Contributions to Mineralogy and Petrology (2019) 174:1

https://doi.org/10.1007/s00410-018-1536-4

ORIGINAL PAPER

Methane-bearing fluids in the upper mantle: an experimental

approach
Vladimir Matjuschkin1 · Alan B. Woodland1 · Gregory M. Yaxley2

Received: 15 February 2018 / Accepted: 16 November 2018

© Springer-Verlag GmbH Germany, part of Springer Nature 2018

Abstract
The main obstacle to understanding of the geological role of reduced, ­CH4-bearing fluids is the absence of a reliable experi-
mental technique applicable to solid-media high-pressure apparatuses, allowing their observation and direct characterisation
under laboratory conditions. In this study, we describe the main pitfalls of earlier designs and technical aspects related to
achievement of strongly reduced oxygen fugacity (fO2) conditions (i.e., Fe–FeO, IW) and maintenance of a constant fluid
equilibrium during an experiment. We describe a new triple-capsule design made of an Au outer capsule with an Au-inner
capsule containing a metal/metal oxide oxygen buffer and water, as well as an inner olivine container filled with a harzburgitic
sample material and Ir powder that serves as a redox sensor. The bottom of the outer capsule is covered with a solid fluid
source (e.g., stearic acid). The outer capsule is surrounded by a polycrystalline ­CaF2 pressure medium to minimise ­H2-loss
from the assembly. Application of this design is limited to temperatures below the melting temperature of Au, which is pres-
sure dependent. Metals other than Au can lead to fluid disequilibrium triggered by a dehydrogenation and carbonation of the
methane. Test experiments were carried out at 5 GPa, temperatures < 1300 °C, at Mo–MoO2 and Fe–FeO buffer conditions.
IrFe alloy sensors demonstrate successful achievement and maintenance of reduced fluid environment at ∆logfO2 ≈ IW + 0.5.
The fluid phase was trapped in numerous inclusions within the olivine sample container. Raman spectra reveal that the fluid
consists mainly of C ­ H4, along with small amounts of higher hydrocarbons like C ­ 2H6. No water was detected, but H ­ 2 was
found to be present in fluid and incorporated into the olivine structure. Our results are inconsistent with published fluid
speciation models that predict significant ­H2O contents at these fO2 conditions. It is also apparent that fluids with significant
­CH4 contents are likely to be stable under the conditions recorded by some mantle samples.

Keywords  Reduced fluid · Methane · Upper mantle · High pressure · Experiments · Oxygen fugacity buffer · Graphite
saturation

Introduction

The role of fluids is fundamental for most geological pro-

Communicated by Jochen Hoefs.
Electronic supplementary material  The online version of this
article (https​://doi.org/10.1007/s0041​0-018-1536-4) contains
supplementary material, which is available to authorised users.
* Vladimir Matjuschkin
v.matjuschkin@em.uni‑frankfurt.de
1
Institut für Geowissenschaften, Goethe-Universität Frankfurt
am Main, Altenhöferallee 1, 60438 Frankfurt am Main,
Germany
2
Research School of Earth Sciences, The Australian National
University, Canberra, ACT​ 2601, Australia
cesses. For instance, they control the solidus temperature of
rocks as well as the physical parameters of subsequent melts,
such as viscosity and density. Fluid components of mag-
mas also affect their crystallisation sequence and eruption
behaviour (Blundy and Cashman 2008; Blundy et al. 2010;
Melekhova et al. 2013; Zellmer et al. 2015). The extreme
mobility and high redox potential of fluids containing C,
O, and H (and also S) means that they are important meta-
somatic agents and can exert a strong influence on oxida-
tion–reduction reactions, largely contributing to the forma-
tion of redox heterogeneities within the Earth (Arculus 1985;
Evans and Tomkins 2011; Zellmer et al. 2015; Matjuschkin
et al. 2016; Uenver-Thiele et al. 2017). Clearly, the nature

