Garnet in the Earth’s Mantle

Bernard J. Wood*, Ekaterina S. Kiseeva* and Andrew K. Matzen*

1811-5209/13/0009-421$2.50 DOI: 10.2113/gselements.9.6.421

luminous garnet, (Mg,Fe2+,Ca)3 (Al,Cr) 2Si3O12 , is an important constit-

A
roxene in addition to olivine and
uent of mantle peridotite (~10%) and of the other abundant upper orthopyroxene. Harzburgites and
lherzolites are generally thought
mantle rock, eclogite (~50%). Its unusual crystal chemistry means that to be related to one another,
it strongly prefers some trace elements and confers a “garnet signature” on with harzburgite being the solid
mantle melts. As depth increases from 250 to 600 km, garnet increases in residuum after partial melting of
more fertile “primitive” lherzolite.
abundance in mantle rocks, dissolving large fractions of the other silicates This relationship led Ringwood
and becoming Si rich (majoritic). These compositional changes are observed (1962) to propose that the primi-
in some garnets found as inclusions in diamond. Garnet disappears from tive, or unmelted, mantle has a
composition that is a mixture
mantle assemblages at about 700 km depth, where it is replaced by an even
of residual peridotite (75%) and
denser silicate, perovskite. basalt (25%). In this mantle
KEYWORDS : phase transformations, garnet, mantle peridotite, eclogite, diamond composition, which Ringwood
inclusions, majorite named “pyrolite,” garnet becomes
stable at the expense of spinel at
pressures above 2.8 GPa (>85 km
INTRODUCTION depth; FIG. 1) at the solidus. The reaction relationship
Garnet is a common mineral in crystalline rocks of the between the two aluminous minerals (spinel and garnet)
Earth’s upper mantle and lower crust and occasionally may be represented approximately as:
occurs in volcanic liquids. Garnet is unlike most other
crustal minerals in that Mg and Fe2+ are 8-coordinated by 0.4Ca(Mg,Fe2+)Si2O6 + 3.2(Mg,Fe2+)SiO3 + (Mg,Fe2+)Al2O4 =
oxygen while Al occupies a site with 6-fold coordination clinopyroxene orthopyroxene spinel
(1)
(Mg and Fe2+ are usually 6-fold and Al 4-fold coordinated
(Ca,Mg,Fe2+) 3Al2 Si3O12 + (Mg,Fe2+) 2 SiO4
in other minerals) – garnet crystal chemistry is discussed
garnet olivine
further in Geiger (2013 this issue). As a result of their
high cation coordination numbers, garnets have relatively
o
high densities, low compressibilites and increasing stability At the solidus temperature of 1460 C, the transition from
with increasing pressure. In consequence, garnet-bearing spinel lherzolite to garnet lherzolite takes place over a depth
rocks have higher seismic velocities and densities than interval of about 5 km (Robinson and Wood 1998). The
low-pressure, garnet-free rocks of similar composition, a transformation has a positive pressure–temperature slope of
characteristic that has been used in attempts to constrain ~40 bar/degree but is strongly curved because, as tempera-
the compositions of the lower crust, upper mantle and ture decreases, both the solubility of alumina in pyroxene
transition zone. The high coordination numbers also mean and the disorder of Mg and Al in the spinel decrease. These
that garnet residual to, or fractionating from, silicate liquids changes have the effect of flattening the slope of the transi-
imparts a characteristic geochemical signature on the tion in pressure–temperature space (FIG. 1). The overall
trace element pattern of the product igneous rock. These result is that garnet peridotite is stable only in relatively
properties make garnet a petrologically and geochemically cool and deep parts of the mantle (conditions that are often
important constituent of the upper mantle and transition observed beneath thick cratonic lithosphere); elsewhere,
zone. In this article, we explore garnet’s occurrence in spinel peridotite is the stable form.
the mantle and its influence on the physical properties of Compositionally, peridotitic garnets are composed of about
mantle rocks and on the geochemical properties of mantle- 75% pyrope (Mg Al Si O ), 10% grossular (Ca Al Si O )
3 2 3 12 3 2 3 12
derived silicate melts. and 15% almandine (Fe 2+ Al Si O ). They have lower
3 2 3 12
magnesium numbers [Mg# = molar Mg/(Mg+Fe2+)] than
GARNET IN UPPER MANTLE PERIDOTITES coexisting olivines, and the partitioning of Mg and Fe2+
Mantle rocks are observed at the surface either as tectonic between garnet and olivine provides a useful geothermom-
fragments (kilometre scale) or as inclusions in explosive eter for peridotites (O’Neill and Wood 1979).
eruptive rocks (centimetre scale). The majority of samples At pressures above the spinel stability field, garnet incor-
are peridotites, either harzburgites (~85% olivine, 15% porates the chromium and Fe 3+ that are released on
orthopyroxene) or lherzolites, which contain clinopy- spinel breakdown. These elements substitute for Al3+ in
the octahedral site. However, in contrast to the calcium
end-members, Ca3Cr2Si3O12 (uvarovite) and Ca3Fe3+2Si3O12
* Department of Earth Sciences, University of Oxford (andradite), which are stable at crustal pressures, the Mg–
South Parks Road, Oxford OX1 3AN, UK Cr and Mg–Fe3+ end-member garnets are very unstable.
E-mail: berniew@earth.ox.ac.uk

