR study of Mineeva R.M., Bershov L.V. and Petrov I. (1991) EPR of surficially bound Fe3+
substitutional-aluminum-related hole centers in synthetic α-quartz. ions in polycrystalline quartz. Doklady Akademii Nauk SSSR, 321/2, 368–
Journal of Magnetic Resonance, 3, 44–54. 372 [in Russian].
Mao W., Rusk B., Yang F. and Zhang M. (2017) Physical and chemical evolu- Minge, J. Weil J.A. and McGavin D.G. (1989) EPR study of Fe3+ in alpha-
tion of the Dabaoshan Porphyry Mo deposit, South China: Insights from quartz – characterization of a new type of cation-compensated center.
fluid inclusions, cathodoluminescence, and trace elements in quartz. Physical Review B, 40, 6490–6498.
Economic Geology, 112, 889–918. Minge J., Mombourquette M.J. and Weil J.A. (1990) EPR study of Fe3+ in
Maschmeyer D. and Lehmann G. (1983) A trapped-hole center causing alpha-quartz – the sodium-compensated center. Physical Review B, 42,
rose coloration of natural quartz. Zeitschrift für Kristallographie, 163, 33–36.
181–196. Miyoshi N., Yamaguchi Y. and Makino K. (2005) Successive zoning of Al and
Mashkovtsev R.I. and Pan Y. (2011) Biradical states of oxygen-vacancy defects H in hydrothermal vein quartz. American Mineralogist, 90, 310–315.
in alpha-quartz: centers E′′ 2 and E′′ 4. Physics and Chemistry of Minerals, 38, Moiseev B.M. (1985) Radiation Processes in Minerals. Nedra, Moscow, Russia
647–54. [in Russian].
Mashkovtsev R.I. and Pan Y. (2012a) Five new E′ centers and their 29Si hyper- Mombourqette M.J., Tennant W.C. and Weil J.A. (1986) EPR study of Fe3+ in
fine structure in electron-irradiated α-quartz. Physics and Chemistry of alpha-quartz – a reexamination of the so-called I-center. Journal of
Minerals, 39, 79–85. Chemical Physics, 85, 68–79.
Mashkovtsev R.I. and Pan Y. (2012b) Stable states of E′′ defects in α-quartz. Mombourqette M.J., Minge I., Hantehzadeh M.R., Weil J.A. and Halliburton
EPL, 98, 56005. L.E. (1989) EPR study of Fe3+ in alpha-quartz: Hydrogen-compensated cen-
Mashkovtsev R.I. and Pan Y. (2013) Nature of paramagnetic defects in ter. Physical Review B, 39, 4004–4008.
α-quartz: Progresses in the First Decade of the 21st Century. Pp. 65–104 Monecke T., Kempe U., Petersen S., Götze J., Herzig P. and Wolf D. (1999)
in: New Developments in Quartz Research: Varieties, Crystal Chemistry Trace element characteristics of quartz from the TAG hydrothermal
and Uses in Technology (B. Novak and P. Marek, editors). Nova Science mound. Pp. 551–554 in: Mineral Deposits: Processes to Processing
Publishers, New York, USA. (C.J. Stanley et al., editors). Balkema, Rotterdam, Netherlands.
Mashkovtsev R.I. and Pan Y. (2014) Triplet states of oxygen-vacancy defects in Monecke T., Bombach G., Klemm W., Kempe U., Götze J. and Wolf D. (2000)
α-quartz: Center E"9. EPL, 107, 36005. Determination of trace elements in quartz standard UNS-SpS and in natural
Mashkovtsev R.I. and Pan Y. (2016) New E′ centers in neutron-irradiated quartz by ICP-MS. Geostandards Newsletter, 24/1, 73–81.
α-quartz. EPL, 113, 64004. Monecke T., Kempe U. and Götze J. (2002) Genetic significance of the trace
Mashkovtsev R.I. and Pan Y. (2018) EPR study of new E‘ centers in element content in metamorphic and hydrothermal quartz: A reconnais-
neutron-irradiated α-quartz. EPL, 124, 54001. sance study. Earth and Planetary Science Letters, 202, 709–724.