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and dynamics of magmatic fluids are important parameters
to constrain. Their composition and thermodynamic proper-
ties are all strong functions of oxygen fugacity (fO2) (French
1966; Zhang and Duan 2010) and pressure, owing to their
high compressibility compared to solid phases. This makes
modelling fluid compositions very challenging.
Information about the behaviour of deep-seated mag-
matic fluids or those existing in the Earth’s upper mantle is
mostly derived from experimental studies. Thermodynamic
calculations rely on experimental calibrations, which are
difficult to produce at geologically relevant high pressures
and temperatures, where fO2 must also be controlled and
well monitored. At low pressures (< 0.5 GPa), externally and
internally heated gas-pressure vessels can be employed with
fO2 controlled by directly changing the hydrogen fugacity
(fH2) of the gas-pressure medium. Such control is not pos-
sible at higher pressures using solid-media apparatuses (e.g.,
piston–cylinder 0.5–3 GPa, belt apparatus 3–6.5 GPa, and
multi-anvil press > 7 GPa), and fluid composition is usu-
ally fixed following the double-capsule buffering technique
developed by Eugster (1957). This approach is less accurate
and reliable (Matjuschkin et al. 2015), particularly at low fO2
and a number of pitfalls need to be avoided when assembling
and running a successful experiment.
In this contribution, we first focus on common problems
related to the control and monitoring of fO2 and fluid spe-
ciation, especially under strongly reducing conditions (i.e.,
around the iron–wüstite, IW, oxygen reference buffer), where
­H2 and ­CH4 are expected to be significant fluid components.
We then go on to describe a new, modified capsule design
that aims to solve or at least minimise the main drawbacks
and problems of existing designs. All of our test experi-
ments were performed with a harzburgitic bulk composition
at pressures of 3–5 GPa and temperatures up to 1300 °C, in
a belt apparatus. However, such a design can be applied to
fluid-bearing experiments in any other solid-media apparatus
having a cell volume of > 200 mm3 (i.e., piston–cylinder,
large volume multi-anvil press).
Important aspects related to the control
and monitoring of fO2
“Intrinsic” fO2 control
In absence of a fO2 buffer, the sample of a high-pressure
experiment is essentially ‘unbuffered’. Such an experiment
approaches the fO2 of the apparatus as dictated by its con-
stituent parts (e.g., furnace, pressure cell materials, etc.)
and chemical environment (e.g., fH2), and this is referred
to as ‘intrinsic fO2 control’ or ‘intrinsically buffered fO2’.
This term is very misleading, since no actual control is
provided and fO2 can vary with run duration, sample bulk
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Contributions to Mineralogy and Petrology (2019) 174:1
composition or even with the humidity in the laboratory
(e.g., Matjuschkin et al. 2015). Intrinsic fO2 results from the
hydrogen exchange between the sample and the surround-
ing parts of the apparatus, which is a strong function of the
experiment temperature. Intrinsically controlled water-rich
samples often suffer from water loss, followed by strong oxi-
dation of the sample material and then later by a reduction to
the ‘intrinsic value’. This fO2 value generally varies between
− 0.5 and + 3 log units relative to the synthetic fayalite–mag-
netite–quartz oxygen buffer (i.e., FMQ − 0.5 to FMQ + 3) for
a piston–cylinder or belt apparatus at 3 GPa and ~ 1000 to
1200 °C (unpub. Data; also see Jakobsson 2012; Jakobsson
et al. 2014a, b; Stamper et al. 2014). Intrinsic fO2 control is
often employed in combination with relatively “dry” sample
materials and is not suited for studying fluid-rich samples at
any fO2, since equilibrium conditions cannot be guaranteed
nor subsequently demonstrated.
Existing fH2‑buffering techniques and their
limitations
To solve the fO2 problem for high-pressure experiments,
Eugster (1957) introduced the double-capsule technique,
which relies on the principle of hydrogen exchange between
a solid oxygen buffer assemblage (e.g., Mo–MoO2) and the
sample materials that are separated by a metal membrane
that is permeable to ­H2. When fH2 equilibrium between
buffer and sample is achieved, a sample containing a pure
­H2O fluid (aH2O = 1) also attains the oxygen fugacity of the
metal buffer through the reaction:
H2 O = H2 + 0.5O2 , (1)
as long as the fluid phase in the sample and buffer assem-
blage is pure water. However, at high pressures and tem-
peratures, the fluid may contain significant dissolved com-
ponents, causing a systematic shift in the desired fO2 due to
a deviation from unit water activity (Sisson et al. 2005). In
addition, as the sample equilibrates at the new fO2 imposed
by the buffer assemblage it will either gain or lose water
depending on whether it underwent relative reduction or oxi-
dation, respectively (i.e., the forward or reverse of reaction
1, respectively). This effect is important to consider when
determining the relative size of the buffer employed and the
amount of added ­H2O.
The original double-capsule designs and their modifica-
tions (e.g., Eugster 1957; Jakobsson et al. 2014a, b; Moore
et al. 2008; Sokol et al. 2009; Tiraboschi et al. 2016) have
since undergone several improvements. Another recent
modification was introduced by Matjuschkin et al. (2015)
and consists of a triple-capsule arrangement with an exter-
nal Pyrex sleeve, which together help to (1) reduce ­H2 loss
and promote the early achievement of fO2 equilibrium in the
sample (2) reduce the temperature gradient in the assembly
Contributions to Mineralogy and Petrology (2019) 174:1 Page 3 of 14  1
owing to the large amount of H ­ 2O present in the outer cap-
sule and (3) prevent chemical interaction between the sample
and the buffer assemblage.
In principle, the designs of Eugster (1957) and
Matjuschkin et al. (2015) can be used in combination with
a variety of available redox buffers. In the following text,
we will demonstrate that these designs are only suited for
experiments with pure ­H2O as the fluid phase or for rela-
tively oxidised, ­H2O–CO2 fluids lying in the fO2 region at or
above the ‘water maximum’ (see Woermann and Rosenhauer
1985).
Solid and fluid fO2 buffers
A variety of materials can be employed as redox buffer
assemblages. Metal–metal oxide pairs together with ­H2O are
generally favoured due to the rapidity with which the buffer
equilibrium and the appropriate fH2 can be established soon
after the onset of the experiment. In addition, such assem-
blages also have the advantage of a high buffering capac-
ity per unit volume. Common buffers that cover a range in
fO2 include Re–ReO2, Ni–NiO, Co–CoO, and Mo–MoO2 as
well as the Fe-bearing pairs F­ e2O3–Fe3O4 (HM), F ­ e3O4–FeO
(WM) and Fe–FeO (IW). Depending on whether the sample
fO2 is to be significantly shifted during the experiment, the
relative proportion of metal to oxide in the buffer assem-
blage should be adjusted to improve its buffering capacity
(i.e., a high M/MO for achieving reduction of the sample and
the opposite if a net oxidation is desired). This is particularly
the case when the target fO2 significantly deviates from the
intrinsic fO2 of the pressure cell and apparatus. The average
run time required to effect a significant change in ­Fe3+/∑Fe
or ­S6+/∑S of the sample is about 12–24 h, assuming that the
mass of the sample is relatively small compared to that of the
buffer [< 1/3 of mbuffer, (Matjuschkin et al. 2015)].
Metal–metal oxide buffers can be physically separated
from the sample in their own capsule (e.g., Eugster 1957;
Matjuschkin et al. 2015; Moore et al. 2008) or be in direct
contact (Matveev et al. 1997). In the latter case, potential
reactions with the sample must be considered, such as the
undesired formation of mineral solid solutions or dissolution
in a melt phase.
Compared to solid-state buffers, fluids (e.g., COH flu-
ids) exhibit much lower buffering capacity. However, the
choice of fluid components can aid in the rapid attainment
of the target fO2. For example, ­CO2–H2O components can
be accurately added as hydroxides, carbonates, and oxa-
lates (e.g., Holloway et al. 1968). These components must
be prepared and stored under relatively dark, cold, and
dry conditions to avoid adsorption of C ­ O2 (hydroxides,
oxalates) or oxidation (oxalates) (Boldyrev 2002a, b). A
variety of other COH-bearing substances that are solid at
room temperature, but break down at elevated temperature,
are also available for producing fluids at carbon saturation
(e.g., tartaric acid, stearic acid, and lauric acid). In practice,
solid-organic materials require ~ 2 h equilibration time at
T > 1100 °C (Sokol et al. 2017) and reach slightly higher fO2
