Contrib Mineral Petrol (2005)

DOI 10.1007/s00410-005-0037-4

O R I GI N A L P A P E R

Roland Stalder Æ Stephan Klemme Æ Thomas Ludwig

Henrik Skogby

Hydrogen incorporation in orthopyroxene: interaction

of different trivalent cations

Received: 12 July 2005 / Accepted: 14 September 2005

Springer-Verlag 2005

Abstract The incorporation of hydrogen into ferrosilite,

Fe-bearing enstatite and orthopyroxene containing dif-
ferent trivalent cations (Cr3+ and Al3+, Cr3+ and Fe3+)
was investigated experimentally at 25 kbar. Hydrogen
concentration was determined by FTIR-spectroscopy on
oriented crystal sections and by secondary ion mass
spectroscopy, whereas Mößbauer spectroscopy and
optical spectroscopy were used to characterise the va-
lence state of Fe in orthopyroxene. Results suggest that
hydrogen incorporation in ferrosilite is achieved by a
similar mechanism as in pure enstatite. In Cr-bearing
samples, however, hydrogen incorporation is reduced by
the presence of other trivalent cations by an increased
tendency to form Tschermaks substitutions, e.g. Si4+T +
Mg2+M1 , Al 3+
T + Cr 3+
M1 . Thus, hydrogen solubility in
natural orthopyroxenes from the Earth’s mantle, con-
taining significant amounts of Cr3+, Al3+, and Fe3+,
may be much more limited than expected from their
trivalent cation content, as a large fraction of the tri-
valent cations does not participate in H-incorporating
reactions as 2 Mg2+ 3+
M1 , MM1 + VM1 + Hi .
+
Keywords Orthopyroxene Æ Hydrogen incorporation Æ
Trivalent cation Æ High pressure Æ Spectroscopy
Communicated by J. Hoefs
R. Stalder (&)
Abteilung Angewandte und Experimentelle Mineralogie,
Geowissenschaftliches Zentrum der Universität Göttingen,
Goldschmidtstraße 1, 37077 Göttingen, Germany
E-mail: rstalde@gwdg.de
S. Klemme Æ T. Ludwig
Mineralogisches Institut der Universität Heidelberg,
Im Neuenheimer Feld 236, 69120 Heidelberg, Germany
H. Skogby
Naturhistoriska riksmuseet, Sektionen för mineralogi,
Box 50007, 10405 Stockholm, Sweden
Introduction
The knowledge of the water content of the Earth’s upper
mantle is crucial for understanding many upper mantle
processes such as mantle melting and physical properties
such as rheology (Mackwell et al. 1985; Mei and Kohl-
stedt 2000). It is now widely accepted that many nomi-
nally anhydrous minerals dissolve significant amounts of
hydrogen under upper mantle conditions (Skogby and
Rossman 1989; Bell and Rossman 1992; Ingrin and
Skogby 2000). Orthopyroxene, next to olivine the most
abundant constituent of the Earth’s upper mantle, is
able to incorporate several hundred ppm (wt) H2O
(Skogby et al. 1990; Bell and Rossman 1992; Rossman
1996; Peslier et al. 2002; Rauch and Keppler 2002;
Stalder 2004), and might therefore be a major host for
water in the Earth’s upper mantle. Water solubility in
both olivine (Bai and Kohlstedt 1992; Kohlstedt et al.
1996) and orthopyroxene (Rauch and Keppler 2002) is
strongly dependent on pressure by generating increasing
amounts of point defects in the lattice; in contrast to
olivine, orthopyroxene is able to incorporate trivalent
cations on a much larger scale, thus opening the possi-
bility for incorporation of additional water on a large
scale by other types of point defects (Rauch and Keppler
2002; Stalder and Skogby 2002; Stalder 2004), e.g.
2 Mg2+ 3+
M1 , M M1 + VM1 + Hi , where M
+ 3+
is a tri-
3+ 3+ 3+
valent cation as Al , Cr and Fe , and M1 and i are
M1-position and interstitial position in the lattice,
respectively. Actually, the position of the proton is not
very well defined; in some cases it could even be close to
M1, but usually it is rather charge balancing this va-
cancy than filling it. In any case, H is small enough to be
in the ‘‘interstitial’’ position, i.e. not associated with any
particular vacancy, but it is always located very close to
an oxygen, therefore also referred to as ( OH
)O (e.g.
Wright and Catlow 1994), meaning an (OH) on an
oxygen position.
However, the hydrogen budget of orthopyroxenes
may not just be a simple function of the total amount of
trivalent cations; for example, as demonstrated by Kle-
mme and O’Neill (2000), Cr influences the Al-incorpo-
ration in orthopyroxene, and therefore the presence of
different trivalent cations may influence the defect
chemistry of orthopyroxene significantly, which is ex-
pected to have a large impact on the extent of coupled
substitutions involving hydrogen. In this study we report
experimental results on water solubilities in ferrosilite
and enstatite single crystals doped with Fe, Fe+Cr, and
Al+Cr in order to assess the interaction of different
trivalent cations in processes producing OH-defects.
Even if it is widely accepted that hydrogen (or more
correctly protons) is incorporated by point defects in
nominally anhydrous minerals, the terms hydrogen
incorporation and water incorporation are used synony-
mously throughout this article, as oxygen is the charge
balancing anion in the crystal. However, water content
and hydrogen content (wt ppm) differ by a factor of 9.
Experimental and analytical procedure
Orthopyroxene crystals were synthesised by applying the
method described by Stalder (2002). The starting mix-
tures (corresponding to orthopyroxene + quartz in the
weight proportions of 3:1) were prepared from oxides
(99.999 wt% purity), to which different amounts of
Fe2O3, 57Fe2O3 (57Fe/Fetot = 0.96), Cr2O3 and Al2O3
were added. Approximately, 55 mg oxide mixtures and
14 mg H2O were sealed in a Pt-capsule with an outer
(inner) diameter of 4.0 (3.6) mm. For the ferrosilite
synthesis fayalite was pre-synthesised at 1,000C and
one atmosphere ðfO2 ¼ IW þ 0:5Þ: A mixture of fayalite,
quartz and water (corresponding to a 3:1:1 mixture (by
weight) of ferrosilite, quartz, and water) was sealed in a
Pt-capsule lined with a cylinder of pure iron with an
outer (inner) diameter of 3.5 (3.0) mm in order to min-
imise Fe-loss and to control the oxygen fugacity during
the run. All syntheses were conducted in half inch
talc-pyrex cells with alumina spacers in an end-loaded
piston cylinder apparatus at 25 kbar by slow cooling
(11–13/h) from 1,400C to 1,150C (1,300C to 1,050C
for ferrosilite synthesis). In synthesis runs RS084 and
RS091 higher cooling rates (36 and 40/h, respectively)
were applied, leading to the same phase assemblage
and slightly smaller crystals (i.e. £ 1 mm3). Tempera-
tures were measured by S-type thermocouples; no pres-
sure correction has been applied to the EMF of the
thermocouple. The pressure was calibrated against the
reactions anorthite + gehlenite + corundum = Ca-Al-
pyroxene (Hays 1966) and quartz–coesite (Bose and
Ganguly 1995). To account for internal friction of the
talc-pyrex assembly, 10% were added to the nominal
load; pressures are estimated to be correct within
±1 kbar.
After the run, all charges were checked for leakage. In
all successful runs, run products consisted of large
orthopyroxene crystals (approximately 1 mm3), amor-
phous quench material and water. Hematite occurred as
additional phase in runs RS064, RS072 and RS084. In
run RS054 ferrosilite was accompanied by quartz and a
greenish quench. Charge RS072 revealed a systematic
zoning resulting in two groups of differently coloured
orthopyroxene crystals; one group (listed as RS072a in
Table 1) exhibited a yellowish-brownish colour with a
significant pleochroic behaviour (absorptions were most
intense for E//c); from the second group only two crys-
tals (RS072b and RS072c) could be prepared success-
fully; they appeared greenish in unpolarised light, but
showed strong pleochroic behaviour in polarised light
(E//c: reddish, E//a,b: greenish), similar to Cr-doped
enstatites (Stalder 2004). As expected, crystals from the
first group turned out to be more Fe-rich and poorer in
Cr (Table 1). Apart from a chemically zoned rim
(approximately 100 lm wide) with increasing Fe- and
decreasing Cr-contents towards the edge of the crystal
(which also is reflected in the shape of the IR-spectra),
individual crystals from run RS072 exhibit a homoge-

