Phys Chem Minerals (2015) 42:5362

DOI 10.1007/s00269-014-0699-4

ORIGINAL PAPER

OHpoint defects inquartz inB andLibearing systems andtheir

application topegmatites
M.A.Baron R.Stalder J.Konzett
C.A.Hauzenberger

Received: 8 May 2014 / Accepted: 22 July 2014 / Published online: 22 August 2014
Springer-Verlag Berlin Heidelberg 2014

Abstract OH incorporation in quartz in Al-, B- and Libearing systems (granitic systems containing tourmaline or
spodumene) was studied experimentally in order to investigate the effect of pressure, temperature and chemical
impurities on the generation of OH-defects. High-pressure
experiments were carried out at pressures between 5 and
25kbar and temperatures between 800 and 900C, and
OH-contents in quartz were calculated from IR absorption
spectra measured on oriented quartz crystals. IR absorption features were assigned to impurity substitutions,
such as AlOH (3,420, 3,379 and 3,315cm1) and BOH
(3,595cm1), LiOH (3,483cm1), and hydrogarnet substitution (4H)Si defects (3,583cm1). Results indicate a
negative correlation of incorporated Al-specific OH-defect
content versus pressure (630130wtppm H2O at 5kbar
to 1026wtppm H2O at 25kbar), but no clear correlation of B-specific OH-defects with pressure. In runs initially containing spodumene, virtually OH-free quartzes
were observed at pressures 10kbar, where impurity cations compensate each other forming an anhydrous eucryptite-defect component. In contrast, at 5kbar, both Li- ad
Al-specific OH-defects are observed (corresponding to
47075wtppm H2O). Results from this study may therefore be used to monitor formation conditions of quartz in
M.A.Baron
Centre forEarth Evolution andDynamics (CEED), University
ofOslo, P.O. Box 1048, Blindern, 0316Oslo, Norway
M.A.Baron R.Stalder(*) J.Konzett
Institut fr Mineralogie und Petrographie, Universitt Innsbruck,
Innrain 52, 6020Innsbruck, Austria
e-mail: roland.stalder@uibk.ac.at
C.A.Hauzenberger
Institut fr Erdwissenschaften, Universitt Graz,
Universittsplatz 2, 8010Graz, Austria

terms of pressure and trace metal saturation of the crystallizing petrological system. IR spectra obtained from natural
quartz grains from a tourmaline-bearing pegmatite exhibit
B- and Al-related OH-bands. The B-related OH-band is
also exhibited in quartz from a tourmaline+spodumenebearing pegmatite. Li- and Al-related OH-bands, however,
are subordinate or not observed at all in the spodumenebearing system, which suggests that OH-vibrations do not
reflect absolute Li-contents in quartz due to efficient coupled substitution involving Al. Data from experimental runs
and natural specimens indicate that the B-related OH-band
can be used as a rough proxy for B-contents in quartz, confirming the previously postulated charge balance equation
[H+]=[B3+]+[Al3+][Li+][K+][P5+].
Keywords Quartz OH-defects IR spectroscopy
Granite Pegmatite

Introduction
Quartz is one of the most important nominally anhydrous
minerals of the Earths crust and occurs in many different
geodynamic environments both as a primary phase in igneous and metamorphic rocks or as important constituent of
sedimentary rocks. It has been known since long that it is
able to incorporate traces of hydrogen as OH-point defects
(Bambauer 1961; Kats 1962). Moreover, the structurally
bound hydrogen commonly acts as a charge compensator
for trace metal ions, such as Al3+, Fe3+ and B3+ (Bambauer 1961; Kats 1962; Aines and Rossman 1984; Mller
and Koch-Mller 2009). Li+, Na+ and P5+commonly
incorporated in combination with Al3+may also charge
balance the incorporation of OH to a small extent. The
occurrence of hydrogen affects thermodynamic properties

13


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Phys Chem Minerals (2015) 42:5362

of quartz and can dramatically change physical behaviour

(Griggs and Blacic 1965) and even small amounts of OH
might be a key to understand dynamical and chemical
processes.
Due to its ubiquitous presence in nearly all types of
crustal rocks, quartz has a high potential to be used as a
tracer for formation conditions. A large proportion of
crustal quartz crystallizes originally in granitic intrusions,
and particularly quartz from water-rich late-stage igneous
environments may play a key role in our understanding of
incorporation mechanisms of light elements such H, B, and
Li, which are enriched in late-stage igneous systems.
The aim of this study was to understand the effects of
pressure and temperature on OH-point defect generation in
quartz in B- and Li-bearing granitic systems, representative
of the upper continental crust using high-pressure experiments combined with the evidence from natural granitic
rocks containing B- and Li-saturating phases.