than expected, since theoretical calculations for estimating
fluid composition often ignore the presence of hydrogen.
For instance, during heating stearic acid (­ C18H36O2) breaks
down to ­8CH4 + 2H2O + 10C with a ­CH4-to-H2O ratio of 4:1,
which is used to calculate the equilibrium fO2 of the experi-
ment. However, amount of ­CH4 is actually somewhat lower,
because part of it reacts to C + 2H2 to produce the required
fH2 dictated by the buffer.
Monitoring of fO2
Tracking and monitoring fO2 can be achieved by various
means. It can be calculated from mineral compositions (e.g.,
QUILF, Andersen et al. 1993; spinel–olivine–orthopyroxene
assemblages; Wood 1990; Ballhaus et al. 1991) mineral-
melt equilibria (e.g., ol-melt, Matzen et al. 2011) or from
melt composition (e.g., ­Fe3+/∑Fe Borisov et al. 2015; Kress
and Carmichael 1991). However, many of these approaches
are not applicable as redox sensors in experiments, particu-
larly under reduced conditions, due to their relatively low
precision.
A number of different metals coexisting with oxides or
silicates have been calibrated as redox sensors. For example,
(Ni,Mn)O/Ni (Pownceby and O’Neill 1995) and (Co,Mn)O/
Co (Pownceby and O’Neill 2000), along with Ni–Pd/NiO
(Pownceby and O’Neill 1994a, b) and Co–Pd (Taylor et al.
1992), can deliver precise results over different ranges of
fO2. However, these may be difficult to use if they are to be
in physical contact with samples having natural rock com-
positions, since Ni, Co, and Mn can be readily incorporated
in many geologically relevant phases. It is known that some
experimentalists separate sensors by placing them next to
the capsule assembly. Such sensors are physically separated
from the sample and the capsule by zirconia tubes or other
materials. In this case, sensor readings might be interpreted,
as “intrinsic fO2” values of the apparatus, however, do not
represent the fO2 inside the sample (see further effects of
pressure medium material, hydrogen loss, water loss, and
Fe loss).
Redox sensors based upon Fe-bearing noble metal alloys
offer a way around the “sample contamination” problem,
since solid solution of noble metals is limited in minerals
under the majority of redox conditions of geologic interest.
The most commonly used alloys are Pt–Fe (Jamieson et al.
1992), Pd–Fe (Borisov and Palme 2000), and Ir–Fe (Wood-
land and O’Neill 1997). More complex ternary alloys of
Au–Pd–Fe (Barr and Grove 2010) have also be employed.
The use of Ir–Fe alloys has several advantages over those
with Pt or Pd. The first is the stability of face-centred cubic
13
 1  Page 4 of 14
(fcc) γ–Ir–Fe across the entire binary over a large tempera-
ture range, without intervening intermediate phases (at least
at 1 bar, Cahn 1991). Second, the solubility of Ag and Au in
Ir is very low (Cahn 1991), which is of importance, because
Ag and Au are potential capsule materials for high-pressure
experiments. Finally, low carbon solubility in γ–Ir–Fe allows
their use in reduced carbon-bearing systems. The activity
coefficient of Fe in Ir–Fe alloys is also well constrained,
allowing the activity of Fe in the experimental assem-
blage to be accurately calculated from microprobe analysis
(Woodland and O’Neill 1997). This result can subsequently
be applied to Fe-bearing redox equilibria to derive the fO2
during the experiment.
Reduced environments at high pressures
Achieving and maintaining reducing conditions (i.e., at or
near IW) in high-pressure experiments present additional
challenges for a number of reasons. One important aspect is
the high fH2 that must be maintained in the capsule, but the
intrinsic fO2 of the apparatus normally defines a much lower
fH2. This leads to a strong fH2 gradient between the sample
and the assembly outside of the capsule and can facilitate
rapid ­H2 loss from the sample. It is essential that H
­ 2 loss is
minimised in order for a constant fO2 to be maintained for
the duration of the experiment (Matveev et al. 1997). This
requires careful consideration of the type of materials used
for the capsule as well as for the parts of the pressure cell
directly around the capsule. Further complications of experi-
ments at low fO2 include the potential for substantial Fe loss
from the sample to the capsule. In C-bearing experiments,
fluids will be ­CH4 rich, meaning that speciation is more
complex, with H being distributed between multiple spe-
cies, potentially including higher order hydrocarbons. There
is also the possibility that unwanted fluid–metal reactions
may compromise fO2 buffering in an experiment. We now
address these potential problems in turn and provide recom-
mendations on how to solve or at least mitigate these effects.
Choice of capsule material
Aside from the normal constraints of isolating the sam-
ple from its surroundings, fluid-bearing experiments
necessitate the use of metal capsules. As demonstrated
by Matjuschkin et al. (2015), at high pressure and tem-
peratures, hydrogen leakage from the capsule assembly is
inevitable, since all noble metals are permeable to hydro-
gen to some degree or other at > 650 °C (also see Chou
1986; Truckenbrodt and Johannes 1999). This is useful in
double and triple-capsule assemblies, as it allows rapid
equilibration of fH2 between the buffer and sample assem-
blages. On the other hand, ­H2 loss from the outer capsule
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Contributions to Mineralogy and Petrology (2019) 174:1
is detrimental to a successful experiment. Hydrogen per-
meabilities vary widely between the different noble met-
als with Pd > Ag70Pd30 > Ag80Pd20 ≥ Pt > > Ag > Au (Chou
1986; Matjuschkin et al. 2015).
Au exhibits the lowest ­H2 permeability, but nevertheless
has often been successfully used as a hydrogen membrane
at > 800 °C (Matjuschkin et al. 2016) or even at lower tem-
peratures in long-duration cold-seal experiments (Mutch
et al. 2016). Hence, Au can be used in reduced experiments,
where high volume of hydrogen transfer from buffer to sam-
ple is required. The fact that Au can be easily welded means
that failure due to catastrophic fluid loss is rare. The opera-
tional temperature range is from 650 to 1250 °C at ~ 3.5
GPa (Akella and Kennedy 1971). Below 650 °C, hydrogen
diffusion through Au is so slow that the metal effectively
becomes a permeability barrier (Chou 1986). Somewhat,
higher temperatures can be reached at higher pressures as the
melting point of Au increases (Akella and Kennedy 1971).
Another consideration for reduced experiments is the
potential loss of Fe to the capsule material during the experi-
ment. This can not only modify the bulk composition of the
sample, but also cause oxidation via
FeO + M = MFe + 0.5O2
, (2)
sample capsule capsule sample
where M is the capsule metal. At fO2 above the ‘water
maximum’ (i.e., graphite saturation, Woermann and Rosen-
hauer 1985), Fe incorporation in AuPd or Pt ranges from 0
to 30 mol % as a function of fO2, and this limited amount
may not be viewed as a serious problem (e.g., Borisov and
Palme 2000). Fe loss can be minimised by pre-saturating the
capsule materials with Fe (which might make welding more
difficult) or using Au capsules. However, at more reducing
conditions, significant Fe loss can be expected to occur even
with pure Au metal (Cahn 1991; Borisov and Palme 2000;
Ratajeski and Sisson 1999). Under such reduced conditions,
Pd and Pt-bearing alloys can incorporate substantial amounts
of Fe and their use for capsules should be avoided. The lack
of significant alloying between Fe and Ag (Massalski et al.
1986) makes the later an ideal capsule material as long as the
relatively low maximum working temperature is compatible
with the required experimental conditions. Otherwise, Au
can be employed, keeping in mind that oxidation due to Fe
loss must be compensated for in one way or another (i.e., by
an internal buffer or fluid phase, see below).
Working with C-bearing fluids adds an additional consid-
eration to the choice of capsule material, since some metals
can induce chemisorption and carbonisation reactions. It is
known that reduced, ­CH4 rich, COH fluids are unstable in
the presence of Pt, Pd, or AuPd alloys at T > 600 °C (and
other metals as Ni, Co, Fe, Mo, Ir, Rh, Ru, etc.) (Concha
et al. 1984; Hanley et al. 1991; Rostrup-Nielsen 1993; Soly-
mosi and Erdohelyi 1980; Vannice 1977; Christensen et al.
Contributions to Mineralogy and Petrology (2019) 174:1 Page 5 of 14  1
2006). For instance, contact of C
­ H4 with Pd causes a step-
wise dehydrogenation reaction (Rostrup-Nielsen 1993):
CHfluid
4
+ Pd → ⋯ → C − Pd + 2H2 , (3)
or
CH4 − Pd → CH3 − Pd + 1∕2H2 → CH2 − Pd + H2 → CH − Pd + 3∕2H2 → C − Pd + 2H2 .
Similar chain reactions are expected for other hydrocar-
bons via (Rostrup-Nielsen 1993)
m
Cn Hm → ⋯ → nC + H. (5)
2 2