E LEMENTS , V OL . 9, PP. 421–426 421 D ECEMBER 2013

 3.5 of the transition zone (410–660 km depth). In this depth
interval, fertile peridotitic mantle becomes a biminer-
GPa 100 alic rock consisting of ~65% wadsleyite or ringwoodite
3 (both high-pressure forms of olivine) and ~35% garnet

Depth
(Ringwood 1991). The increase in the modal proportion

km
of garnet takes place gradually over a wide depth interval
2.5 Garnet due to pyroxene breakdown and its dissolution into the
75 garnet structure as Mg and Si are transferred from 6- and
peridotite 4-coordination in pyroxene to mixtures of 8- and 6-coordi-
2 nation and 6- and 4-coordination, respectively, in garnet.
The continuous reactions result in increasing densities and
Solidus seismic velocities of the mantle and may be simplified as
1.5 Spinel 50 follows:
peridotite
4(Mg,Fe2+)SiO3 = (Mg,Fe2+) 3 (MgSi)VISi3O12 (3)
1 orthopyroxene majoritic garnet
800 900 1000 1100 1200 1300 1400 1500
Temperature (oC) 2Ca(Mg,Fe2+)Si2O6 = Ca 2 (Mg,Fe2+)(MgSi)VISi3O12 (4)
clinopyroxene majoritic garnet
FIGURE 1 The stability fields of spinel peridotite and garnet
peridotite in pressure–temperature space. The inter- NaAlSi2O6 + Ca(Mg,Fe2+)Si2O6 = NaCa(Mg,Fe2+)(AlSi) (5)
VI Si O
section with the solidus is from Robinson and Wood (1998). The 3 12
extension of the field boundary to lower temperatures is from a clinopyroxene majoritic garnet
number of experimental studies.