Methodology
Experimental techniques
Quartz crystals were grown in two systems: B-bearing:
granite-tourmaline water system (SM1) and Li-bearing:
granite-spodumene water system (SM2). All starting mixtures contained synthetic quartz (AlfaAesar 99.995%
purity), synthetic simplified muscovite-granite powder
(74.66wt% SiO2, 15.55wt% Al2O3, 4.29wt% Na2O,
3.08wt% K2O, 0.42wt% FeO, 0.42wt% CaO, for more
details see Huang and Wyllie 1973) and distilled water. The

SM1 system was doped with natural schorl-rich tourmaline

(derived from the Passeier Valley, South Tyrol, Italy). The
Li-bearing phase in the SM2 system is a natural gem-quality spodumene (kunzite) from Pakistan. Modal compositions and experimental run conditions (pressure, temperature and duration) are listed in Table1.
All syntheses were performed in an end-loaded piston
cylinder apparatus at the University of Innsbruck. Mixtures were sealed in a Pt capsule with a 4.0mm diameter
and inserted in a BN sleeve, which in turn was inserted
in NaCl or NaClPyrex assemblies. The majority of the
experimental runs were performed by heating to 1,050C,
keeping this temperature for 1h, cooling down to 900C
with a cooling rate of 3C/min, and quenching after 72h
by turning off the power. Some runs were also performed
by directly heating to the final temperature. Details are
listed in Table1. Temperatures were measured using a NiCrNi thermocouple and computer-controlled through the
entire run duration. All run products consisted of quartz
crystals, amorphous silicate quench material and liquid
water. Grain sizes of the quartz crystals were up to 200m
in some runs, but sometimes below 100m. From each
experiment, the largest single quartz crystals were handpicked, mounted in thermoplastic resin and oriented parallel to the c-axis with a polarising microscope. Successfully
oriented crystals revealed a birefringence of =0.009 in
orthoscopic illumination and flash figure in conoscopic
illumination. Crystals were manually ground and polished
on both sides, and the resin was removed by dissolution in
acetone. The thickness of each crystal was measured with
a mechanical Mitutoyo micrometer with an accuracy of
2m.

Table1Run conditions and starting materials

Run #

Assembly
( mm)

Capsule
( mm)

Quartz (mg)

Granite (mg)

Tourmaline
(mg)

E2
E2B

NaCl 12.7
NaCl 12.7

Pt 4.0
Pt 4.0

19.35
21.38

19.40
21.38

E3
E4
E5
E6
E8
E9
E10
E11
E12
E13

NaCl 12.7
NaCl 12.7
NaCl 12.7
NaClPyrex 22
NaCl 12.7
NaCl 12.7
NaCl 12.7
NaCl 12.7
NaCl 12.7
NaCl 12.7

Pt 4.0
Pt 4.0
Pt 4.0
Pt 4.0
Pt 4.0
Pt 4.0
Pt 4.0
Pt 4.0
Pt 4.0
Pt 4.0

19.04
19.35
19.26
20.61
18.59
19.13
22.72
24.85
23.96
23.66

19.08
19.40
19.31
20.66
18.63
19.17
22.72
24.85
23.96
23.66

E15

NaClPyrex 22

Pt 4.0

23.96

23.96

Temperature with ramp

13

Spodumene
(mg)

Water (mg)

P (kbar)

4.35
2.25

5.6
4.3

15
15

900
900a

4.28
4.35
4.33
4.63
4.18
4.30
1.37
2.37
3.10
3.81

6.0
5.1
6.0
5.1
5.5
5.1
5.1
5.0
4.8
4.6

25
10
20
5
15
15
15
15
15
10

900a
900a
900a
900a
800a
900
900
900a
900a
900a

81
81
81
81
81
86
72
72
81
81
81

4.50

4.5

900

72

T (C)

Run time (h)

81

Phys Chem Minerals (2015) 42:5362

BOH

55

AlOH
5

o
e

Absorbance/mm

o-e
1

o-e (B-corr.)