Even more oxidised CO-bearing fluids are at risk of ‘car-
bon loss’ at pressures < 3 GPa, unlike C
­ O2-fluid that remains
nearly unaffected by contact with Pd or Pt (Solymosi and
Erdohelyi 1980; Evans et al. 2006). We suspect that this may
be the reason for the CO-fluid component being so difficult
to detect in experimental run products. The dehydrogenation
of hydrocarbons is a clear problem and makes the predic-
tion of and the maintenance of fO2 very challenging. Short-
duration experiments (i.e., 1–3 h) do not provide a solution,
since fluid–mineral equilibrium cannot be assured, but long
durations can lead to severe changes in the fluid composi-
tion. Graphite-lined capsules can be used to slow down the
‘carbon loss’ reaction, but do not eliminate it. The references
given above provide numerous examples of this effect in
industrial processes.
In contrast to Pt, Pd, or AuPd alloys, Au does not inter-
act with the fluid and can preserve fluid composition much
longer, provided that fH2 is externally buffered and main-
tained (this study at high-pressures; also see Kratzer et al.
1996). Thus, it is advisable for reduced experiments contain-
ing methane to only use Au capsules.
Producing reduced COH fluids
Under reduced conditions, below the ‘water maximum’,
­CH4 and ­H2O are the dominant fluid species in a COH fluid.
Such compositions can be added in the form of solid-organic
compounds with low thermal stabilities, which helps to ini-
tially establish a low fO2 fluid without exhausting the capac-
ity of the buffer assemblage. For instance, anthracene or
docosane ­(CH4/H2O ≈ 1:0), stearic acid (4:1), or lauric acid
(5:2) can be used to rapidly achieve logfO2 levels from ~ IW
to ~ IW + 3, respectively (calculated from Belonoshko and
Saxena 1992; Zhang and Duan 2010). The breakdown of
these compounds also produces variable amounts of car-
bon, i.e., one mole of stearic acid yields ten moles of C:
­C18H36O2 = 8CH4 + 2H2O + 10C. The “missing” ­H2 nec-
essary for an equilibrium COH fluid at fO2 of IW will be
generated by a combination of the partial breakdown of
­CH4 ­(CH4 = C + 2H2) and H ­ 2 provided by an internal buffer
assemblage. Without a metal–metal oxide buffer, the fluid
composition shifts to more oxidised field towards the water
maximum (Matveev et al. 1997). Other materials, such as
­Al4C3–Al(OH)3, have also been used (Taylor and Green
1987; Taylor and Foley 1989), but this combination yields
(4)
­Al2O3 that can contaminate a sample. It also produces essen-
tially pure C
­ H4 that must then further react to form an equi-
librium fluid composition containing H ­ 2 and H­ 2O, placing
an even higher demand on the buffer assemblage for ­H2 than
substances like stearic or lauric acid.
The importance of the material surrounding
the capsule
The surrounding pressure medium (‘spacer’, ‘packing mate-
rial’) is a critical part of the experimental assembly. Ideally,
it creates a chemically closed environment around the outer
capsule and protects it from physical damage. For instance,
soft metal capsules (e.g., Au, ­Au90Pd10, and Ag) placed
in a material with a large porosity (e.g., pressed powders,
crushable alumina, or MgO) can experience strong degra-
dation or failure within 24–48 h (Fig. 1a, b). This problem
can be avoided using less porous materials or glasses (e.g.,
‘Pyrex’ glass, soda–lime–silica glasses, and polycrystalline
­CaF2). Harder capsule materials (Pt and Au–Pd alloys with
Pd > 20 mol %) are more resistant to failure (Rosenbaum and
Slagel 1995), but are not suitable for low fO2 experiments,
as previously described.
Apart from protecting the capsule, the surrounding pres-
sure medium is also very important for slowing down ­H2 loss
and helping to maintain fluid inside the sample capsule. Poor
hydrogen isolators are porous, crushable materials, powders,
vesicle-rich glasses, or very soft materials (e.g., commonly
used crushable alumina and MgO or NaCl). Such materials
lead to uncontrolled H ­ 2 exchange between the capsule and
external parts of the assembly (Fig. 1b) and press (Freda
et al. 2001). Note that industrial ceramic (­ Al2O3) is a good
hydrogen isolator, but is useless as a pressure medium, since
it cannot provide a hydrostatic pressure distribution around
the capsule (Matjuschkin et al. 2015; Serra et al. 2005).
Thus, the physical properties and quality of the material
determine its suitability as a pressure medium, particularly
in fluid-rich experiments under reducing conditions.
OH-bearing materials (i.e., unfired pyrophyllite or talc)
are often used to prevent the water loss by increasing the
overall ‘intrinsic fH2’ of the assembly (Freda et al. 2001;
Truckenbrodt et al. 1997). Such materials are typically
used for short-duration experiments, since these materi-
als dehydrate over time, effectively changing the external
13
 1  Page 6 of 14
Fig. 1  a Example of metal capsule degradation as illustrated by two
(soft) Au capsules in a hard, porous pressure medium material com-
posed of a crushable ­Al2O3 from a piston–cylinder experiment at
0.7 GPa, and 850  °C, with a 72-h run duration (photo, courtesy of
Richard Brooker). The coloured dots in ­Al2O3 is Au from the capsule
material that was pressed into the pressure medium material during
fH2 during the course of the experiment. This may lead to
inconsistent results within a series of experiments con-
ducted at different temperatures or durations and is unsuit-
able for experiments, where exact fO2 control is desired.
Pyrex glass helps to significantly retard ­H 2 loss, but
cannot guarantee the maintenance of constant fH 2 in
experiments longer than ~ 24 h (Matjuschkin et al. 2015).
Therefore, fluid-buffered experiments with low buffering
capacity always run at the risk of being exhausted unless
an additional buffer is present.
As an alternative to Pyrex, we tested the use of dense
polycrystalline ­CaF2 (not pressed powder, C.Giese GmbH
& Co.KG, Idar-Oberstein, Germany) as the pressure
medium surrounding the capsule, as well for the entire
pressure cell (Brey et al. 1990). As the ability of ­CaF2 to
inhibit ­H2 migration is currently unknown, we performed
two experiments with our assembly following the approach
of Matjuschkin et al. (2015). Two 3-mm Au capsules were
prepared, each containing C ­ o28Pd72 and ­Ni64Pd36, as fO2
sensors (Pownceby and O’Neill 1994a; Taylor and Foley
1989) together with 4.5-µL ­H 2O. The two alloys were
separated from each other and from the capsule walls by
­Al2O3 powder to avoid unwanted reaction. The capsules
were welded shut and inserted into C ­ aF2 pressure cells,
where they were run at 3 GPa and 1000 °C for 12 and
­ 2 loss is low, water will remain in
24 h, respectively. If H
the capsule and both sensors will equilibrate/react to simi-
lar fO2 values. If progressive ­H2 loss occurs, water will
also be lost, leading to continuous fH2 disequilibrium and
13
Contributions to Mineralogy and Petrology (2019) 174:1
the experiment. b Focused hydrogen diffusion through the bottom of
an outer gold capsule caused hydrogen corrosion (darker dots within
the Au). This was triggered using a porous crushable MgO disk at
the base of the assembly, whilst other walls were protected by a
solid Pyrex-glass sleeve. Assembly from an experiment at 1 GPa and
1000 °C for 24 h (after Matjuschkin et al. 2015)
discordant fO2 values registered by the two sensors, as well
as different results as a function of experiment duration.
Upon opening the capsules, ~ 3.4-µL H ­ 2O (of 4.5 µL)
was emitted, indicating substantial conservation of the ini-
tial water content. Analysis of the sensor alloys by EPMA
(see supplementary information) revealed homogeneous
compositions with no obvious zonation. Compositions of
­Co25Pd75 and N ­ i42Pd58 produced in the 12-h experiment
and are almost identical those obtained from alloys in the
24-h experiment ­(Co27Pd73, ­Ni46Pd54) (Fig. 2). Thus, no sig-
nificant shift in internal fO2 occurred over a 24-h period,
indicating that dense polycrystalline C­ aF2 is an ideal pres-
sure cell material for fluid-bearing experiments requiring a
constant fH2.
The new experimental design
Taking the above considerations into account, we have
developed an experimental design that allows us to reach
and maintain reducing conditions for sample bulk composi-
tions relevant to the Earth’s mantle. The setup was conceived
for a belt apparatus, but can just as well be employed in
a piston–cylinder apparatus or a large volume multi-anvil
press. In the latter case, a 25-mm octahedron pressure cell
is necessary to accommodate the capsule. The design com-
prises three major parts: (1) a 4.4-mm diameter Au outer
capsule that encloses; (2) a small fO2-buffer capsule; and (3)
an olivine capsule that contains the sample mixture (Fig. 3).
Contributions to Mineralogy and Petrology (2019) 174:1 Page 7 of 14  1

