Lithos 220–223 (2015) 200–220

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Lithos
journal homepage: www.elsevier.com/locate/lithos

Invited review article

Diamond formation — Where, when and how?

T. Stachel ⁎, R.W. Luth
Department of Earth and Atmospheric Sciences, University of Alberta, Edmonton, AB, T6G 2E3, Canada

a r t i c l e i n f o a b s t r a c t

Article history: Geothermobarometric calculations for a worldwide database of inclusions in diamond indicate that formation of the
Received 25 August 2014 dominant harzburgitic diamond association occurred predominantly (90%) under subsolidus conditions. Diamonds
Accepted 29 January 2015 in eclogitic and lherzolitic lithologies grew in the presence of a melt, unless their formation is related to strongly
Available online 14 February 2015
reducing CHO fluids that would increase the solidus temperature or occurred at pressure–temperature conditions
below about 5 GPa and 1050 °C. Three quarters of peridotitic garnet inclusions in diamond classify as “depleted”
Keywords:
Inclusion in diamond
due to their low Y and Zr contents but, based on LREEN–HREEN ratios invariably near or greater than one, they nev-
Diamond formation ertheless reflect re-enrichment through either highly fractionated fluids or small amounts of melt. The trace element
Solidus signatures of harzburgitic and lherzolitic garnet inclusions are broadly consistent with formation under subsolidus
Redox reaction and supersolidus conditions, respectively. Diamond formation may be followed by cooling in the range
Peridodite of ~ 60–180 °C as a consequence of slow thermal relaxation or, in the case of the Kimberley area in South
Eclogite Africa, possibly uplift due to extension in the lithospheric mantle. In other cases, diamond formation and
final residence took place at comparable temperatures or even associated with small temperature increases
over time.
Diamond formation in peridotitic substrates can only occur at conditions at least as reducing as the EMOD buffer.
Evaluation of the redox state of 225 garnet peridotite xenoliths from cratons worldwide indicates that the vast
majority of samples deriving from within the diamond stability field represent fO2 conditions below EMOD.
Modeling reveals that less than 50 ppm fluid are required to completely reset the redox state of depleted cratonic
peridotite to that of the fluid. Consequently, the overall reduced state of diamond stable peridotites implies that
the last fluids to interact with the deep cratonic lithosphere were generally reducing in character. A further
consequence of the extremely limited redox buffering capacity of cratonic peridotites is that redox reactions
with infiltrating fluid/melt likely cannot produce large diamonds or high diamond grades. Evaluating the shift
in maximum carbon content in CHO fluids during either isobaric cooling or ascent along a cratonic geotherm,
however, reveals that isochemical precipitation of carbon from CHO fluids provides an efficient mode of diamond
crystallization. Since subsolidus fluids are permissible in harzburgites only, and supersolidus melts in lherzolite
we suggest that CHO fluid metasomatism may explain the long observed close association between diamonds
and harzburgitic garnets. In the absence of thermodynamic data we cannot evaluate if supersolidus carbonate-
bearing melts, stable at fO2 conditions below EMOD, would experience a similar decrease in maximum carbon
solubility during cooling or ascent along a geotherm. The absence of a clear association between diamond and
lherzolitic garnets, however, suggests that this is not the case. A very strong association between diamond and
eclogite likely relates to the fact that the transition from carbonate to diamond stable conditions occurs at
redox conditions that are at least about 1 log unit more oxidizing than EMOD. At this time we cannot quantita-
tively evaluate the redox buffering capacity of cratonic eclogites but given their much higher Fe contents it has
to be significantly higher than for peridotites. Alternatively, diamond in eclogite may precipitate directly from
cooling carbonate-bearing melts that may be too oxidizing to crystallize diamond in olivine-bearing lithologies.
© 2015 Elsevier B.V. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 201
2. Diamond substrates in Earth's mantle . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 201

⁎ Corresponding author.
E-mail address: tstachel@ualberta.ca (T. Stachel).

http://dx.doi.org/10.1016/j.lithos.2015.01.028
0024-4937/© 2015 Elsevier B.V. All rights reserved.
 T. Stachel, R.W. Luth / Lithos 220–223 (2015) 200–220 201