3600

3400

3200

0
3000

Wavenumber [cm-1]
Fig.1Polarised IR spectra of one particular quartz grain crystallised from the B-bearing starting material. o: E||no, e: E||ne, o e:
E||noE||ne, oe B-corr: E||noE||ne with boron correction (see
text)

Analytical methods andcalculation ofwater content

Mid-infrared absorption spectra were recorded using
Bruker Vertex 70 FTIR spectrometer, which was continuously flushed with dried air to minimise water vapour
background, coupled to a Hyperion 3000 microscope
using a liquid nitrogen-cooled MCT-D316-025 detector,
a globar light source, a KBr beamsplitter and a wire-grid
polariser. Depending on the size of the prepared crystal section, 32300 scans between 550 and 7,500cm1
were recorded at room temperature on an area of
100 100m2 to 3030m2 with a spectral resolution of 2cm1. In order to eliminate the molecular water
trapped as fluid micro-inclusions or in quenched hydrous
melt inclusions, two measurements, parallel to no and ne,
on the same spot were performed on each specimen, and
the ne-component was subtracted from the no-component
of the OH absorption pattern according to the procedure
described by Stalder and Konzett (2012). By doing so,
the isotropic component is deleted (Fig.1), and in the
worst case, the derived water content is up to 20% too
low, as the orientation of the OH dipole may slightly
deviate the direction of no. In contrast to the Al-related
OH-defect, the B-related OH-defect exhibits a significant component for E||ne. Therefore, the respective range

(3,5853,605cm1) in the IR spectrum was corrected (in

the following referred to as boron correction). In particular, the total absorbance in the spectral range 3,585
3,605cm1 was calculated by adding 1.5 times the E||ne
component to the E||no E||ne difference, resulting in
E||no +0.5 E||ne for this region [o e (B-corrected)
in Fig.1]. For calculating the water content, the boroncorrected spectrum was multiplied by two, so that for the
BOH region, the components 2o+e were considered as
total absorbance (as physically correct for trigonal crystals, Rossman 2006; Stalder and Neuser 2013), and in the
remaining part of the spectrum, the total absorbance was
calculated as 2(o e) =2o 2e (as necessary for the
fluid inclusion correction). The subtracted and corrected
spectra were further used for the characterisation of the
OH-point defects, and the water content was calculated
according to the calibration of Libowitzky and Rossman
(1997).
Trace element analysis
Trace element concentration in quartz grains was analysed
with a LA-ICP-MS system (Laser ablation unit: ESI NWR
193; ICP-MS: Agilent 7500ce) at the Central Lab for
Water, Minerals and Rocks, NAWI Graz, Karl-FranzensUniversity of Graz and Graz University of Technology).
The material was ablated by using an ArF excimer laser
(193nm) pulsed at 9Hz, 50m spot size corresponding
to a fluence of ~6.8Jcm2 at the sample surface. Helium
5.0 was used as carrier gas at a flow rate of 0.7l/min. For
each analysis, a 30s gas blank was obtained for background correction, followed by 60s of active laser and a
washout time of 45s. The standard glass NIST612 was
used for standardisation and drift correction, while standards NIST614 and SL-1 (G-Probe proficiency programme,
www.geoanalyst.org) were analysed as unknowns to monitor the accuracy of the measurements. Both standards
could be reproduced within 10% of the recommended
values. Data reduction was done using the software Glitter
with silicon as internal standard. For NIST612, the concentration values reported by Jochum etal. (2011) were
used.
Electron microprobe
Samples from experimental runs that were analysed by
LA-ICP-MS were additionally inspected by electron microprobe analysis (EMPA). Microprobe analyses were performed with a JEOL JXA-8100 superprobe using 15kV
acceleration voltage and 20 nA beam current. Quartz crystals were measured 100s on peaks and 50s on backgrounds
of the Al-K line; standards used are synthetic SiO2 for Si
and synthetic Al2O3 for Al.