-7
3 GPa, 1000°C For the fO2 buffer (IW, Mo–MoO2), only the metal compo-
NiPd sensor nent (Fe or Mo) is loaded together with 3.5-µL H ­ 2O into a
CoPd sensor IW +6
3.0-mm Au capsule and welded shut. The oxide component
-8 forms at the onset of the experiment and starting with just
IW +5
metal maximises the buffering capacity. The capsule is then
stable ƒH2 pressed from all sides to form a sphere. Round buffer cap-
logƒO2

-9 no further oxidation
sules are more stable during pressurization and remain cen-
ion
ibrat IW +4 tred, without tilting towards the walls of the outer capsule.
uil NNO buffer
eq
-10 The buffer capsule is placed into the outer capsule on top
of stearic acid powder that serves as the source of the COH
IW +3
fluid (Fig. 3). The use of Au avoids potential dehydrogena-
-11
0 10 20 30
tion reactions with the subsequent reduced, C ­ H4-rich fluid.
Run duration, hours The mass of stearic acid is 7 wt% of the total mass of the
sample, producing 4 wt% ­H2O + CH4 fluid and 3 wt% solid
Fig. 2  Test of hydrogen loss in an Au capsule surrounded by ­CaF2 C at the beginning of the run. The buffer and outer capsules
pressure medium material at 3 GPa and 1000 °C. Experimental pro- are physically separated by a filler powder that has the same
cedure is similar to that reported by Matjuschkin et  al. (2015). Col- bulk composition as the sample. For our test experiments,
oured symbols represent the readings of CoPd, NiPd redox sensors.
Comparing experiments with 12–24-h duration, the composition of
the sample comprised a finely ground powder of hand-
the sensor did not shift, indicating the absence of hydrogen exchange picked natural olivine and orthopyroxene (F7, Lazarov et al.
with the surrounding pressure medium material. Results are similar to 2009). The sample itself contained an additional 5 wt% of
those reported for Pyrex by Matjuschkin et al. (2015) ≤ 60-µm Ir powder to serve as a fO2 sensor. The sample is
packed into a 4-mm diameter olivine container (San Carlos)
that is inserted above the buffer into the outer Au capsule
(Fig. 3). The outer capsule is then welded shut and placed
into a polycrystalline ­CaF2 pressure cell.
Our test experiments were performed in a belt apparatus
at the Universität Frankfurt at 5 GPa and temperatures from
1100 to 1300 °C. The temperature was controlled using a
Type-B ­Pt70Rh30–Pt94Rh6 thermocouple, with ± 7 °C accu-
racy. Pressure calibration for the C ­ aF2 pressure cell was
sample reported by Brey et al. (1990). The experimental duration
+ varied from 12 to 24 h, depending on temperature (Table 1).
ƒO2 Experiments were quenched isobarically by shutting off the
sensor power supply to the graphite furnace. The recovered Au
capsule was embedded in epoxy and ground down until the
olivine
sample inside the olivine container was exposed. Paraffin
was used as a grinding medium, since liquid oils can pen-
ƒO2 Au etrate deep into graphite pockets and are difficult to remove.
buffer
sample
+H2O