https://doi.org/10.1180/mgm.2021.72 Published online by Cambridge University Press

 662 Jens Götze et al.

Monecke T., Dulski P. and Kempe U. (2007) Origin of convex tetrads in rare Nuttall R.H.D. and Weil J.A. (1981b) The magnetic properties of the oxygen-
earth element patterns of hydrothermally altered siliceous igneous rocks hole aluminum centers in crystalline SiO2. II. [AlO4/H+]+ and [AlO4/Li+]+.
from the Zinnwald Sn-W deposit, Germany. Geochimica et Cosmochimica Canadian Journal of Physics, 59, 1709–1718.
Acta, 71, 335–353. Nuttall R.H.D. and Weil J.A. (1981c) The magnetic properties of the oxygen-
Monnier L., Lach P., Salvi S., Melleton J., Bailly L., Béziat D., Monnier Y. and hole aluminum centers in crystalline SiO2. III. [AlO4]+. Canadian Journal of
Gouy S. (2018) Quartz trace-element composition by LA-ICP-MS as proxy Physics, 59, 1886–1892.
for granite differentiation, hydrothermal episodes, and related mineralization: O’Brien M.C.M. (1955) The structure of the colour centres in smoky quartz.
The Beauvoir Granite (Echassières district), France. Lithos, 320, 355–377. Proceedings of the Royal Society, A231, 404–414.
Monnier L., Salvi S., Pochon A., Melleton J., Béziat D., Lach P. and Bailly L. Owen M.R. (1988) Radiation-damage halos in quartz. Geology, 16, 529–532.
(2021) Antimony in quartz as a vector to mineralization: A statistical Pacák K., Zacharias J. and Strnad L. (2019) Trace-element chemistry of barren
approach from five Variscan Sb occurrences (France). Journal of and ore-bearing quartz of selected Au, Au-Ag and Sb-Au deposits from the
Geochemical Exploration, 221, 106705. Bohemian Massif. Journal of Geosciences, 64, 19–35.
Müller A. and Knies J. (2013) Trace elements and cathodoluminescence of Pan Y. and Nilges M.J. (2014) Electron paramagnetic resonance (EPR) spec-
detrital quartz in Arctic marine sediments – a new ice-rafted debris proven- troscopy: Basic principles, experimental techniques and applications to
ance proxy. Climate Past, 9, 2615–2630. Earth and planetary sciences. Pp. 655–690 in: Spectroscopic Methods in
Müller A. and Koch-Müller M. (2009) Hydrogen speciation and trace element Mineralogy and Material Sciences (G.S. Henderson, D.R. Neuville and
contents of igneous, hydrothermal and metamorphic quartz from Norway. R.T. Downs, editors). Reviews in Mineralogy and Geochemistry, Volume
Mineralogical Magazine, 73, 569–584. 78. The Mineralogical Society of America and the Geochemical Society,
Müller A., Kronz A. and Breiter K. (2002) Trace elements and growth patterns Chantilly, Virginia, USA.
in quartz: a fingerprint of the evolution of the subvolcanic Podlesi granite Pan Y., Botis S. and Nokhrin S. (2006) Applications of natural
system (Krušné Hory, Czech Republic). Bulletin of the Czech Geological radiation-induced paramagnetic defects in quartz to exploration in sedi-
Survey, 77, 135–145. mentary basins. Journal of China University of Geosciences, 17, 258–271.
Müller A., Wiedenbeck M., Van den Kerkhof A.M., Kronz A. and Simon K. Pan Y., Nilges M.J. and Mashkovtsev R.I. (2008) Radiation-induced defects in
(2003) Trace elements in quartz – a combined electron microprobe, second- quartz. II. W-band single-crystal EPR study of natural citrine. Physics and
ary ion mass spectrometry, laser-ablation ICP-MS, and cathodolumines- Chemistry of Minerals, 35, 387–397.
cence study. European Journal of Mineralogy, 15, 747–763. Pan Y., Nilges M.J. and Mashkovtsev R.I. (2009) Radiation-induced defects in
Müller A., Breiter K., Seltmann R. and Pécskay Z. (2005) Quartz and feldspar quartz: a multifrequency EPR study and DFT modelling of new peroxy radi-
zoning in the eastern Erzgebirge volcano-plutonic complex (Germany, cals. Mineralogical Magazine, 73, 519–536.