Table 1 Chemical composition of the synthetic orthopyroxenes determined by electron microprobe

Doped cation SiO2 wt% MgO wt% Al2O3 wt% Cr2O3 wt% FeO* wt%

RS054 Fs 46.00 (0.16) 0.09 (0.02) 53.68 (0.40)

57
RS063 En Fe 59.21 (0.26) 39.44 (0.37) 0.98 (0.41)
57
RS064 En Fe 58.71 (0.74) 37.96 (1.59) 3.18 (2.11)
57
RS084 En Fe 57.75 (0.45) 35.03 (0.88) 7.24 (1.20)
RS088 En Al, Cr 60.04 (0.22) 39.47 (0.17) 0.17 (0.06) 0.68 (0.13)
RS067 En Al, Cr 59.28 (0.22) 39.80 (0.19) 0.17 (0.08) 0.46 (0.12)
RS065 En Al, Cr 59.09 (0.24) 39.82 (0.11) 0.18 (0.05) 0.39 (0.04)
RS085 En Al, Cr 58.94 (0.35) 38.95 (0.18) 0.75 (0.29) 1.05 (0.16)
RS053 En Al, Cr 58.72 (0.27) 39.60 (0.21) 0.63 (0.28) 0.47 (0.11)
RS091 En Al, Cr 58.89 (0.50) 38.98 (0.39) 1.50 (0.80) 0.90 (0.21)
RS087 En Al, Cr 59.19 (0.39) 39.32 (0.34) 1.30 (0.69) 0.36 (0.09)
RS072a En Fe, Cr 58.82 (0.20) 36.98 (0.22) 0.56 (0.04) 3.76 (0.08)
RS072b En Fe, Cr 59.25 (0.07) 37.72 (0.17) 0.68 (0.14) 2.56 (0.05)
RS072c En Fe, Cr 59.32 (0.25) 37.31 (0.20) 1.21 (0.12) 2.51 (0.10)