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Phys Chem Minerals (2015) 42:5362

BOH

AlOH

LiOH

AlOH

5
4.5

4
6

E6 (5 kbar)
E4 (10 kbar)
E2/E9 (15 kbar)
E8 (15 kbar)

4
3

3
E15 (5 kbar)

E2B (15 kbar)

E5 (20 kbar)

E13 (10 kbar)

E12 (15 kbar)

1.5

E11 (15 kbar)

E10 (15 kbar)

2.5

Absorbance/mm

Absorbance/mm

3.5

0.5

E3 (25 kbar)
3700

3500

3300

3100

0
2900

Wavenumber [cm -1]

3700

3500

3300

3100

0
2900

Wavenumber [cm -1]

Fig.2IR spectra of quartz synthesised from the tourmaline-bearing

starting material shown as E||noE||ne after boron correction and
normalisation to 1mm thickness). Each spectrum represents the average of several crystals (see Table2). Spectra are offset for clarity

Fig.3IR spectra of quartz synthesised from the spodumene-bearing

system shown as E||noE||ne (normalised to 1mm thickness). Each
spectrum represents the average of several crystals (see Table2).
Spectra are offset for clarity

Results

the magnitude of B-specific OH-defects, suggesting that

the level of doped tourmaline was sufficient for saturation
with tourmaline at run conditions.
Another information revealed from IR spectra is derived
from the region around 1,300cm1, where BOH-bending
modes and BO-stretching modes (Li etal. 1995) occur. In
case of quartz, the absorption edge at 1,280cm1 (B-free
quartz) shifts to 1,400cm1 (quartz synthesised in a B2O3rich melt, unpublished data), and spectra from B-bearing
quartz crystals from this study show a slight shift towards
1,300cm1, indicating the presence of B. However, the
band is rather broad and interferes with other modes and
the attempt to gain quantitative information was not
successful.

Bbearing system
All IR spectra of synthesised quartz crystals in the
granite-tourmaline water system exhibit (1) a band triplet at 3,430, 3,379 and 3,315cm1 (Fig.2), assigned
to AlOH defects and caused by coupled substitutions
Si4+ =Al3+ +H+ (Kats 1962; Bambauer 1963), that is
most strongly evolved at low pressures, and (2) a sharp
absorption band at 3,595cm1, which is interpreted as
a B-related OH-defect (Mller and Koch-Mller 2009);
it does not reveal a clear systematic trend, but tends
to show the highest absorbance at intermediate pressures (15kbar). In runs carried out at the lowest pressure (5kbar), a weak absorption band at 3,475cm1 is
observed, most likely associated with LiOH-interstitials
(Bambauer 1963; Aines and Rossman 1984; see more
below). Another absorption band at 3,583cm1 is very
weak at low pressures and most strongly exhibited in runs
at the highest pressure (25kbar), in accord to Stalder and
Konzett (2012). This band is related to hydrogarnet (4H)Si
substitution, typically for synthetic quartzes (Chakraborty
and Lehmann 1976; Paterson 1986; Rovetta 1989). The
amount of tourmaline in the starting material (runs E2
and E2B, Table1) does not have a significant effect on

13

Libearing system
Quartz crystals formed in the spodumene-bearing system at
10kbar are almost free from OH-related defects (Fig.3).
A very weak absorption band at 3,585cm1 is detectable,
most probably caused by hydrogarnet substitution (4H)Si.
In contrast, quartz crystals equilibrated at 5kbar show a
strong absorption band at 3,483cm1 that can clearly be
assigned to a Li-related OH-defect, in accord to previous studies (Bambauer 1963; Aines and Rossman 1984).
The characteristic band triplet of Al-related OH-defect

Phys Chem Minerals (2015) 42:5362

BOH

LiOH

57

AlOH

0.7
NBP04

0.6
NBP03

0.5

0.4
NBP01

0.3
NLP03

Absorbance/mm

NBP02

0.2

Fig.5BSE image from experimental run E6 showing quartz (Qz)

intergrown with water-saturated melt

NLP02

LAICPMS andelectron microprobe results

0.1
NLP01

3700

3600

3500

3400

3300

0
3200

Wavenumber [cm-1]
Fig.4IR spectra of natural quartz crystals from a tourmaline-bearing pegmatite (NBP) from Texel Group (tztal Alps, Italy) and a spodumene-bearing pegmatite (NLP) from Koralpe (Austria). All spectra
are shown as E||noE||ne after boron correction. Spectra are normalised to 1mm thickness and offset for clarity