Results
fluid source
Run products
CaF2
All experimental run products consist of re-equilibrated
olivine (ol) and orthopyroxene (opx) grains, graphite
1mm ­( C gr), together with a COH fluid (fl) (Table 1; Fig. 4a).
Analytical methods are described in the supplementary
materials. Olivine and orthopyroxene in the olivine con-
Fig. 3  New experimental setup (see text). Fluid source is thermally
tainer are compositionally uniform. The sample contact
unstable stearic or lauric acid. ­CaF2 is a solid polycrystalline mate-
rial enclosing the entire capsule assembly and separating it from the with the olivine container is sharp (Fig. 4a). In contrast,
thermocouple wire sample powder placed as filler next to the outer Au capsule

13
 1  Page 8 of 14 Contributions to Mineralogy and Petrology (2019) 174:1

Table 1  Overview of run conditions and experimental run products

Experiment P, GPa/T, °C Duration, h Buffer Mg# ol/opx XFe in Ir logfO2 sensor Sensor ∆ IW Fluid composition

1571 3/1150 24 IW 94/94 – – – CH4–H2, ­HCa

1572 5/1250 24 IW – – – – CH4–H2, ­HCa
1580 5/1250 24 IW 92/93 0.32 − 8.75 IW + 0.69 CH4–H2, ­HCa
1581 5/1280 18 IW 92/94 0.31 − 8.38 IW + 0.74 CH4–H2, ­HCa
1583 5/1200 20 IW 93/94 0.35 (14) − 9.53 (90) IW + 0.46 (90) CH4–H2, ­HCa
1585 5/1250 23 Mo–MoO2 93/94 0.30 − 8.66 IW + 0.78 CH4–H2, ­HCa
1586 5/1250 15 Mo–MoO2 93/94 0.30 − 8.18 IW + 0.73 CH4–H2, ­HCa
1587 5/1280 12 Mo–MoO2 93/94 0.34 − 8.61 IW + 0.50 CH4–H2, ­HCa
1611 5/1280 12 Mo–MoO2 94/94 0.33 − 8.45 IW + 0.47 CH4–H2, ­HCa

Ol and opx are re-equilibrated grains measured inside the ol-container (Mg#88) and are protected from the iron loss or buffer contamination,
respectively. Absence of some fO2 measurements is due to the sample loss during the preparation. Conservative uncertainty of fO2 measurements
is ± 0.05 log units and is a statistical value calculated from 5 to 20 analyses in each sample. High uncertainty of measurements in exp. 1583 are
due difficulty in analysing needle-like sensor aggregates (see text)
a
 Unspecified higher hydrocarbons, including ­C2H6

experienced strong Fe loss and resulted in up to 40%

Fig. 4  a Experimental run products: the inner sample material with
Ir sensor inside the olivine container in run 1581. b Effect of Fe loss
to the outer Au capsule, which affects the olivine composition and
causes some transformation to orthopyroxene
FeO removal in olivine and up to 10% in orthopyroxene,
respectively (Fig. 4b).
Graphite is present in all experiments as a breakdown
product of stearic acid and appears either as needles and
clots filling the space between mineral grains or within
fluid inclusions. Some graphite was deposited on the walls
of the outer Au capsule or along cracks in the olivine con-
tainer indicating fluid circulation during the course of the
experiment.
Interestingly, no fluid was observed upon opening the
capsule. However, based upon textural evidence from
BSE images, a fluid phase was equally distributed within
the capsule (Fig. 4a). Considering that only 4 wt% fluid
equivalent was packed into the capsule, it appears that
the majority of the fluid has been trapped as inclusions
within the olivine container (Fig. 5a, b) or it occurred in
the pockets of graphite. Analysis of the fluid inclusions
by Raman spectroscopy reveals that they are composed of
methane and very minor ethane ­(C2H6) (Fig. 5c, d). Graph-
ite is present in some, but not all inclusions. No H­ 2O was
detected in any fluid inclusion. ­H2 was rarely detectable
as an additional fluid component from a Raman peak at
4155 cm−1 (Fig. 5d). In addition, some spectra of olivine
in non-confocal mode revealed the presence of ­H2 with a
broad peak position at 4119 cm−1 (Fig. 5d). This shift in
the peak position suggests that this ­H2 was incorporated
in the olivine structure, where it is better retained (Yang
et al. 2016). It is likely that H
­ 2 readily escapes from the
fluid during polishing (Yang et al. 2016) and when the
sample is placed under vacuum during EPMA investiga-
tion, thus lowering the probability of detecting this spe-
cies in inclusions. The dominant presence of C ­ H 4 ± H 2
qualitatively testifies to the reducing conditions achieved
in our experiments.

13
Contributions to Mineralogy and Petrology (2019) 174:1 Page 9 of 14  1

Fig. 5  a, b Reflected polarised

light images of fluid inclusions (a) (b)
in the olivine container from
experiments 1585 and 1611,
respectively. c, d Representative gr
Raman spectra of fluid inclu- ol
sions in the olivine host. The
broad peak around that for C ­ H4 gr
at 2917 cm−1 is attributable to ol
other hydrocarbons, like C ­ 2H6
at 2948 cm−1 (Table 1) fluid
fluid
20µm 30µm

(c) 1586
C (d)
2722
arbitary arbitary
C
units units
2917 CH4 (L)
2917 CH (L)

2441 3065 H
CH (L) exp. 1580
C
2329
1358 N (air)
host olivine C 3247
H in host olivine:
C
host olivine 3065
1586 2722 CH (L)
- CH Mo-Mo Mo-Mo
C C 3247
stretching exp. 1586 exp. 1587
C
2869
1000 2000 3000 4000 cm-1 1000 2000 3000 4000 cm-1