Standard deviations are given in brackets

*Total Fe
Fs Ferrosilite, En Enstatite
neous composition; as all FTIR-spectra were recorded at
the centre of each individual crystal, chemical compo-
sitions given in Table 1 represent the core compositions
of the respective crystals.
From each experimental charge several clear crystals
were handpicked and orientated in a thermoplastic resin
according to the crystallographic axes with help of their
optical properties (birefringence and angle between both
optical axes), and ground and polished on both sides.
Wafers oriented parallel (100) and wafers parallel (010)
were produced in this way. After preparation specimens
were between 30 and 360 lm thick. Polarised IR-spectra
of each sample were recorded parallel to the main
refractive indices a, b and c in transmitted light using a
Bruker IFS 88 FTIR-spectrometer coupled to a Bruker
microscope IR scope II at the University of Hannover.
Measurements were taken using a MIR globar light
source, a KBr beamsplitter and a wire-grid polariser.
For each spectrum 64 scans in the range between 400
and 6,000 cm1 were acquired with a spectral resolution
of 2 cm1. Background corrections were usually carried
out by adjusting a linear baseline at 2,500–2,600 cm1
and 3,700–4,000 cm1. Total absorption was obtained
by integration over the wavenumber range from
3,000 cm1 to 3,640 cm1. In order to get more infor-
mation about the nature of the defects, additional IR-
spectra were recorded from polished crystals of ferrosi-
lite and an iron-doped enstatite after thermal treatment
in air and/or hydrogen atmosphere at 1 bar.
As the determination of water content by FTIR-
spectroscopy is an indirect method and recent studies
(e.g. Bell et al. 2003) have shown that independent
methods for water analysis in nominally anhydrous
phases deviate significantly from FTIR-results, some
selected crystals previously analysed by FTIR (Stalder
2004) were analysed by secondary ion mass spectrome-
try (SIMS) at the University of Heidelberg. Hydrogen
analyses were performed on a Cameca ims 3f at low-
mass resolution (m/D m=400), at an offset of 75 eV and
with the energy window set to 40 eV. The primary beam
was formed by 16O-ions at a net energy of 14.5 keV and
with beam currents ranging from 5 nA to 50 nA. In situ
contamination with water was minimised with a liquid
nitrogen cooling finger in the sample chamber. The H-
background was further minimised using the method
described in Ludwig et al. (in preparation) and is esti-
mated to be <10 ppm (wt) H. Quantification was done
using relative ion yields (reference isotope 30Si). Three
different tourmalines were used as standard (Dyar et al.
2001). The range of relative ion yields for these tour-
malines (0.08–0.12) suggests an accuracy of approxi-
mately ±20% for the SIMS analyses of H.
The valence state and structural distribution of Fe in
samples RS063, RS064, RS084 (doped with 57Fe2O3)
and RS054 (ferrosilite) was determined by Mößbauer
spectroscopy at 298 K and 77 K; due to the high
enrichment in 57Fe or the high concentration in iron
1 mg of each sample turned out to be sufficient material
for a high-quality spectrum. Mößbauer spectra were
measured both at room and liquid-nitrogen tempera-
tures using a conventional spectrometer system operated
in constant acceleration mode, with a 57 Co source in Rh
matrix. Absorbers were prepared by pressing 1–5 mg
finely ground sample material mixed with an acrylic
resin (transoptic powder) to self-supporting 12 mm
discs. To minimise texture effects, the absorbers were
held at an angle of 54.7 to the incident beam. Spectra
collected over 1,024 channels were velocity-calibrated
against a-Fe, folded, and further reduced to 256 chan-
nels before fitting using a least-squares fitting program
(Jernberg and Sundqvist 1983) assuming Lorentzian
peak shapes. All spectra were fitted with two doublets
assigned to Fe2+ in the M1 and M2 positions; spectra
of the Fe3+-containing samples were fitted with two
additional doublets assigned to Fe3+ in octahedral and
tetrahedral coordination. No constraints of spectral
parameters were applied during the fitting procedure.
To estimate the maximum ferric iron content, in
addition to Mößbauer spectroscopy a thin wafer of
one crystal from run RS054 (ferrosilite) and RS063
(57Fe-doped enstatite) were investigated by optical
absorption spectroscopy at the Swedish Museum of
Natural History in Stockholm. Polarised spectra were
measured in the 5,000–27,000 cm1 wavenumber range
with a Zeiss MPM800 single-beam spectrometer, using
Zeiss Ultrafluar10x lenses as objective and condenser.
For the UV/VIS spectral range a 75-W Xenon arc lamp
was used as source and a photo multiplier as detector,
whereas a 100-W halogen lamp and a photoconductive
PbS cell detector was used for the NIR range (5,000–
12,500 cm1). Measurements were performed with the
beam collimated with a circular aperture (100 lm in
diameter) on the sample, and spectral resolutions of
2.5 nm and 10 nm for the UV/VIS and NIR ranges,
respectively.
Out of each charge several crystals were selected for
microprobe analysis. In case of charge RS072, the same
crystals as prepared for FTIR-analyses were used.
Crystals were embedded in epoxy and were analysed
with a JEOL JXA 8900 RL electron microprobe using
an accelerating voltage of 15 kV and a sample current of
15 nA. For Fe, Cr and Al the analysis time lasted 30 s
on the peak and 15 s on the background, for Si and Mg
the analysis time lasted 15 s on the peak and 5 s on the
background. The detection limits for Fe, Cr and Al were
below 150 ppm, no elements other than Mg, Si, Fe, Cr,
Al and O were detected. Usually, 10 points were mea-
sured on each crystal. Analytical results are given in
Table 1.
Results
All IR-spectra show several absorption bands in the
spectral region between 3,000 and 3,600 cm1 (Fig. 1),
which have previously been assigned to OH-stretching
modes; H2O-contents were calculated by adding the
averaged a-, b- and c-absorbances measured by FTIR
Fig. 1 a FTIR-spectra (E//c) of ferrosilite and Fe-bearing enstatite;
the spectrum for pure enstatite is from Stalder (2004), and
En(+Fe)hyd is taken from a Fe-bearing enstatite (2 wt% FeO,
total iron expressed as FeO) from Stalder (2004) which was
thermally treated in H2-atmosphere; b FTIR-spectra (E//c) of
Cr+Al-doped enstatites; the spectrum labelled Al(Al+Cr) = 0
(Table 2) on 2–5 individual crystals from one charge
using the calibration of Libowitzky and Rossman
(1997). Generally, the c-component contributed more
than 60% to the absolute absorbance. H2O-contents
measured by SIMS are given in Table 3.
In addition to the observed OH-absorption bands
at 3,070 and 3,361 cm1 in pure enstatite, Fe-bearing
and Al(Al+Cr) = 1 are taken from Stalder (2004) from synthetic
enstatites containing 0.5 wt% Cr2O3 or 1.2 wt% Al2O3, respec-
tively; c FTIR-spectra (E//c) of Fe+Cr-doped enstatites; the
spectrum labelled Fe3+/Cr = 0 and Cr/Fe3+ = 0 are taken from
Stalder (2004) from synthetic enstatites containing 0.7 wt% Cr2O3
or 2.0 wt% FeO (total iron as FeO), respectively
enstatite crystals from RS063, RS064 and RS084 exhibit
two new bands at 3,328 cm1 and 3,461 cm1, their
intensity being dependent on the Fe3+-content of the
sample. After thermal treatment in hydrogen atmo-
sphere, the latter two peaks disappeared ((En(+Fe)hyd),
Fig. 1a); the remaining spectrum shows nearly identical
OH-band positions as pure enstatite, suggesting a
Table 2 Hydrogen incorporation in doped orthopyroxenes