Czech Republic): evidence of multiple magma mixing. Lithos, 80, 201–227. Pan Y., Li D., Feng R., Wiens E., Chen N., Götze J. and Lin J. (2021) Uranyl
Müller A., Ihlen P.M. and Wanvik J.E. (2007) High-purity quartz mineralisa- binding mechanism in microcrystalline silicas: A potential missing
tion in kyanite quartzites, Norway. Mineralium Deposita, 42, 523–535. link for uranium mineralization by direct uranyl co-precipitation and
Müller A., Wiedenbeck M., Flem B. and Schiellerup H. (2008) Refinement of environmental implications. Geochimica et Cosmochimica Acta, 292,
phosphorus determination in quartz by LA-ICP-MS through new reference 518–531.
material values. Geostandards and Geoanalytical Research, 32, 361–376. Perlson B.D. and Weil J.A. (2008) Electron paramagnetic resonance studies of
Müller A., Herrington R., Armstrong R., Seltmann R., Kirwin D.J., Stenina the E′ centers in alpha-quartz. Canadian Journal of Physics, 86, 871–881.
N.G. and Kronz A. (2010) Trace elements and cathodoluminescence of Perny B., Eberhardt P., Ramseyer K. and Mullis J. (1992) Microdistribution of
quartz in stockwork veins of Mongolian porphyry-style deposits. aluminium, lithium and sodium in quartz: Possible causes and correlation
Mineralium Deposita, 45, 707–727. with short-lived cathodoluminescence. American Mineralogist, 77, 534–544.
Müller A., Wanvik J.E. and Ihlen P.M. (2012) Petrological and chemical Peterková T. and Dolejš J. (2019) Magmatic-hydrothermal transition of
characterisation of high-purity quartz deposits with examples from Mo-W-mineralized granite-pegmatite-greisen system recorded by trace ele-
Norway. Pp. 71–118 in: Quartz: Deposits, Mineralogy and Analytics. ments in quartz: Krupka district, Eastern Krušné hory/Erzgebirge. Chemical
(J. Götze and R. Möckel, editors). Springer Geology, Heidelberg- Geology, 523, 179–202.
New York-Dordrecht-London. Plötze M. and Wolf D. (1996) EPR- and TL-spectra of quartz: Irradiation
Müller A., Ihlen P.M., Snook B., Larsen R.B., Flem B., Bingen B. and dependence of [TiO-4/Li+]– centres. European Journal of Mineralogy, 8,
Williamson B.J. (2015) The chemistry of quartz in granitic pegmatites of 217 [in German].
Southern Norway: Petrogenetic and economic implications. Economic Potrafke A., Stalder R., Schmidt B.C. and Ludwig T. (2019) OH defect contents
Geology, 110, 1737–1757. in quartz in a granitic system at 1–5 kbar. Contributions to Mineralogy and
Müller A., Romer R.L. and Pedersen R.-B. (2017) The Sveconorwegian peg- Petrology, 174, 98.
matite province – Thousands of pegmatites without parental granites. The Potrafke A., Breiter K., Ludwig T., Neuser R.D. and Stalder R. (2020)
Canadian Mineralogist, 55, 283–315. Variations of OH defects and chemical impurities in quartz within igneous
Müller A., Herklotz G. and Giegling H. (2018) Chemistry of quartz related to bodies. Physics and Chemistry of Minerals, 47, 24.
the Zinnwald/Cínovec Sn-W-Li greisen-type deposit, Eastern Erzgebirge, Pott G.T. and McNicol B.D. (1971) Spectroscopic study of the coordination
Germany. Journal of Geochemical Exploration, 190, 357–373. and valence of Fe and Mn ions in and on the surface of aluminas and silicas.
Müller A., Keyser W., Simmons W.B., Webber K., Wise M., Beurlen H., Discussion Faraday Society, 52, 121–131.
Garate-Olave I., Roda-Robles E. and Galliski M.A. (2021) Quartz chemistry Rakov L.T., Milovidova N.D., Kuvshinova K.A. and Moiseev B.M. (1985)
of granitic pegmatites: Implications for classification, genesis and explor- Investigation of Ge-centres in natural polycrystalline quartz using EPR.
ation. Chemical Geology, https://doi.org/10.1016/j.chemgeo.2021.120507. Geokhimiya, 9, 1339–1344 [in Russian].
Nilges M.J., Pan Y. and Mashkovtsev R.I. (2008) Radiation-induced defects in Ramseyer K. and Mullis J. (1990) Factors influencing short-lived blue cathodo-
quartz. I. Single-crystal W-band EPR study of an electron irradiated quartz. luminescence of alpha-quartz. American Mineralogist, 75, 791–800.