The result of dissolution of “excess” Mg (and other divalent

The substitution of Cr and Fe3+ for Al is facilitated by the
addition of Ca to the garnet, an example of the “reciprocal
solution” effect (Wood and Nicholls 1978).
The 6-fold-coordinated sites in garnet can incorporate
enough Fe3+ that their contents can be easily measured
by Mössbauer spectroscopy and calibrated as an oxygen
barometer for garnet peridotites (Gudmundsson and Wood
1995; Stagno et al. 2013). There are several possible ways to
represent the equilibrium between the three iron-bearing
phases, the simplest being:
2Fe2+ 3Fe3+2 Si3O12 = 4Fe2+2 SiO4 + 2Fe2+ SiO3 + O2
garnet (skiagite) olivine orthopyroxene
As mentioned earlier, garnets have higher coordination
numbers and higher densities than olivines or pyroxenes;
“skiagite” garnet, Fe 2+ 3Fe3+ 2 Si3O12 , is no different. This
means that, as pressure increases, the reaction will favour
the reactant, or “skiagite,” side. As a result, at a fi xed oxygen
fugacity relative to a standard buffer, such as fayalite-
magnetite-quartz (FMQ), garnet will become richer in
cations) and Si into garnet (the “majorite” substitution)
is that its Al 2O3 content declines gradually from ~22 to
8 wt% while its CaO content increases from ~4 to 7 wt%
as pressure increases from 3 to 19 GPa and pyroxenes are
absorbed into its structure (Wood 2000).
Beyond 19 GPa (550 km depth), CaSiO3 perovskite becomes
stable in peridotite (FIG. 2) and increasing depth leads to
progressive extraction of Ca from garnet; for example,
at ~23 GPa, which corresponds to the appearance of
(Mg,Fe2+)SiO3 perovskite, the CaO contents of garnet are
lower than 4 wt% (Wood 2000). Perovskite initially forms
at the expense of ringwoodite, but as pressure increases,
(2) the majoritic [(Mg,Fe2+) 3 (MgSi)VISi3O12 ] component of the
garnet begins to dissolve in the (Mg,Fe)SiO3 perovskite,
increasing the alumina content of the remaining garnet
(Wood 2000). Eventually the (Mg,Fe 2+)SiO3 perovskite
dissolves the remaining aluminous garnet as the compo-
nents Al 2O3, Fe3+ AlO3 and (Mg,Fe 2+)(Al,Fe3+)O2.5 (Frost
and Langenhorst 2002), and garnet disappears from the
peridotite assemblage.
200

Pressure
Fe3+ with increasing pressure. Alternatively, with increasing
Olivine Pyroxene
Depth

GPa
depth, a garnet of fi xed composition (Fe3+ content) will be 300
km

(Mg,Fe) SiO
stabilised at progressively lower oxygen fugacity relative 2 4

to FMQ. Woodland and Koch (2003) measured garnets 400 13

from Kaapvaal craton peridotites and found modest Wadsleyite
increases in Fe3+/Fe 2+ with increasing pressure, due, in 500 Garnet
part, to transfer of Fe3+ from clinopyroxene to garnet
with increasing temperature. Calculated oxygen fugacities, 600 Ringwoodite 21
however, decline relative to the FMQ buffer in the same P–T
interval (Woodland and Koch 2003) because of the stabi- 700 (Mg,Fe)SiO3 perovskite
lisation of skiagite with increasing pressure. Some of the
interesting side effects of this change are that coexisting with up to 5% Al O CaSiO3
800 2 3 29
C–H–O fluid phases should change from CO2 rich to CH4 + (Mg,Fe)O perovskite
rich with increasing depth and that the mantle may have a
900
low enough oxygen fugacity to precipitate Ni-rich metallic 0.4 0.5 0.6 0.7 0.8 0.9 1
alloy at depths greater than 300 km.
Volume fraction
With increasing pressure, mantle peridotite undergoes
several important phase transitions in which garnet is a FIGURE 2 Mineral proportions in fertile peridotite (pyrolite) as
a function of depth in the mantle (Ringwood 1991).
key player (Ringwood 1991). FIGURE 2 shows the proportions Note the increasing modal amount of garnet with depth from
of different phases in peridotitic mantle as a function of 200 to 450 km due to the dissolution of pyroxene into garnet.
depth. The modal amount of garnet increases from about Garnet becomes more majoritic in this depth interval (see text).
10% at the spinel–garnet transition to 35% in the middle