(absorption bands at 3,430, 3,379 and 3,315cm1) consistently occurs with pronounced intensity in the 5kbar run.
Natural quartz frompegmatites
Quartz from two natural rocks was used for comparison
with the experimentally equilibrated quartz crystals:
1. Quartz from a tourmaline-bearing pegmatite from Texel
Group, tztal Alps, Italy (Melcher etal. 2010) exhibits a
very sharp absorption band at 3,597cm1 and at approximately 3,379cm1 (Fig.4), assigned as B-specific and
Al-specific OH-defects, respectively. Individual grains
also show a weak absorption band at 3,585cm1, probably due to hydrogarnet defect (4H)Si generation.
2. Quartz from a tourmaline- and spodumene-bearing pegmatite from Koralpe, Austria (Gd 1989) also exhibits
the B-specific OH-band, but surprisingly OH-bands that
can be assigned to Li- and Al-related OH-defects are
only faintly visible in one individual grain (Fig.4).

LA-ICP-MS results from experimental runs as well as from

the two natural quartz samples are listed in Table3. Results
could only be obtained from 3 experimental run products
due to small grain size and/or frequent inclusions and mixtures with melt, which formed in the course of the experiments (Fig.5). Two criteria were used to test, whether melt
inclusions contributed to the trace element inventory of the
analysed spot: (1) if the concentration of K as extremely
incompatible, element was unreasonable high and/or (2) if
the Al-content measured by LA-ICP-MS deviated by more
than 3 error from the value determined by electron microprobe, the data point was not further considered.
Quartz grains from experiment E2 (15kbar and 900C,
synthetic quartz+granite+schorl) contain ~0.5ppm Li,
~17ppm B, 482512ppm Al, 2226ppm Ti and traces of
Sn (<1ppm), and one quartz grain from experiment E11
(spodumene doped series, 15kbar and 900C) showed a low
B-content of <9ppm, Li-contents of ~611ppm, 67ppm Al,
27ppm Ti, as well as traces of Ge and Sn. The two natural
quartz samples from the Texel Group (TG), northern Italy and
Koralpe (KA), southern Austria exhibit Li values of 69ppm
(TG), 3050ppm (KA), 59ppm B (TG and KG), Al concentrations of ~50ppm (TG), 130220ppm (KA). Ti, Ge and
Sn are found in both samples in concentrations <5ppm.

Discussion
Water content asOHdefects
The water contents of quartz incorporated as OHpoint defects were calculated from the IR spectra using

13


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Phys Chem Minerals (2015) 42:5362

Table2OH-concentrations (as wt ppm water) of all measured crystals

Sample

Origin

Pressure (kbar)

T (C)

Thickness (m)

Water content (ppm)

Water as B-OH (ppm)

T (09)

L&R (97)

A (84)

T (09)

L&R (97)

E6C1

Syn.

900

62

736

733

760

14

31

E6C2

Syn.

900

48

456

461

471

11

26

E6C4

Syn.

900

84

538

564

555

15

35

E6C5

Syn.

900

92

777

770

802

14

33

E4C1

Syn.

10

900

83

359

364

371

10

22

E4C2

Syn.

10

900

74

283

295

292

10

23

E4C3

Syn.

10

900

55

260

273

268

10

22

E8C1

Syn.

15

800

66

227

239

230

17

E8C2

Syn.

15

800

65

147

162

147

10

23

E8C3

Syn.

15

800

48

173

193

172

11

24

E2C1

Syn.

15

900

110

230

262

237

18

41

E2C2

Syn.

15

900

120

170

188

175

11

25

E2C3

Syn.

15

900

97

211

236

218

13

31

E2C4

Syn.

15

900

68

213

242

220

18

42

E2BC1

Syn.

15

900

45

258

293

267

11

25

E2BC3

Syn.

15

900

68

156

164

161

E9C1

Syn.

15

900

75

185

206

190

10

23

E5C1

Syn.

20

900

59

91

111

94

10

24

E5C2

Syn.

20

900

67

163

189

168

13

31

E5C3

Syn.

20

900

65

175

202

181

13

31

E5C4

Syn.

20

900

50

73

95

75

20

E3C1

Syn.

25

900

76

72

94

75

11

26

E3C2

Syn.

25

900

70

83

107

86

12

26

E3C3

Syn.

25

900

60

79

106

81

14

31

E15C1

Syn.

900

85

359

366

370

n.d.

n.d.