Physics and Chemistry of Minerals, 35, 103–115. Ramseyer K., Baumann J., Matter A. and Mullis J. (1988) Cathodoluminescence
Nilges M.J., Pan Y. and Mashkovtsev R.I. (2009) Radiation-induced defects in colours of alpha-quartz. Mineralogical Magazine, 52, 669–677.
quartz. III. EPR, ENDOR and ESEEM characterization of a peroxy radical. Remond G., Cesbron F., Chapoulie R., Ohnenstetter D., Roques-Carmes C.
Physics and Chemistry of Minerals, 36, 63–71. and Schvoerer M. (1992) Cathodoluminescence applied to the microcharac-
Nuttall R.H.D. and Weil J.A. (1980) Two hydrogenic trapped-hole species in terization of mineral materials: a present status in experimentation and
α-quartz. Solid State Communications, 33, 99–102. interpretation. Scanning Microscopy, 6, 23–68.
Nuttall R.H.D. and Weil J.A. (1981a) The magnetic properties of the oxygen- Richter D.K. (1971) Fazies- und Diagenesehinweise durch Einschlüsse in
hole aluminum centers in crystalline SiO2. I. [AlO4]0. Canadian Journal of authigenen Quarzen. Neues Jahrbuch Geologie Paläonthologie,
Physics, 59, 1886–1892. Monatshefte, 10, 604‒622.

https://doi.org/10.1180/mgm.2021.72 Published online by Cambridge University Press

 Mineralogical Magazine 663

Rink W.J., Rendell H., Marseglia E.A., Luff B.J. and Townsend P.D. (1993) Soong R. and Blattner P. (1986) Biterminal authigenic 18O-enriched quartz in
Thermoluminescence spectra of igneous quartz and hydrothermal vein a subbituminous coal seam, Charleston, New Zealand. New Zealand Journal
quartz. Physics and Chemistry of Minerals, 20, 353–361. of Geology and Geophysics, 29, 141‒145.
Rinneberg H. and Weil J.A. (1972) EPR Studies of Ti3+-H+ centers in Stalder R. (2021) OH point defects in quartz – a review. European Journal of
X-irradiated alpha-quartz. Journal of Chemical Physics, 56, 2019–2028. Mineralogy, 33, 145–163.
Rossman G.R. (1994) Colored varieties of the silica minerals. Pp. 433–467 in: Stalder R., Potrafke A., Billström K., Skogby H., Meinhold G., Gögele C. and
Silica: Physical Behavior, Geochemistry, and Materials Applications Berberich T. (2017) OH defects in quartz as monitor for igneous, meta-
(P.J. Heaney, C.T. Prewitt, and G.V. Gibbs, editors). Reviews in morphic, and sedimentary processes. American Mineralogist, 102, 1832–
Mineralogy, Vol. 29. Mineralogical Society of America, Washington DC. 1842.
Rossman G.R., Weis D. and Wasserburg G.J. (1987) Rb, Sr and Sm concentra- Stalder R., von Eynatten H., Costamoling J., Potrafke A., Dunkl I. and
tions in quartz. Geochimica et Cosmochimica Acta, 51, 2325–2329. Meinhold G. (2019) OH in detrital quartz grains as tool for provenance
Rusk B. (2012) Cathodoluminescent textures and trace elements in hydrother- analysis: Case studies on various settings from Cambrian to Recent.
mal quartz. Pp. 307–330 in: Quartz: Deposits, Mineralogy and Analytics. Sedimentary Geology, 389, 121–126.
(J. Götze and R. Möckel, editors). Springer Geology, Heidelberg- Stegger P. and Lehmann G. (1989) The structures of three centers of trivalent
New York-Dordrecht-London. iron in alpha-quartz. Physics and Chemistry of Minerals, 16, 401–407.
Rusk B., Reed M.H., Dilles J.H. and Kent A.J.R. (2006) Intensity of quartz cath- Stenina N.G. (2004) Water-related defects in quartz. Bulletin of Geosciences,
odoluminescence and trace-element content in quartz from the porphyry 79, 251–268.
copper deposit at Butte, Montana. American Mineralogist, 91, 1300–1312. Stevens-Kalceff M.A. (2009) Cathodoluminescence microcharacterization of
Rusk B., Lowers H.A. and Reed M.H. (2008) Trace elements in hydrothermal point defects in α-quartz. Mineralogical Magazine, 73, 585–606.
quartz: Relationships to cathodoluminescent textures and insights into vein Stevens-Kalceff M.A. and Phillips M.R. (1995) Cathodoluminescence micro-
formation. Geology, 36, 547–550. characterization of the defect structure of quartz. Physical Reviews B, 52,
Rusk B., Koenig A. and Lowers H. (2011) Visualizing trace element distribu- 3122–3134.
tion in quartz using cathodoluminescence, electron microprobe, and laser Stevens-Kalceff M.A., Phillips M.R., Moon A.R. and Kalceff W. (2000)
ablation-inductively coupled plasma-mass spectrometry. American Cathodoluminescence microcharacterization of silicon dioxide polymorphs.