E LEMENTS 422 D ECEMBER 2013

GARNET AND SEISMIC VELOCITIES mantle eclogite xenoliths are Cr-poor, Ca-rich pyrope–
IN THE MANTLE grossular–almandine mixtures with wide variations in the
grossular content (Jacob 2004). Arguably, the most impor-
The densities and elastic properties of garnet and the
tant feature of eclogites is that their bulk compositions
other silicates of the mantle may, in principle, be used
often closely resemble the compositions of basalts. The
to investigate radial and lateral variations in mantle
amount of eclogite in the mantle, its origins, and the part
bulk composition. For example, using predominantly
it plays in petrogenesis are subjects of considerable debate.
low-pressure–low-temperature elastic data, Anderson and
Noting that basalts and eclogites are compositionally
Bass (1986) suggested that the transition zone (410–660
similar but that garnet-rich eclogites are the denser, high-
km) is composed of a relatively garnet-rich composition,
pressure form, it was suggested on a number of occasions
which they called “piclogite.” Piclogite is similar to pyrolite
in the early to mid 20th century that the Moho corresponds
in that it is a mixture of depleted peridotite and basalt, but
to the phase transformation of basalt to eclogite and that
piclogite has much more basalt. The result is that, under
the upper mantle is eclogitic rather than peridotitic.
upper mantle conditions, a piclogitic mantle would have
This model, which would explain basalt genesis as near
abundant pyroxene and garnet and only ~30% olivine
total melting of the upper mantle, was discredited by the
(compared to ~65% olivine for pyrolite). A transition zone
experimental work of D. H. Green and A. E. Ringwood on
of piclogite would move the mantle Mg/Si ratio closer to
the basalt–eclogite transformation (Green and Ringwood
that of the Sun, something that is cosmochemically attrac-
1967). These authors found that the conditions of the
tive. Piclogite’s lower olivine content generates smaller 410
transformation are such that eclogite is stable throughout
and 660 km p-wave discontinuities (olivine–wadsleyite and
most of the continental crust and hence could not be
ringwoodite–perovskite transitions; FIG. 2) than pyrolite,
responsible for the Moho discontinuity under the conti-
but a steeper velocity gradient between the 410 and 660 km
nents. Furthermore, the transformation is spread out over a
discontinuities because of the greater extent of transforma-
considerable pressure interval, unlike the seismically sharp
tion of pyroxene to garnet and higher modal proportion
Moho. With increasing pressure, the pyroxene–plagioclase
of the latter (Anderson and Bass 1986). P-wave velocities
assemblage of basalt is joined by garnet at about 1 GPa,
of piclogite are reasonably consistent with those of the
which grows in modal amount at the expense of plagio-
Preliminary Reference Earth Model (PREM; Dziewonski
clase and pyroxenes. Eventually plagioclase is eliminated
and Anderson 1981), which has discontinuities of 2.6%
when the pressure is sufficiently high for clinopyroxene
and 4.8% in p-wave velocity at 400 and 670 km, respec-
to accommodate all the sodium in the rock as NaAlSi2O6
tively. PREM is based largely on the free oscillations of the
and NaFe3+ Si2O6 components (~2.5 GPa).
Earth, however, and a model based purely on p- and s-wave
velocities, such as ak135 (Kennett et al. 1995), gives larger Although not responsible for the Moho, the basalt–eclogite
discontinuities of 4.0% at 410 km and 5.8% at 660 km. transformation must occur at the tops of subducting slabs
The difficulty of arriving at a defi nitive compositional where mid-ocean ridge basalt (MORB) is converted to the
model based solely on wave speeds is compounded by eclogite assemblage of garnet plus clinopyroxene. At still
lateral variations in seismic velocities and uncertainties higher pressures, eclogite undergoes further phase transfor-
in the elastic properties of the minerals of interest at high mations analogous to those in peridotite, principally, the
pressures and temperatures. Most recent work suggests a conversion of pyroxene components into garnet. FIGURE 4
mantle that is broadly peridotitic (pyrolitic) but with an (Irifune et al. 1986; Ricolleau et al. 2010) illustrates the
increasing proportion of basaltic component in the transi- phase relations of eclogite as a function of depth in the
tion zone and lower mantle (Cobden et al. 2009). Earth. The dissolution of pyroxene components into garnet
leads to a rock that is ~95% garnet at depths of about
ECLOGITES AND RELATED ROCKS 500 km, the remainder being small amounts of excess
IN THE MANTLE SiO2 which crystallises as stishovite at any pressure above
9 GPa. As pressure increases, as for peridotitic composi-
Although most upper mantle xenoliths are peridotites
tions, CaSiO3 perovskite becomes stable at about 18 GPa.
(FIG. 3B), eclogites are a second major lithology in kimber-
As the modal proportion of CaSiO3 perovskite increases,
lite and dominate the xenolith lithologies in five well-
the CaO content and modal proportion of garnet gradu-
documented diamondiferous kimberlite pipes: Roberts
ally decline until (Mg,Fe)SiO3 perovskite becomes stable
Victor and Bobbejaan (South Africa), Zagadochnaya
at about 23 GPa (~660 km). Thereafter, the fraction of
(Russia), Orapa (Botswana) and Koidu (Sierra Leone).
garnet rapidly declines such that beyond 750 km depth,
Eclogites are rocks composed mostly (≥75%) of subequal
(Mg,Fe)SiO3 perovskite, CaSiO3 perovskite, stishovite and a
amounts of garnet and omphacitic clinopyroxene (FIG. 3C).
new aluminous (NAL) and/or a calcium ferrite phase make
Unlike garnets from peridotite lithologies, garnets from