FTIR Haexcess Al ppm Cr ppm Fe ppm Fe3+/Fe M3+ Al/(Cr+Al) Hexcess/M3+

H2O ppm ppm (wt) (wt) (wt) (wt) (at)c (at)c corr.b (at)c
(wt)

RS054 336 8 417,500 <0.002 <15 >0.5

RS063 300 4 7650 <0.01 <1.4 >2.8
RS064 454 21 24,830 0.09 40 0.74
RS084 580 35 56,530 0.10 101 0.49
RS088 787 58 900 4,653 123 0.27 0.86
RS067 533 30 900 3,148 94 0.36 0.63
RS065 482 24 953 2,668 87 0.41 0.59
RS085 955 77 3,971 7,184 285 0.52 0.66
RS053 622 40 3,335 3,216 185 0.67 0.68
RS091 825 62 7,941 6,158 413 0.71 0.52
RS087 566 34 6,882 2,463 302 0.84 0.52
RS072a 1,323* 103 3,830 29,240 n.d.d 99 1.04
RS072b 1305* 101 4,650 19,910 n.d.d 107 0.95
RS072c 1,746* 150 8280 19,520 n.d.d 176 0.85
a
Compared to pure enstatite (Stalder 2004), containing 264 wt ppm H2O
b
H contents determined by FTIR are corrected by a factor of 1.4; only 1/6 of Al participates in H incorporation (see text)
c
=ppm (wt)/molar mass
d
Fe3+ contributing to H incorporation was estimated to be similar to RS084
*
H-content determined by SIMS