E15C3

Syn.

900

71

487

508

503

n.d.

n.d.

E15C4

Syn.

900

70

526

533

542

n.d.

n.d.

E13C1

Syn.

10

900

19

n.d.

n.d.

n.d.

n.d.

n.d.

E13C2

Syn.

10

900

65

n.d.

n.d.

n.d.

n.d.

n.d.

E13C3

Syn.

10

900

53

n.d.

n.d.

n.d.

n.d.

n.d.

E10C1

Syn.

15

900

50

n.d.

n.d.

n.d.

n.d.

n.d.

E10C2

Syn.

15

900

60

n.d.

n.d.

n.d.

n.d.

n.d.

E10C3

Syn.

15

900

66

n.d.

n.d.

n.d.

n.d.

n.d.

E11C2

Syn.

15

900

100

n.d.

n.d.

n.d.

n.d.

n.d.

E11C3

Syn.

15

900

62

n.d.

n.d.

n.d.

n.d.

n.d.

E11C4

Syn.

15

900

55

n.d.

n.d.

n.d.

n.d.

n.d.

E12C1

Syn.

15

900

55

n.d.

n.d.

n.d.

n.d.

n.d.

E12C5

Syn.

15

900

52

n.d.

n.d.

n.d.

n.d.

n.d.

NBP01

Texel Group

150

NBP02

Texel Group

135

NBP03

Texel Group

70

NBP04

Texel Group

65

NLP01

Koralpe

50

n.d.

n.d.

NLP02

Koralpe

60

n.d.

n.d.

NLP03

Koralpe

107

n.d.

n.d.

T(09)=according to calibration of Thomas etal. (2009)

L&R (97)=according to calibration of Libowitzky and Rossman (1997)
A(84)=according to calibration of Aines etal. (1984)
n.d. not detected (<1ppm)

13

Phys Chem Minerals (2015) 42:5362

59
800

800

600

wt ppm water

wt ppm water (L&R97)

600

y = 1.02x

y = 1.14x

400

400

200

200

10

15

20

25

30

p (kbar)

200

400

600

800

wt ppm water (T09)

Fig.7OH-defect concentration (expressed as wt ppm water using

the calibration of Libowitzky and Rossman 1997) of quartz synthesised from the tourmaline-bearing system as a function of pressure.
Error bars correspond to 10%
50

Fig.6Comparison of the OH concentrations (as wt ppm water) from

the calibrations of Libowitzky and Rossman (1997) and Thomas etal.
(2009) of all synthetic crystal. Crystals with spectra dominated by the
BOH band (filled symbols, crystals were grown in the tourmalinebearing starting material at P15kbar) show systematic deviations
for both calibrations, whereas from all other crystals (open symbols)
comparable results are derived

40

wt ppm water as B-OH

mineral-specific (Aines etal. 1984; Thomas etal. 2009)

and general wavelength-specific (Libowitzky and Rossman 1997) calibrations (Table2). Although the differences
in results between those methods are negligible for most of
the crystals (Fig.6), we noticed that for crystals from the
B-bearing system concentrations based on the calibration
of Libowitzky and Rossman (1997) are often about 20ppm
higher than mineral-specific calibrations from Aines etal.
(1984) and Thomas etal. (2009). The explanation for this
feature is trivial, as the wavelength-specific calibration
yields higher values for spectra with absorptions in the high
wavenumber range. As long as spectra are dominated by
the Al-specific band, all calibrations yield similar results,
but for spectra dominated by high wavenumber bands, significant deviations are expected (Stalder and Konzett 2012).
In the B-bearing system, calculated OH-defect concentrations (expressed as wt ppm water) show a clear negative

45

35
30
25
20
15
10
5
0

10

15

20

25

30

p [kbar]
Fig.8Contribution of the BOH-defect to the total water content as
function of pressure

13


60

Application aspetrogenetic indicator

Impurity-induced OH-defects are strongly dependent on
the availability of the respective impurity in the system, so
extreme concentration ratios of two different impurities in
the system leads to unusual ratios of the OH-bands in the
IR spectra. Generally spoken, OH-bands in quartz can only
be used as a reliable proxy if the impurities are saturated,
i.e. controlled by a modally coexisting phase, e.g. tourmaline for B or spodumene for Li (Jacamon and Larsen 2009).
The different response of the B-specific and the Alspecific OH-defects to pressure may be applied as geobarometer, where a high ratio of B-specific to Al-specific
OH-bands points to a high-pressure origin. However,