A B C

FIGURE 3 (A) Garnet inclusion in diamond. (B) Garnet peridotite xenolith. (C) Eclogite xenolith.
IMAGES COURTESY OF Z. SPETSIUS (A) AND K. MACDONALD (B)

E LEMENTS 423 D ECEMBER 2013

 200 of other high-pressure minerals trapped as inclusions in

Pressure
diamonds (Harte 2010) reinforce the hypothesis that some
Depth
300 of the diamonds have originated well below the cratons.
Pyroxene
km

GPa
400 13 GARNET AND GEOCHEMISTRY
OF VOLCANIC ROCKS
500 Garnet Considerable effort in both experimental and observational
geochemistry has been expended in trying to understand
600 the controls on the major and trace element composi-
21
tions of melts that are erupted at the surface of the Earth.
Garnet does not crystallise at low pressures in most igneous
700
systems but, in a fertile peridotite, it is stable below ~85 km
(Mg,Fe)SiO3 depth (2.8 GPa) at the mantle solidus (see FIG. 1). Thus, if
800 SiO2 CaSiO3 29
perovskite NAL we can identify a “garnet signature” in eruptive products
stish perovskite
phase we have good reason to believe that there was, at least,
900 some melting taking place at depths greater than 85 km.
0 0.2 0.4 0.6 0.8 1.0
Seismological evidence of melt at the lithosphere–astheno-
Volume fraction
sphere boundary to at least 75 km depth (Qi et al. 1997)
suggests that garnet is likely to be present in the source
FIGURE 4 Composite diagram (Irifune et al. 1986; Ricolleau et al.
2010) showing phase transformations and proportions region of at least some basalts. In this section we review
for an eclogite composition as a function of depth in the Earth. how the presence, or absence, of garnet in the source region
Note that eclogite becomes essentially a garnetite in the deeper affects the trace element geochemistry of melts that we
parts of the transition zone (410–660 km). Stish = stishovite. observe at the surface.
NAL = new aluminous phase, Na-rich
FIGURE 6 shows the chondrite-normalised rare earth element
up the modal mineralogy. Ringwood (1991) argued that (REE) contents of clinopyroxene and garnet from peridotite
subducted oceanic crust would be dominantly composed xenoliths found in the Vitim volcanic field (Ionov et al.
of garnet at 650 km depth and that this “garnetite” should 1993). Although the xenoliths all contain olivine, orthopy-
be less dense than the surrounding peridotite and have the roxene, clinopyroxene and either garnet or spinel, clino-
potential to form a perched basaltic layer in the mantle. pyroxene and garnet are the only minerals that contain
More recent density data indicate, however, that eclogite is significant concentrations of REEs. In spinel peridotites
denser than ambient mantle throughout the lower mantle clinopyroxene is the dominant reservoir of REEs and in
(Ricolleau et al. 2010) and that recycled basalt can subduct garnet peridotite both clinopyroxene and garnet contain
to the core–mantle boundary. significant amounts of REEs. Garnet has a strong preference
for the heavy REEs (HREEs), which means that clinopy-
INCLUSIONS IN DIAMONDS roxene coexisting with garnet is depleted in these elements
(FIG. 6). This leads to the question: if the residue of partial
Although experiments provide constraints on the majorite
melting contains garnet, can its presence in the source
substitution mechanisms (reactions 3–5) in mantle garnet,
region be inferred by examining the REE pattern of the
natural occurrences of majoritic garnet are rare because
eruptive products?
most xenoliths have apparent equilibration pressures of
<7 GPa (<220 km). Under these conditions, as can be seen
from FIGURE 2, the dissolution of pyroxene into garnet has
hardly begun. Therefore, in order to fi nd natural examples
we need to turn to mineral inclusions in diamond (FIG. 3A).
As the most common silicate inclusion in diamonds, garnet
has the potential to provide unique information about old
continental cratons, whose keels extend to depths of more
than 200 km.
Garnets trapped as inclusions in diamonds are generally
attributed to either eclogitic or peridotitic paragenesis
(E-type or P-type, respectively), although there are rare
websteritic varieties. E-type garnet is Cr poor (<0.4 wt%
Cr2O3) and Ca rich, and has lower and more variable Mg#
(45–70). P-type garnet is Cr rich and Ca poor, and has
higher and more consistent Mg# (~80–92) (Stachel and
Harris 2009).
FIGURE 5 shows the compositions of high-pressure garnets
from diamond inclusions (Harte 2010) plotted so as to
highlight the majorite substitutions. As can be seen,
increasing majorite content leads to increasing Si4+, Ti4+
and Na + at the expense of Al3+, Cr3+ and divalent cations.
Although most of the world’s diamonds are interpreted to
have formed within the cratonic lithosphere at depths to
~250 km (Stachel and Harris 2009), comparison of majoritic
garnet inclusions with those of garnet generated in high-
pressure experiments (Kiseeva et al. 2013) indicates that
these particular inclusions come from deeper in the mantle FIGURE 5 Compilation of majoritic garnet compositions
from inclusions in diamonds.
at transition zone depths (410–660 km). Moreover, findings Note that end-member majorite would plot at x = 4, y = 4.
M = divalent cations; pfu = per formula unit.