complete reduction of the ferric iron to the ferrous state. (Fig. 3), and based on the absorption intensity and
In comparison, the IR spectrum of pure ferrosilite shows Fe3+-content of the (Fe3+, Al)-doped sample (Steffen
one major absorption band, which is broader than for et al. 1988) we infer that Fe3+/Fetot < 0.002 for sample
pure enstatite and shifted to slightly lower wavenum- RS054. Optical spectroscopy was not useful for Fe3+-
bers. Thermal treatment of ferrosilite in both air and detection in case of the Fe-doped enstatites, as the
hydrogen resulted in nearly identical spectra, exhibiting intensity of the charge transfer band is dependent on the
a narrower main absorption band (Fig. 1a) and another product of the Fe2+- and the Fe3+-concentration
very small absorption band close to 3,450 cm1. (Steffen et al. 1988).
Interestingly, infrared spectra from enstatites con- H-concentrations determined on crystals from run
taining both Cr and Al only exhibit OH-bands diag- RS072 are listed in Table 2. Results from all SIMS-
nostic for Cr-bearing enstatites (i.e. at 3,449 cm1, measurements suggest 40–60% higher water concentra-
Stalder 2004), if the Al/(Al+Cr) atomic ratio was tions than FTIR (Fig. 4). This finding is in accord with
smaller than about 0.6; on the other hand OH-bands the results of experimental water incorporation in Cr-
typical for Al-bearing enstatite (i.e. between 3,500 and doped enstatites (Stalder 2004), where the water con-
3,600 cm1) are visible in all studied enstatites contain- centration determined by FTIR using the calibration of
ing Al (Fig. 1b). For crystals containing both Cr Libowitzky and Rossman (1997) or Bell et al. (1995) was
and Fe3+ the positions of OH-bands inherent from 40% lower than expected for the most probable substi-
Cr-defects or Fe3+-defects are not easy to distinguish, as tution mechanism Cr3+ + H+ = 2 Mg2+. Figure 5a
the presence of Fe3+ and Cr in enstatite leads to very shows a hydrogen concentration profile along the crys-
similar spectra. However, the continuous shift of
the 3,330 cm1 and the 3,550 cm1-bands with varying Table 3 Hydrogen contents: SIMS versus FTIR
Cr/Fe-ratio (Fig. 1c) indicate that both types of defects
are present. H2O H (wt ppm) H (wt ppm)
Mößbauer spectra for pure ferrosilite and 57Fe-doped (wt ppm) FTIR SIMSa
FTIR
orthopyroxenes are shown in Fig. 2 and site occupancies
are listed in Table 4. No ferric iron could be observed in *En 264 29 44
ferrosilite and in RS063, suggesting Fe3+/Fetot < 0.01. *Opx Al 5 309 34 65
However, due to the high Fe-content of ferrosilite, even *Opx Al 9 543 60 87
still smaller Fe3+/Fetot-ratios could lead to significant *Opx Al 17 1443 160 308
*Opx Cr 0.1 377 42 76
Fe3+-defects in ferrosilite; therefore one ferrosilite wafer *Opx Cr 0.4 708 79 133
was analysed by optical spectroscopy (Fig. 3). In optical *Opx Fe 2 288 32 44
absorption spectra of a (Fe3+, Al)-doped ferrosilite, *Opx Fe 9 581 65 103
Steffen et al. (1988) observed a band at 12,500 cm1 *Opx Fe 18 1206 134 173
RS072a 779 87 147
polarised in the c-direction that they assigned to Fe2+–
Fe3+ intervalence charge transfer. Such a band is not *Samples described in Stalder (2004)
a
present in the c-spectrum of our ferrosilite sample RS054 Analytical accuracy is estimated to be 20%
Fig. 2 Mößbauer spectra of ferrosilite a and 57Fe-doped orthopyroxenes b–d recorded at 77 K. Assignment of absorption doublets:
dashed line: Fe2+ (M1), dashed-dotted line: Fe2+ (M2), dotted line: VI Fe3+, solid line: IV Fe3+. Summed spectrum indicated by thicker
solid line (quantitative values see Table 4)
tallographic c-axis of RS072c. If a similar zonation in all
directions of the crystal is assumed, the significantly
lower H-content close to the rim correlates well with the
amount of Me3+-related OH-defects. The chemical
zonation of RS072c is illustrated in Fig. 5b using
an electron microprobe data profile parallel to the
crystallographic b-axis, calculating the amount of
Me3+-related OH-defects assuming coupled substitution
of Cr3+ and H+, and Fe3+ and H+; for the latter it
was taken into account that Fe3+ is partly incorporated
by other substitutions; the fraction of Me3+ coupled to
H+ (which is equal to the ratio (H+ incorporated due to
Me3+)/Me3+) is given in Table 2 (last column).
Discussion
Quantification of FTIR spectra of nominally anhydrous
minerals is not straightforward. There are uncertainties
related to background subtractions, extinction coeffi-
cients and absorption from non-point defect OH.
Especially, concerning background subtraction there is
an ongoing discussion (Grant et al. 2005), suggesting
that point defect OH may be systematically lower in
orthopyroxene. However, both results from secondary
ion mass spectrometry (SIMS) and previous FTIR-data
from a series of synthetic enstatites doped with Cr
(Stalder 2004) suggest that OH-concentrations deter-
mined by FTIR are underestimated. For the majority of
samples in this study, where OH was only determined by
FTIR we will assume in the following discussion that
water contents determined by FTIR are underestimated
by a factor of 1.4. In addition, taking into account that
pure enstatite also incorporates hydrogen by creating
Mg-vacancies, we define Hexcess (Table 2) as the amount
of H incorporation due to coupled substitution with a
trivalent cation. H incorporation in different orthopy-
roxenes will be discussed separately.
Ferrosilite
Even if Mößbauer spectroscopy and optical spectros-
copy cannot exclude that ferric iron contributes signifi-
Fig. 3 Optical absorption
spectrum of ferrosilite (RS054)
polarised in c-direction.
Spectrum obtained on a 47 lm
thick wafer parallel to (100).
Peaks at 8,000–11,000 cm1
are caused by spin-allowed
Fe2+ d-d transitions; peaks
near 20,000 cm1 are caused
by spin-forbidden Fe2+
transitions. Absence of a
Fe2+–Fe3+ charge transfer
band at 12,500 cm1 (cf. Steffen
et al. 1988) indicate a very low
Fe3+ content (Fe3+ /
Fetot<0.002 corresponding to
Fe2O3 £ 0.10 wt-%)

cantly to hydrogen incorporation, IR spectra re-
veal—even after thermal treatment—only one major
defect associated with hydrogen. The fact that thermal
treatment in both air and hydrogen atmosphere furnish
the same spectra suggests that almost no hydrogen is
associated to Fe3+. Thus Fe2+ -vacancies
H2 O þ FexM1 ¼ V00M1 þ FeO þ 2H
i ;
are the most probable defect, analogous to the point
defect in pure enstatite.
H2 O þ Fe2 O3 þ 2SixT ¼ 2SiO2 þ 2Fe0T þ 2H
i ; ð3Þ
where MgxM1 and SixT
indicate Mg on a M1-site and Si on
a tetrahedral site; Fe
M1 and Fe0T indicate ferric iron
on a M1 and on a tetrahedral site, and V00M1 and H
i a
M1-vacancy and a hydrogen interstitial (Kröger and
Vink, 1956). Combination of (2) and (3) furnishs a
ð1Þ Fe-equivalent of the Tschermaks substitution:
Fe2 O3 þ MgxM1 þ SixT ¼ Fe
M1 þ Fe0T þ MgO þ SiO2 :
ð4Þ