The fO2 buffer
Results of test runs demonstrate that the use of appropriate
buffer components, in addition to their correct installation,
can significantly contribute to the overall success of an
experiment. Under strongly reducing conditions, employ-
ing only metal is advantageous, since the significant ­H2
supply required is derived from equilibrium (1). This liber-
ates oxygen that readily produces the MO buffer couple.
Fe-bearing buffers, like IW, tend to react even with the
Au under such conditions. However, as long as both Fe
and FeO are present in the capsule after the experiment,
no significant deviation in the imposed fO2 is expected.
Our results indicate that the buffer capsule remains
sealed, as Fe is incorporated in the Au, even at temper-
atures near the nominal melting point of pure Au (i.e.,
exp. 1581 at 1280 °C and 5 GPa, Table 1). This contrasts
with experiments at the higher fO2 of the Re–ReO2 buffer,
where Au–Re alloying causes capsule failure after < 12 h
(Matjuschkin, unpub. data). However, we do observe Fe
diffusion through the buffer capsule (Fig.  6a). This is
apparent in backscattered electron images as flame-like
Fe-rich zones emanating from the capsule into the adjacent
olivine (Fig. 6b). Such a phenomenon needs to be carefully
monitored to assure that the Fe enrichment does not reach
the sample. This is an advantage of the olivine container
in that it can readily incorporate this excess Fe (Fig. 6b).
An alternative is to use the Mo–MoO2 buffer, which lies
only ~ 0.5 log units below IW (O’Neill 1986). In experi-
ments conducted at the same pressure and temperature as
those with the IW buffer, we observed no migration of Mo
(i.e., diffusion) through the buffer capsule (exp. 1585–1612,
Table 1) (Fig. 6c).
Ir sensor and fO2 equilibrium
Initially, a small quantity of Ir powder was mixed with the
starting composition to sense the oxygen fugacity distri-
bution inside the sample. At T ≥ 1250 °C, metal powder
reacted to a homogeneous alloy with platelets up to 30 µm
across ideally suitable for the electron-probe microanaly-
sis (EPMA). Below 1250 °C, Fe alloyed more slowly with
the Ir, resulting in the formation of needle-like aggregates,
of which only few grains could be analysed (exp. 1583).
To improve the measurement statistics, the run time was
increased by several hours. In IW-buffered experiments, this
led to more progressive reaction of Au with the buffer and
Fe gain in the surrounding sample material, respectively. To
solve the problem with the texture of the sensor platelets in
IW-buffered runs, we recommend using > 6 µm Ir powder
rather than increasing the run time.
The EPMA measurements of the IrFe alloy reveal small
amounts of carbon, Au, and Ni (see supplementary infor-
mation). Gold is present in the sample in the form of small
nuggets often attached to the sensor, which made it difficult
to analyse. Such analyses were not taken into account when
determining the alloy composition. Ni contents vary from
0.3 to 2.5 wt% (see supplementary data).
Results of the sensor evaluation demonstrate a homoge-
neous fO2 distribution in the sample material, with ∆logfO2
values near IW + 0.5 (Table 1). If the small Ni impurity is
considered together with Fe, the resulting alloy composition