E LEMENTS 424 D ECEMBER 2013

 U4+ is closer to ro than Th4+. Therefore, in the presence of
garnet, the higher U bulk partition coefficient leads to a
melt enriched in Th compared to U. This means that the
excesses of 230 Th relative to its parent, 238U, observed in
many MORB samples are most readily explained by melting
in the garnet peridotite stability field (Beattie 1993).
Application of the principles discussed above to identi-
fying and quantifying the presence of garnet in the source
regions of igneous rocks is not always unequivocaI. If garnet
was present as a residual phase, we would expect fraction-
ation of MREEs from HREEs, and this has frequently been
reported. For example, Shen and Forsyth (1995) showed
that Sm/Yb ratios in MORB correlate with other geochem-
ical parameters that are believed to indicate melting in
the deeper parts of the asthenosphere. After correcting
for variable enrichment of incompatible elements, they
concluded that the areas with the strongest “garnet signa-
ture” are the areas with the thinnest crust. In these regions,
the relatively cold lithosphere inhibits shallow melting;
Chondrite-normalized rare earth element concentra- thus a greater fraction of the observed MORB was, they
FIGURE 6 argued, produced deep, in the garnet stability field (Shen
tions in clinopyroxene (Cpx) and garnet (Grt) from
spinel (Sp) peridotite and garnet peridotite of Vitim Plateau and Forsyth 1995), and melting ceased relatively deep. In
(Ionov et al. 1993) contrast to this result, Bourdon et al. (1996) showed that
some MORBs have 230 Th/238U activity ratios above unity,
implying melting in the presence of residual garnet. More
FIGURE 7 shows garnet–liquid and clinopyroxene–liquid importantly, these high 230 Th/ 238U activity ratios were
partition coefficients determined in one experiment at observed at ridges with thick crust (Bourdon et al. 1996).
3.0 GPa (Pertermann et al. 2004). The partition coefficients This identification of the isotopic “garnet signature” in
are given by: areas with thick crust is directly opposite to the inferences
[i] xtal of Shen and Forsyth (1995), who identified the “garnet
(Di = ), where [i] xtal and [i] melt signature” in areas of thin crust. One possible way to recon-
[i] melt
cile these confl icting results is through the melting of a
refer to weight concentrations in the crystal and melt heterogeneous source that is a mixture of spinel peridotite
phases. As anticipated, the garnet–liquid partition coeffi- and garnet pyroxenite (Hirschmann and Stolper 1996), but
cients for the heavy REEs, (those with the smallest ionic it is apparent that there is no clear unequivocal interpreta-
radii) are significantly higher than the clinopyroxene– tion of the “garnet signature” in mid-ocean ridge basalts.
liquid values. While the clinopyroxene–liquid partition
coefficients for all REEs are below 1, the garnet–liquid parti-
tion coefficients for the smaller HREEs are close to 10,
with the light REEs (LREEs) being progressively excluded
as the ionic radius increases. The result means that melting
in the presence of significant amounts of residual garnet
will generate liquids exhibiting depletions in the HREEs
relative to the LREEs.
The roughly parabolic relationship between the parti-
tion coefficient and ionic radius was fi rst observed in
the 1960s (Onuma et al. 1968) and quantified in terms
of strain energy by Blundy and Wood (1994). The latter