13

800

wt ppm H2O (measured)

trend against pressure (Fig.7) with 450750ppm H2O at

5kbar to 70110ppm H2O at 25kbar. This trend is entirely
based on the behaviour of the Al-related OH-defects, since
the intensity of the B-related OH-band is not sensitive to
pressure (Fig.8).
In the Li-bearing system, the virtually OH-free quartzes
derived at 1015kbar may be explained by the coupled
incorporation of Li+ and Al3+ and the formation of a dry
defect. This interpretation is substantiated by previous
experimental studies, which suggest the stability of virgilite, a LiAlsilicate with high-quartz structure, above
the solidus in a model system for Li-pegmatites (London
1984). Within the scope of this study, it is, however, unclear
why the absence of OH-defects is only observed at higher
pressures. Quartz crystals from runs at 5kbar contained
350550ppm H2O (Table2) and exhibit both Li- and Alrelated OH-bands, indicating that Li+ and Al3+ do not combine completely with anhydrous defects.
Water concentrations determined in this study are half
an order of magnitude higher than in a previous study (Stalder and Konzett 2012). Partly, this is due to the existence
of the Li- and B-related OH-defects, but it also has to be
mentioned that the Al-related OH-defect is more intensive
than previously observed at similar PT conditions in a
modally tourmaline- and spodumene-free system. Strong
differences between the systems quartzalbitewater and
granitewater have previously been observed (Stalder and
Konzett 2012), but the responsible chemical parameter
could not be identified within the scope of this study. In
cases where a reliable determination of trace contents of
Al, Li and B was possible, the calculated defect water content based on coupled substitution [H+]=[B3+]+[Al3+]
[Li+][K+][P5+] is in pretty good agreement with
the water content determined by IR spectroscopy (Fig.9;
Table3). As already noted above, the proposed charge balance equation can only be regarded as approximation, as
Al-specific and Li-specific OH-defects may occur together
and do not totally compensate each other.

Phys Chem Minerals (2015) 42:5362

600

1:1

400

200

0
0

200

400

600

800

wt ppm H2O (calculated)

Fig.9Water contents determined by FTIR in comparison with water
contents calculated based on trace impurities according to Table3

several factors that interfere with this relation have to be

considered: (1) availability of other impurities such as
Al3+ that are involved in coupled substitution with H, (2)
water activity and (3) stability and mobility of OH-defects.
As far as (2) is concerned, reduced water activity has been
shown to affect the formation of OH-defects selectively,
where hydrogarnet substitution reacts much more sensitive than OH-defects induced by impurities (Stalder and
Konzett 2012), but the effect of water activity on the different impurity-induced OH-defects is hitherto unknown.
Probably, in this respect, the most important factor is point
(3), the thermal stability, because OH-defects generated
during magmatic (including pegmatitic and hydrothermal)
crystallisation may later be affected by metamorphic overprint, which usually leads to hydrogen loss. Hydrogen loss
is governed by distinct diffusion mechanisms, and different
types of defects are expected to exhibit individual decomposition kinetics, therefore specifically biasing the original
magmatic OH-defect inventory.
OH-bands observed in Qz crystals from the tourmaline-bearing pegmatite from Texel Group (this study) are
more similar to those observed in quartz crystals from
high-pressure (15kbar) runs, which contradict the general subordinate occurrence of hydrogarnet substitution
in the analysed crystals. The reason for the observed low
concentration of Al-specific OH-defects may be the formation of anhydrous LiAl defects. Absolute concentrations of B-specific OH-defects are one order of magnitude lower than observed in the experimental products,
suggesting a rather low water activity. Alternatively,

Phys Chem Minerals (2015) 42:5362

61

Table3Trace element contents in quartz and expected H incorporation

Origin

LA-ICP-MS
Spots

E2 (15kbar, B series)
E6 (5kbar, B series)
E11 (15kbar, Li series)
E11 (15kbar, Li series)
nat. Qz (Texel Group), grain 1
nat. Qz (Texel Group), grain 2
nat. Qz (Koralpe), grain 1
nat. Qz (Koralpe), grain 2

2
1
1
3
3
4
3
2

0.48 (0.17) 16.8 (1.8)