Fe-bearing enstatite As the M2-site in orthopyroxene is slightly larger than

For Fe-bearing enstatite different types of defects
involving hydrogen and iron can be encountered,
H2 O þ Fe2 O3 þ 4MgxM1 ¼ 4MgO þ 2Fe
M1 þ 2V00M1
þ 2H
i ;
the M1-site, ferric iron is preferentially incorporated on
the M1-site and ferrous iron on the M2-site (Shi et al.
1992). If only Eqs. 2, 3, 4 are considered, hydrogen
incorporation by one single mechanism seems improbable
on the basis of the present data; if all ferric iron is assumed
ð2Þ to participate in hydrogen incorporation (Eqs. 2 and 3),

Table 4 Mößbauer parameters

for synthetic orthopyroxene Assignment RS054 RS063 RS064 RS084 RS054 RS063 RS064 RS084
obtained at room temperature RT RT RT RT 77 K 77 K 77 K 77 K
and 77 K. Hyperfine
parameters are given in mms1 Fe2+ (M1)
Int 51.7 18.6 16.3 16.2 50.1 16.9 15.9 16.4
fwhm 0.27 0.26 0.25 0.28 0.25 0.24 0.26 0.29
cs 1.18 1.16 1.15 1.14 1.29 1.26 1.26 1.27
dq 2.48 2.47 2.47 2.48 3.09 3.02 2.99 3.00
Fe2+ (M2)
Int 48.3 81.4 74.1 73.3 49.9 83.1 75.9 74.2
fwhm 0.27 0.24 0.25 0.27 0.25 0.25 0.27 0.29
cs 1.12 1.14 1.14 1.13 1.23 1.24 1.24 1.25
dq 1.92 2.10 2.10 2.10 1.98 2.14 2.14 2.13
Fe3+ (oct)
int 6.0 6.8 5.0 4.9
fwhm 0.27 0.27 0.30 0.29
cs 0.45 0.47 0.48 0.45
dq 0.68 0.63 0.79 0.82
Fe3+ (tetr)
int intensities given in % of int 3.6 3.8 3.2 4.6
total absorption area, fwhm full fwhm 0.33 0.32 0.30 0.30
width at half maximum, cs cs 0.26 0.29 0.35 0.35
centroid shift, dq quadrupole dq 1.47 1.44 1.43 1.38
splitting
Fig. 4 Hydrogen contents (in wt ppm H) determined by FTIR
compared to those measured by SIMS; measured samples are a
suite of synthetic doped orthopyroxenes (black squares) from
Stalder (2004) and one of the Fe-Cr-doped enstatite crystals from
this study (RS072a, open circle). Samples RS072b and RS072c are
not shown in this diagram as they consisted both of one single
hydrogen contents would be higher than observed (Fig. 6,
black triangles); if all tetrahedral Fe3+ is assumed to
participate in Fe-Tschermaks-substitution (Eq. 3),
hydrogen contents would be lower than observed (Fig. 6,
grey circles). Octahedrally coordinated Fe3+ show the
best correlation to the observed hydrogen content (Fig. 6,
open circles), but in order to achieve charge balance for
the tetrahedrally coordinated Fe3+, the most realistic
explanation is a combination of (2), (3) and (4).
Multiple doped enstatite
Water concentrations in multiple doped enstatites are
lower than expected from the concentration of trivalent
cations (Table 2, last column). In enstatites doped with
both Al and Cr several reactions creating defects may be
formulated:
H2 O þ Al2 O3 þ 4MgxM1 ¼ 4MgO þ 2Al
M1 þ 2V00M1
þ 2H
i ; ð5Þ
H2 O þ Al2 O3 þ 2SixT ¼ 2SiO2 þ 2Al0T þ 2H
i ; ð6Þ
H2 O þ Cr2 O3 þ 4MgxM1 ¼ 4MgO þ 2Cr
M1 þ 2V00M1
þ 2H
i ; ð7Þ
Al2 O3 þ MgxM1 þ SixT ¼ Al
M1 þ Al0T þ MgO þ SiO2 ;
ð8Þ
Al2 O3 þ Cr2 O3 þ 2MgxM1 þ 2SixT
¼ 2Cr
M1 þ 2Al0T þ 2MgO þ 2SiO2 : ð9Þ
As IR spectra from single doped enstatites show
specific OH-absorption bands for each trivalent cation
crystal (i.e. only one orientation) and therefore quantitative
H-determination by FTIR was not possible. The error given for
the SIMS analyses represents the estimated accuracy (±20%);
the error given for FTIR analyses represents the average
standard deviation for measurements on several crystals of the
same charge
associated with a hydrogen defect (Fig. 1b), it is possi-
ble to deduce the nature of the defects in multiple doped
samples. In the case of enstatite containing both Al3+
and Cr3+, Al-related hydrogen defects can be identified
in all studied samples containing Al. In contrast, only
samples with Al/(Al+Cr) smaller than about 0.6 exhibit
Cr-related OH-peaks. It is therefore concluded that in
samples with Al/(Al+Cr) > 0.6, the incorporated Cr3+
is not directly associated with hydrogen. Therefore the
only possible mechanism is substitution (9). If
Al/(Al+Cr) > 0.6, at least three types of associated
defects are present, namely {Al
M1 + Al0T }, {Cr
M1 +
Al0T } and {Al
M1 + V00M1 + H
i }, and maybe also {Al0T
+ H
i }. If Al/(Al+Cr) < 0.6, {Cr
M1 + V00M1 + H
i },
{Cr
M1 + Al0T } and {Al
M1 + V00M1 + H
i } (and maybe
also {Al0T + H
i }) are present. If Al/(Al+Cr)  0.6,
all Cr is related to {Cr
M1 + Al0T } defects, and some Al is
linked to hydrogen. In order to model the defect chem-
istry defect–defect interactions can be formulated as
fAl
M1 þ V00M1 þ H
i g þ fAl0T þ H
i g
¼ fAl0T þ Al
M1 g þ H2 ð10Þ
fCr
M1 þ V00M1 þ H
i g þ fAl0T þ H
i g
¼ fAl0T þ Cr
M1 g þ H2 ð11Þ
fCr
M1 þ V00M1 þ H
i g þ fAl0T þ Al
M1 g
¼ fAl
M1 þ V00M1 þ H
i g þ fAl0T þ Cr
M1 g ð12Þ
with the equilibrium constants
 