authors showed that the elastic strain energy introduced
into the crystal lattice when an ion of radius r i is parti-
tioned into a site of radius ro can be systematized and
quantified. If the ion has radius ro then there is no strain
energy of substitution and the partition coefficient, Do, is a
maximum for ions of that charge (Blundy and Wood 1994).
The strain energy of substitution increases in an approxi-
mately parabolic way with the difference between r i and ro ,
yielding a parabolic decrease of D i with radius difference,
as observed (FIG. 7). The ro value of the garnet X-site is
smaller than the ro value of the M2 site in clinopyroxene,
and the garnet site is much “stiffer,” with a higher Young’s
modulus than the clinopyroxene site (Van Westrenen et al.
2001). This means that smaller ions prefer the garnet site
and that garnet discriminates much more strongly than
does clinopyroxene against ions that are different from ro
in radius. Thus, garnets preferentially retain the smaller
HREEs (3 + ions) and are effective at separating, or fraction- FIGURE 7 Experimentally measured crystal–melt partition coeffi -
ating, the middle rare earths (MREEs) from one another. cients for garnet (Grt) and clinopyroxene (Cpx) from a
single experiment at 3 GPa plotted as a function of ionic radius
Similar observations can be made for ions of other charge, (Pertermann et al. 2004). Solid lines are lattice strain fits to the
such as Th4+ and U4+, substituting into garnet and clinopy- data using the model of Blundy and Wood (1994). The filled circles
roxene. Th4+ is larger than U4+ and, in peridotitic garnet, indicate the “best-fit” radius ro.

E LEMENTS 425 D ECEMBER 2013

CONCLUDING REMARKS
We have shown that garnet is an extremely important phase
at high pressures and temperatures in the mantle. Garnet
is denser than other low-pressure ferromagnesian silicates
because of the relatively high coordination numbers of Mg2+
and Fe2+ (both 8-coordination) and Al3+ (6-coordination).
This means that once garnet becomes stable in peridotite
(>85 km depth), it increases in modal amount, from ~10%
to ~35%, by dissolving the low-pressure pyroxenes (which
have the same number of cations per 12 oxygens) into its
structure. A similar but more pronounced change in modal
proportions is found in eclogite compositions in which the
garnet–clinopyroxene assemblage becomes stable at about
70 km depth (Green and Ringwood 1967) and progres-
sively changes from ~30% to ~95% garnet as clinopyroxene
dissolves into the garnet and the latter becomes increas-
ingly majoritic in composition.
The relatively high density and cation coordination
numbers of garnet mean that the pyroxene–garnet trans-
formations discussed above have potentially strong seismic
“signatures” and could enable identification of lateral
compositional heterogeneities in the mantle. They also
mean that garnet can have a profound effect on the trace
element concentrations of melts with which it is in equilib-
rium, providing the potential for distinguishing magmas
by depth of melting. As yet, however, other unquantified
effects mask these two potential applications.
ACKNOWLEDGMENTS
We thank E. Baxter, W. Griffi n and J. Van Orman for
reviews and comments that improved the content and
clarity of this article, and K. Macdonald and Z. Spetsius
for the use of their images. We also acknowledge support
from a European Research Council grant 267764.

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