497 (28)
3.6 (0.2) 44.7 (0.6) 1,682 (62)
6.4 (0.5)
8.4 (1.1)
67 (4)
11.2 (0.8)
3.7 (0.4)
24 (2)
6.1 (1.4)
5.4 (0.4)
44 (3)
7.4 (1.2)
8.9 (1.6)
49 (4)
40.6 (2.4)
4.8 (0.7)
188 (12)
29.7 (2.3)
9.3 (1.8)
131 (11)

nat. Qz (Koralpe), grain 3

50.8 (3.9)

Li

11

9.0 (1.8)

27

31

Al

39

n.a.
44.4 (4.6)
n.a.
20.2 (5.9)
22.8 (4.3)
n.a.
17.7 (3.0)
n.a.

217 (18) n.a.

EMPA

wt ppm H2O

Spots Al

Calculateda Measuredb

n.d.
3
n.a.
7
4.7 (0.9) 6
n.a.
n.a.
n.d.
n.a.
n.d.

353 (49)
179
1,450 (310) 580
n.d.
2

232
632
<1

n.d.

1 error based on counting statistics in parentheses

n.d. not detected, n.a. not analysed
a

Calculated from molar proportions of substituting cations: (1/9)[H2O]=[H+]=[B3+]+[Al3+][Li+][K+][P5+]

Average values from Table2 according to calibration of Libowitzky and Rossman (1997)

Indirect tool toquantify traces ofboron

Based on the OH-content calculated from the B-specific
OH-absorption band, it should principally be possible to
quantify the concentration of the charge balancing B3+
and use the IR spectrum as indirect analytical tool to
determine the B3+-content of quartz. Such an analytical
tool could be interesting for samples where inclusions
on a micro- and nanoscale (as documented above) render a direct chemical microanalysis impossible. Samples
that were successfully analysed for B by LA-ICP-MS
exhibit indeed a general trend between the B content
and the intensity of B-specific OH-band is (Fig.10), so
the spectroscopic data may serve at least as a rough estimate of the magnitude of B in quartz. It has, however,
to be noted that impurities can also be incorporated by
other substitutions not involving hydrogen, following the
general charge balance equation [H+] +[A+] =[M3+]
(Bambauer 1961; Miyoshi etal. 2005) or [H+] +[A+
] +[P5+] =[M3+] +[B3+] (Mller and Koch-Mller
2009), with A=alkali and M=metal. Therefore, the
B-content calculated from the B-related OH-band represents a minimum value and cannot be in excess of
the true B-content incorporated as lattice defects. This
is in conflict for one data point for the IR calibration of
Libowitzky and Rossman (1997), but generally applies

80
L&R(97)
T(09)

1:1

wt ppm B (B-OH-defect)

hydrogen was lost during metamorphic overprint of the

alpine metamorphism. Similarly, the low defect water
content in quartz from the spodumene-bearing pegmatite from Koralpe, with Permian intrusion ages and later
alpine metamorphic overprint (Gd 1989), could be
explained.

60

40

20

20

40

60

80

wt ppm B (LA-ICP-MS)
Fig.10Calculated boron content associated with BOH-defects
(Table 2) plotted against B-content measured by LA-ICP-MS
(Table 3). T (09)=calibration of Thomas etal. (2009), L&R
(97)=calibration of Libowitzky and Rossman (1997)

to the B-content derived from the calibration of Thomas

etal. (2009). However, given the strong uncertainty, a
larger data set is necessary to evaluate this issue. Finally,
the rough accordance of the B-content derived from the
B-related OH-band with the direct trace element analysis
is another proof the analysed crystals reported here are
not significantly contaminated by melt inclusions.
In contrast to B, the use of the OH-absorption bands as
analytical tool to determine Li-concentrations in quartz is

13


62

far less promising, mainly due to the strong tendency of

coupling to Al3+.
Finally, as discussed above, the original OH-inventory
may be changed (by dehydration) during metamorphic
events, leaving preferentially the charge balancing cations
behind. Therefore, IR spectra are only valuable for the prediction of trace metal contents, if the sample retained its
original OH-defect content.
Acknowledgments Hannes Witting is thanked for manufacturing
the high-pressure assemblies. Ulf Hlenius and Thomas Gtte are
thanked for constructive reviews.

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