K10 fAl0T þ Al
M1 g
¼    ð13Þ
fH2 fAl0T þ H
i g  fAl
M1 þ V00M1 þ Hi
g
  
K11 fAl0T þ Cr
M1 g here, the equilibrium lays on the right side of Eq. (12);
¼    ð14Þ previous results from a series of Al-doped enstatites
fH2 fAl0T þ H
i g  fCr
M1 þ V00M1 þ Hi
g (Stalder, 2004) suggests that K10/fH2>7.5 (as one out of
 0

 
00
 8.4 Al is coupled to an H) for enstatites with very high
AlT þ CrM1  AlM1 þ VM1 þ Hi
Al/(Al+Cr), but a much lower value is expected for Cr-
K12 ¼  0  
 ð15Þ
AlT þ Al
M1  CrM1 00 þ H

þ VM1 i rich crystals. For crystals with a Al/(Al+Cr) < 0.6 we
can derive the respective defect concentrations according
As all syntheses were carried out under quasi identi- to Eq. (14)
cal conditions and no solid buffer was present, hydrogen  3þ  
  
fugacity probably is given by the talc-pyrex cells (Dunn Cr ¼ CrM1 þ V00M1 þ H
i þ Cr
M1 þ Al0T
1983) and can be regarded as constant over the whole ð16Þ
series. The defect concentrations can be calculated from
the water contents; for our calculations we will use the     
Al 3þ
¼ Al0T þ H
i þ Cr
M1 þ Al0T ð17Þ
water contents determined by FTIR corrected by factor
of 1.4 (referring to the SIMS analyses and the Cr-H- 
  
CrM1 þ Al0T ¼ K Cr
M1 þ V

00
M1 þ Hi


correlation in Cr-doped enstatites). According to Stalder
 AlT þ H
i ð18Þ
(2004), then only one out of 8.4 Al (6*1.4) and one out
of 1.4 Cr is coupled to an H in single doped enstatites. Hexcess as a function of K, [Al3+] and [Cr3+] can be
We then use the above definition for Hexcess as the calculated taking into account that one out of 8.4 Al3+
amount of H incorporation due to coupled substitution
with a trivalent cation, and define K=K11/fH2. If we can
quantify the above equations, a model for hydrogen
incorporation in Al+Cr-doped enstatite can be derived.
Equilibrium constant for reaction (10) and (12) can be
estimated; from the spectroscopic data it can be con-
cluded that K12 1 for Al/(Al+Cr) > 0.6; K12 may be
a function of Al/(Al+Cr), but for all samples studied