Mineralogist, 96, 703–708. Pp. 193–224 in: Cathodoluminescence in Geosciences (M. Pagel, V. Barbin,
Scala C.M. and Hutton D.R. (1976) Site assignement of Fe3+ in alpha-quartz. P. Blanc, and D. Ohnenstetter, editors). Springer, Berlin Heidelberg
Physics status solidi b, 73, K115–K117. New York Tokyo.
Schofield P.F., Henderson C.M.B., Cressey G. and Van der Laan G. (1995) 2p Tollan P., Ellis B., Troch J. and Neukampf J. (2019) Assessing magmatic vola-
X-ray absorption spectroscopy in the earth sciences. Journal of Synchrotron tile equilibria through FTIR spectroscopy of unexposed melt inclusions and
Radiation, 2, 93–98. their host quartz: a new technique and application to the Mesa Falls Tuff,
Scholz R., Chaves M.L.S.C., Krambrock K., Pinheiro M.V.B., Barreto S.B. and Yellowstone. Contributions to Mineralogy and Petrology, 174, 24.
De Menezes M.G. (2012) Brazilian quartz deposits with special emphasis on Toyoda S. (2011) The E′ 1 center in natural quartz: its formation and applica-
gemstone quartz and its color treatment. Pp. 139–159 in: Quartz: Deposits, tions to dating and provenance researches. Geochronometria, 38, 242–248.
Mineralogy and Analytics. (J. Götze and R. Möckel, editors). Springer Toyoda S. (2016) ESR signals in quartz: Applications to provenance research –
Geology, Heidelberg-New York-Dordrecht-London. A review. Quaternary International, 397, 258–266.
Schrön, W., Baumann L. and Rank K. (1982) Zur Charakterisierung von Van den Kerkhof A.M., Kronz A., Simon K. and Scherer T. (2004)
Quarzgenerationen in den postmagmatogenen Erzformationen des Fluid-controlled quartz recovery in granulite as revealed by cathodolumin-
Erzgebirges. Zeitschrift für Geologische Wissenschaften, 10, 1499–1521. escence and trace element analysis (Bamble sector, Norway). Contributions
Schrön W., Schmädicke E., Thomas R. and Schmidt W. (1988) Geochemische to Mineralogy and Petrology, 146, 637–652.
Untersuchungen an Pegmatitquarzen. Zeitschrift für Geologische Walenczak Z. (1969) Geochemistry of minor elements dispersed in quartz
Wissenschaften, 16, 229–244. (Ge, Al, Ga, Fe, Ti, Li and Be). Archivum Mineralogizne, 28, 189–335 [in
Seifert W., Rhede D., Thomas R., Förster H.-J., Lucassen F., Dulski P. and Polish].
Wirth R. (2011) On the origin of igneous blue quartz: inferences from a Walker G. (1985) Mineralogical applications of luminescence techniques. Pp.
multi-analytical study of submicron mineral inclusions. Mineralogical 103–140 in: Chemical Bonding and Spectroscopy in Mineral Chemistry
Magazine, 75, 2519–2534. (F.J. Berry and D.J. Vaughan, editors). Chapman and Hall, London, Great
Siegel G.H. and Marrone M.J. (1981) Photoluminescence in as-drawn and irra- Britain.
diated silica optical fibers: An assessment of the role of nonbridging oxygen Walsby C.J., Less N.S., Claridge R.F.C. and Weil J.A. (2003) The magnetic
defect centres. Journal of Non-Crystalline Solids, 45, 235–247. properties of oxygen-hole aluminum centers in crystalline SiO2. VI. A stable
Sittner J. (2019) Untersuchungen zur Spurenelementgeochemie von AlO4/Li centre. Canadian Journal of Physics, 81, 583–598.