13
 1  Page 10 of 14
Fig. 6  a Effect of Fe gain in the (filler) sample material placed adja-
cent to the IW-buffer capsule (experiment 1581 5  GPa/1280  °C,
24 h). Note that the Fe addition takes place along grain boundaries of
olivine and does not affect the orthopyroxene composition. b Effect
of Fe gain in IW-buffered experiments produces “flame-like” zones
of Fe-enriched olivine in the olivine container in experiment 1571.
c Reaction of Mo–MoO2 buffer in experiment at 1280  °C, 5 GPa
(experiment 1587). Note the absence of reaction between the buffer
and Au capsule. The presence of pore space indicates that H ­ 2O was
present inside the buffer capsule during the experiment
13
Contributions to Mineralogy and Petrology (2019) 174:1
gives ∆logfO2 values that are shifted systematically to more
reducing conditions by < 0.2 log units. The IW buffer itself
is slightly more oxidised compared to Mo–MoO2 and, how-
ever, delivers similar results in experiments. This is likely
to be due to more effective buffering resulting from Fe infil-
tration from the buffer material. Thus, the IW buffer can
be used for faster achievement of fO2 equilibrium, whereas
the Mo–MO2 buffer can be employed, where a chemically
closed environment is required.
Discussion
Fluid speciation at fO2 ≈ IW buffer
Overall, run products and sensor readings demonstrate
achievement of strongly reduced conditions. Despite wide
differences in run times, temperatures and degree of Fe loss,
fluid compositions remained remarkably consistent. Metal
buffers helped to maintain the low fO2 environment; how-
ever, they experienced strong oxidation, by which up to 40%
of metal reacted to the metal -oxide. This is due to a high
demand for ­H2, which is > 7 times higher than more oxidised
Ni–NiO buffer conditions. Clearly, in the absence of metal
buffers, fluids would be unstable and would shift composi-
tionally towards the water maximum:
O2 + CH4 = C + 2H2 O, (6)
O2 + C2 H6 = 2C + 2H2 O + H2 , (7)
where the oxygen is produced by reaction 2 (also see Mat-
veev et al. 1997). Note that Fe loss to the metal is kinetically
slower compared to the fluid equilibration, Fe diffusion in
olivine or the metal–metal oxide buffer reaction (Matveev
et al. 1997).
Even though the fluid and fO2 controls appear to be suc-
cessful, the absence of water peaks in the Raman spectra is
somewhat unexpected. Our results agree with EOS calcula-
tion by Huizenga (2005) with ~ 3.7 mol% ­H2O, but contra-
dict predictions by Belonoshko and Saxena (1992), Matveev
et al. (1997), and Zhang and Duan (2010) suggesting up
to 32 mol% H ­ 2O at 5 GPa, 1280 °C, and IW conditions,
respectively. It also contrasts with fluid compositions given
by Taylor and Foley (1989) who employed the WC–WO2–C
assemblage to buffer fO2, and found measurable H ­ 2O by gas
chromatography. However, their experiments were reported
to be actively undergoing oxidation during the experiment
by ­H2 loss through the A­ g50Pd50 outer capsule. In addition,
the calculated fO2 of this buffer assemblage relative to IW
is based in part upon a fluid speciation model not unlike
those mentioned above, adding significant uncertainty to the
actual redox conditions of these experiments (i.e., they could
easily have been somewhat more oxidising than thought).
Contributions to Mineralogy and Petrology (2019) 174:1 Page 11 of 14  1
Certainly, 10–100 s of ppm of water can be accommodated
as OH in olivine (Mosenfelder et al. 2006) and orthopy-
roxene (Rauch and Keppler 2002) but not in the volumes
predicted by GFluid. In any case, high OH contents in the
silicate phases necessitate a correspondingly high H ­ 2O activ-
ity in the coexisting fluid phase, which we do not observe.
Finally, “unidentified” water might be present in small
amounts in fluid inclusions (< 5 mol%) and be simply invis-
ible to Raman spectroscopy (Lamadrid et al. 2014). In an
attempt to increase the ­H2O concentration in the fluid, an
Mo-MoO2-buffered test experiment was performed during
which it initially equilibrated at 7 GPa and 1250 °C and was
then subjected to a stepwise cooling down to 800 °C over
2 h. Even over this short time period, the fluid apparently
re-equilibrated within the olivine-hosted inclusions, produc-
ing measureable amounts of H ­ 2O along with C
­ H4 that were
detectable in Raman spectra (Fig. 7). This result not only
demonstrates that ­H2O can be readily detected when it is
present, but it also serves as additional proof for the rapid
kinetics of fluid equilibration and the high sensitivity of fluid
speciation to the P, T, and fO2 conditions of an experiment.
Calculations with the GFluid model (Zhang and Duan
2009, 2010) and (Belonoshko and Saxena 1992) are in a
good agreement with high-pressure experiments by Mat-
veev et al. (1997), who described that they had problems
of ­H2 loss, resulting in a shift in fluid composition towards
the water maximum (more oxidised conditions). Hence, it is
likely that our lower water contents are due to the improved
capsule technique and represent more realistic values com-
pared to the earlier studies. As pointed out by Matveev et al.
(1997) and demonstrated by Ardia et al. (2013), theoretical
EOS calculations tend to overestimate water contents and
underestimate the amount of ­CH4 in fluids at high tempera-
tures and pressures. This is not to say that such speciation
Fig. 7  CH4- and H­ 2O-bearing
fluid inclusions produced in an arbitary
experiment at 7 GPa, where the units
temperature was progressively
lowered during the experiment
from 1250 to 800 °C, see text
host olivine
1000
models are not accurate at more oxidising conditions. In fact,
it is likely that the models reliably reproduce fluid specia-
tion for fO2 conditions at and above the “water maximum”,
where compositions are dominated by ­H2O and C ­ O2 (e.g.,
Tiraboschi et al. 2016). However, the EOS and mixing prop-
erties of C­ H4 are not as well constrained, making prediction
of fluid speciation under reducing conditions problematic.
Implications for the Earth’s mantle
The low solubility of ­CH4 in minerals means that reduced
­CH4-bearing COH fluids have the potential of being stable
at redox conditions observed for the deep portions of the
upper mantle (Frost and McCammon 2008; Woodland and
Koch 2003) and are thus capable of transporting significant
amounts of carbon. If at conditions of ∆logfO2 ≈ IW + 0.5
(at 1280 °C and 5 GPa), the fluid phase is essentially H ­ 2O
free (Table 1) as our results indicate, then the change in fluid
composition during oxidation up to the “water maximum”
will be even more pronounced than predicted by available
speciation models like GFluids. For example, at 1280 °C
and 5 GPa, the ­H2O/(CH4 + H2O) will shift from nearly 0
to ~ 0.95 as the ∆logfO2 changes only 2.1 log units from
IW + 0.5 to IW + 2.6 (water max.), assuming that the GFluid
model is accurate at least for fO2 values down to the “water
maximum”. This means that more ­H2O will be produced per
incremental increase in fO2 than previously thought (e.g.,
Huizenga et al. 2012; Luth and Stachel 2014). In the context
of redox melting, where H ­ 2O released during oxidation of a
reduced fluid drives partial melting, our results imply that a
smaller degree of oxidation is necessary to produce a given
degree of melting, since the ­H2O activity should increase
more rapidly with changing fO2. This process is driven
by reaction (6) with the constraint that the surrounding
7 GPa, 6h at 1250°C
+ 2h cooling to 800°C
2917 CH4 (L)
5µm
10µm 2722 H2O
C
2000 3000 4000 cm-1
13
 1  Page 12 of 14
peridotite is able to provide the necessary amount of ­O2,
which may not be the case (Luth and Stachel 2014). The
extent to which reaction (6) can proceed also has a direct
effect on the amount of graphite or diamond that may form.
Alternatively, the oxidation of ­CH4 via the equilibrium:
CH4 = C + 2H2 , (8)
can also contribute the crystallisation of graphite or diamond
without requiring a source of ­O2. In this case, the reaction
would shift from left to right through the preferential loss of
­H2 from the immediate surroundings and no partial melting
would necessarily be induced.
The fluids in our experiments also contain unquantified
amounts of ­C2H6 and ­H2 (Fig. 5). The presence of ­H2 is
indirectly indicated by detectable amounts of H ­ 2 having
been incorporated into the crystal structure of the coexist-
ing olivine (Fig. 5d). Under strongly reducing conditions, the
incorporation of ­H2 in olivine and orthopyroxene provides
a local sink for ­H2. This stored ­H2 also has the potential to
produce ­H2O via reaction (1) during subsequent interactions
with relatively oxidised mantle domains, further enhancing
the redox-melting process. On the other hand, oxidation
would also cause an increase in OH defects in olivine and
other mantle phases (Yang et al. 2016), potentially compen-
sating for this effect.
Conclusions
A new triple-capsule design for high-pressure experiments
was tested. We have demonstrated its ability to attain and
maintain the hydrogen fugacity (fH2) at levels corresponding
to Fe–FeO and Mo–MoO2 buffer conditions. The capsule
design is suitable for experimental investigation of deep
mantle fluids, but has a temperature limit corresponding to
the melting point of gold at the pressure and temperature of
interest. An olivine container was used to prevent the Fe loss
from the sample and as a trap for fluid inclusions. A C ­ aF2
pressure-transmitting medium was used to minimise H ­ 2 loss
from the capsule assembly and to promote faster fH2 equilib-
rium in the assembly. To avoid contamination of the sample
materials by the metal–metal oxide oxygen buffer, Fe or Mo
was packed into a gold capsule. Formation of an Au–Fe alloy
led to Fe gain; however, this can be minimised by employing
shorter run times of ~ 20 h. This is sufficient to reach fO2
equilibrium, provided that the mass of the sample is smaller
than the mass of the buffer. The experimental fluid trapped
in inclusions in an olivine container at fO2 ≈ IW is domi-
nantly ­CH4 and contains no detectable ­H2O. This confirms
the success of our design being able to achieve and main-
tain reducing conditions in the presence of a mantle silicate
assemblage. We suggest that methane-rich fluids can exist
13
Contributions to Mineralogy and Petrology (2019) 174:1
at the fO2 levels relevant for the mantle environment (i.e.,
Frost and McCammon 2008; Woodland and Koch 2003).
Acknowledgements  The Deutsche Forschungsgemeinschaft is grate-
fully acknowledged for funding the project WO652/26-1. This work
has benefited from discussions with Daniel J. Frost and Sonja Aulbach.
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