Fig. 6 Amount of ferric iron that participates in hydrogen

Fig. 5 a H-concentration profile (//c) on RS072c determined by
SIMS; b H-incorporation capacity calculated on the basis of the
Fe3+- and Cr-concentrations determined by electron microprobe
over a profile (//b) on RS072c. Note that both profiles are
measured in different directions and have different scale (1 mm //c,
0.3 mm //b), but show the same principle zonation feature
incorporation versus hydrogen content (determined by FTIR) of
57
Fe-doped orthopyroxenes; ppm (at) refers to ppm (wt)/molar
mass. Ferric iron participating in hydrogen incorporation was
assumed to be either merely octahedral Fe3+ (open circles),
tetrahedral and octahedral Fe3+ (black triangles), or octahedral
minus tetrahedral Fe3+ (grey circles); the last case accounts for Fe-
Tschermaks-substitution. The solid line shows the expected
correlation if ferric iron is incorporated by coupled substitution
with hydrogen; the dashed line shows how the correlation would fit
if 40% higher hydrogen contents are assumed (owing to the results
from SIMS analyses). The arrow indicates that concentration for
Fe3+ may be lower
Fig. 7 Model for defect interactions; ppm (at) refer to ppm (wt)/
molar mass. Solid lines represent theoretical isolines for hydrogen
solubility (in wt ppm H). Black symbols represent enstatites
containing both Cr- and Al-specific OH-defects, grey symbols
exhibit only Al-specific OH-defects. Hydrogen concentration (in wt
and one out of 1.4 Cr3+ is coupled to an H in single
doped enstatites; in model (a) (Fig. 7a) [Al3+] and
[Cr3+] are identical to the real concentrations deter-
mined by microprobe divided by their respective molar
mass. For crystals with a Al/(Al+Cr) > 0.6 other de-
fects than in reaction (11) are introduced and two dif-
ferent Tschermaks pairs (Al3+ + Al3+ and Al3+ +
Cr3+) are present, rendering the model more compli-
cated. In order to account for the additional Al not
ppm H) for each sample is shown inside the symbol. The difference
between model a and b is explained in the text. Al* and Cr* denote
the effective concentration of Al and Cr involved in OH-bonding.
K denotes K11/ fH2
participating in (11), the Al/(Al+Cr) from model (a)
was recalculated dividing [Al] by a factor of 8.4 and [Cr]
by 1.4, respectively (referred to as Al* and Cr* in
Fig. 7); results are shown in Fig. 7b. Comparison of the
experimental results to model (a) show the highest cor-
respondence for K=2 (Fig. 7a); samples containing
{Cr
M1 + V00M1 + H
i } defects (shown as black circles in
Fig. 7) do fit better to model (a) than those without
{Cr
M1 + V00M1 + H
i } defects (shown as grey circles). In
Fig. 7b (Contd.)
contrast, samples without {Cr
M1 + V00M1 + H
i } defects
show a higher correspondence to model (b) (Fig. 7b),
with a higher value for K (between 3 and 8). It is not
surprising that data of samples with a high (Al/
(Al+Cr)) fit better to model (b), as in Al-rich samples
much of the Al will form {Al
M1 + Al0T } defect associ-
ates and therefore the effective concentration of Al in-
volved in OH-bonding will be reduced. Whereas water
concentrations for samples containing {Cr
M1 + V00M1 +
H
i } can be described rather well with model (a), Al-rich
samples would probably be described best by a hybrid
model between (a) and (b), depending on Al/(Al+Cr);
so the K for model (b) does not have a real meaning. As
K=K11/ fH2 we can express the free enthalpy for Eq.
(11) for model (a)
DG11 ¼ R  T  ln K11 ¼ R  T  ln K  R  T  ln fH2
ð19Þ
The only unknown in Eq. (19) is the hydrogen fugacity,
which can be estimated assuming that the oxygen
fugacity was externally buffered by the cell assembly and
therefore close to the C-CO-CO2-O2 buffer (Dunn 1983);
using the equation of state of Saxena and Fei (1987) and
Belonoshko and Saxena (1992), a hydrogen fugacity of
103 bar is obtained. Inserting R (8.3143 Jmol1 K1), T
(1423 K) and K (2) in Eq. (19) we receive a DG11=
90 kJ/mol. As model (b) is strongly dependent on Al/
(Al+Cr) and other defects are present which are not
taken into account, K does not give quantitative infor-
mation concerning the energetics of equilibrium (11). It
also has to be emphasised that Eqs. 10, 11, 13, 14 and 15
could alternatively be formulated with fH2 O (instead of
fH2 ) controlling the equilibrium. The procedure would
be similar as described above; which alternative is more
appropriate could be tested by experiments at different
fO2 and different total pressure.
The model described above is in principal also
applicable to orthopyroxenes containing a combination
of other trivalent cations. However, samples from
RS072, containing both Cr3+ and Fe3+ exhibit only
small deviations of Hexcess/M3+ from unity (Table 2),
and an increased tendency to form Tschermaks-like
defects cannot be proved.
Implications for natural mantle derived orthopyroxenes
IR-spectra taken from natural orthopyroxenes from
upper mantle xenoliths (Bell et al. 1995, Rossman 1996,
Peslier et al. 2002, Stalder 2004) all show OH-absorption
bands specific to a local cation arrangement containing
Al, whereas OH-bands specific for Cr are absent (Stalder
2004). The model presented above explains this behav-
iour satisfactorily, as all {Cr
M1 + V00M1 + H
i } defect
associates are destroyed by reaction (11) and (12) if the
molar ratio of Al/(Al+Cr) is larger than 0.6 (which is
generally the case for upper mantle material).
The tendency of OH-defect destruction in orthopy-
roxenes containing different trivalent cations has
important consequences for hydrogen storage in ortho-
pyroxene. In contrast to previous suggestions that
hydrogen solubility is directly proportional to the con-
centration of trivalent cations (Rauch and Keppler 2002,
Stalder 2004), results from this study suggest much
lower hydrogen solubilities. Natural orthopyroxenes
from the Earth’s mantle show a broad range of trivalent
cation concentrations and are derived from different
depths and temperatures (e.g. Frey and Prinz 1978,
Boyd and Mertzman 1987, Zipfel and Wörner 1992)
affecting the equilibrium constants of the defect reac-
tions, a general statement concerning the hydrogen sol-
ubility is not possible. Further studies investigating the
influence of pressure and hydrogen fugacity are neces-
sary.
Acknowledgements Andreas Kronz (Universität Göttingen) is
thanked for the microprobe analyses, Harald Behrens (Universität
Hannover) is thanked for valuable discussions and for kindly
providing access to the IR-spectroscope. Constructive reviews by
Sergei Matveev and Simon Kohn are kindly acknowledged.
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