Pegmatitquarzen aus der Region Tørdal, Norwegen mittels LA-ICP-MS, Wang D., Liu J., Carranza E.J.M., Zhai D., Wang Y., Zhen S., Wang J., Wang J.,
SIMS und Kathodolumineszenz. Master thesis, TU Bergakademie Freiberg, Liu Z. and Zhang F. (2019) Formation and evolution of snowball
Germany. quartz phenocrysts in the Dongping porphyritic granite, Hebei
Sittner J. and Götze J. (2018) Cathodoluminescence (CL) characteristics of province, China: Insights from fluid inclusions, cathodoluminescence,
quartz from different metamorphic rocks within the Kaoko belt trace elements, and crystal size distribution study. Lithos, 340–341,
(Namibia). Minerals, 8, 190. 239–254.
SivaRamaiah G. and Pan Y. (2012) Thermodynamic properties and magnetic Wark D.A. and Watson E.B. (2006) TitaniQ: a titanium-in-quartz geotherm-
susceptibility of surface Fe3+ species on quartz: Effects of gamma ray irradi- ometer. Contributions to Mineralogy and Petrology, 152, 743–754.
ation and implications for aerosol-radiation interactions. Physics and Watt G.R., Wright P., Galloway S. and McLean C. (1997)
Chemistry of Minerals, 39, 515–523. Cathodoluminescence and trace element zoning in quartz phenocrysts
SivaRamaiah G., Lin J. and Pan Y. (2011) Electron paramagnetic resonance and xenocrysts. Geochimica et Cosmochimica Acta, 61, 4337–4348.
spectroscopy of Fe3+ ions in amethyst: Thermodynamic potentials and mag- Weil J.A. (1971) Germanium-hydrogen-lithium-center in quartz. Journal of
netic susceptibility. Physics and Chemistry of Minerals, 38, 159–167. Chemical Physics, 55, 4685–4698.
Skuja L. (1998) Optically active oxygen-deficiency-related centers in amorph- Weil J.A. (1984) A review of electron spin spectroscopy and its application to
ous silicon dioxid. Journal of Non-Crystalline Solids, 239, 16–48. the study of paramagnetic defects in crystalline quartz. Physics and
Smith G., Vance E.R., Hasan Z., Edgar A. and Runciman W.A. (1978) A Chemistry of Minerals, 10, 149–165.
charge transfer mechanism for the colour of rose quartz. Physica status sol- Weil J.A. (1993) A review of the EPR spectroscopy of the point defects in
idi a, 46, K135–K140. α-quartz: The decade 1982–1992. Pp. 131–144 in: Physics and Chemistry

https://doi.org/10.1180/mgm.2021.72 Published online by Cambridge University Press

 664 Jens Götze et al.

of SiO2 and the Si-SiO Interface 2 (C.R. Helms and B.E. Deal, editors). Wright P.M., Weil J.A., Buch T. and Anderson J.H. (1963) Titanium colour
Plenum Press, New York, USA. centers in rose quartz. Nature, 197, 246–248.
Weil J.A. (1994) EPR of iron centres in silicon dioxide. Applied Magnetic Yang X.H. and McKeever S.W.S. (1990) Point defects and predose effect in
Resonance, 6, 1–16. quartz. Radiation Protection Dosimetry, 33, 27–30.
Wertich V., Leichmann J., Dosbaba M. and Götze J. (2018) Multi-stage evolu- Yang L., Mashkovtsev R., Botis S. and Pan Y. (2007) Multi-spectroscopic study
tion of gold-bearing hydrothermal quartz veins at the Mokrsko gold deposit of green quartzite (Guizhou Jade) from the Qinglong antimony deposit,
(Czech Republic) based on cathodoluminescence, spectroscopic, and trace Guizhou Province, China. Journal of China University of Geosciences, 18,
elements analyses. Minerals, 8, 335. 383–386.
Wood S.A. (1990) The aqueous geochemistry of the rare-earth elements Zolensky M.E., Sylvester P.J. and Paces J.B. (1988) Origin and significance of
and yttrium. 2. Theoretical predictions of speciation in hydrothermal solutions blue coloration in quartz from Llano rhyolite (llanite), north-central Llano
to 350 °C at saturation water vapor pressure. Chemical Geology, 88, 99–125. county, Texas. American Mineralogist, 73, 313–332.

https://doi.org/10.1180/mgm.2021.72 Published online by Cambridge University Press