3. Pressure–temperature conditions of diamond formation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 201

3.1. Peridotitic suite . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 201
3.2. Eclogitic suite . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 203
3.3. Comparison of temperatures derived from non-touching and touching inclusion pairs: evidence for diamond formation during transient
heating events? . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 204
3.3.1. Peridotitic inclusion pairs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 204
3.3.2. Eclogitic inclusion pairs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 204
3.4. Pressure–temperature conditions of diamond formation and solidi of diamond host rocks . . . . . . . . . . . . . . . . . . . . . . . 204
3.5. Evidence from trace elements in support of melt-present and melt-absent diamond formation . . . . . . . . . . . . . . . . . . . . . 205
4. Timing of diamond growth . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 206
5. Diamond forming reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 207
5.1. Diamond formation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 207
5.2. Oxidized and reduced mineral inclusions in diamond . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 207
5.3. Oxidation state of Earth's upper mantle . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 208
5.4. Fluids in the upper mantle . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 210
5.5. Ascent along lithospheric PT–fO2 path . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 213
5.6. “Isochemical” ascent or isobaric cooling of fluids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 213
5.7. Diamond precipitation from ascending or isobarically cooling melts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 213
5.8. The redox buffering capacity of cratonic peridotite . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 215
6. Diamond forming processes based on co-variations in δ13C–N and on fluid inclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 215
7. Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 216
Acknowledgments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 217
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 217

1. Introduction studies have shown that diamonds derive from subcontinental

Following the discovery of the first kimberlite hosted diamond
deposits in South Africa in 1870–1871, diamond formation was initially
linked to reaction of the kimberlite magma with abundant carbonaceous
shale fragments (crustal xenoliths) present in these diatremes (Lewis,
1887). The subsequent proposal of diamond representing a high-
pressure phenocryst in kimberlite was widely accepted (e.g., Williams,
1932) till the advent of geochemical studies of inclusions in diamond
(Meyer, 1968; Meyer and Boyd, 1972; Sobolev et al., 1969) and radio-
metric dating of diamond formation ages (Kramers, 1979; Richardson
et al., 1984), both implying crystallization in Earth's mantle unrelated
to host kimberlite magmatism. The seminal suggestion of a xenocrystic
origin for diamond in kimberlite (based on the observation of diamond-
iferous eclogite xenoliths), however, already dates back to Bonney
(1899). Since the 1970s, numerous studies covering all important de-
posits around the globe have provided a detailed picture on the miner-
alogical and chemical environment for diamond formation, including
the attendant pressure–temperature conditions (reviewed in Gurney,
1989; Meyer, 1987; Stachel and Harris, 2008). Following the recognition
of diamond as mantle-derived xenocrysts in kimberlite, the concept
emerged that diamond forms via redox reactions (Eggler and Baker,
1982; Luth, 1993; Rosenhauer et al., 1977) that relate to migration of a
fluid or melt through a mantle host rock (Haggerty, 1986) and in conse-
quence, diamond is now generally viewed as a metasomatic mineral
(e.g., Stachel and Harris, 1997; Taylor et al., 1998). Little, however, is
known about the exact composition and the redox character
(carbonate- versus methane-bearing) of the fluids or melts that precip-
itate smooth-surfaced monocrystalline diamonds.
In this contribution we use the large body of published data on
diamonds and their mineral inclusions and less plentiful Fe3 +/Fe2 +
determinations on minerals in cratonic garnet peridotites to discuss
the “where, when and how?” of diamond formation and to place
constraints on possible modes of diamond precipitation that invalidate
some popular models.
lithospheric mantle extending into the diamond stability field
(e.g., Boyd and Gurney, 1986) or may have originated at an even greater
depth (extending to at least 700 km) in the sublithospheric mantle (Harte
and Harris, 1994; Moore and Gurney, 1985; Scott Smith et al., 1984).
Sublithospheric diamonds are, however, rare and the subcratonic litho-
spheric mantle represents the primary source of over 99% (by mass) of
the worldwide diamond production (Stachel and Harris, 2008). In addi-
tion, the sublithospheric diamonds studied so far relate to the recycling
of oceanic lithosphere into the deep mantle (Harte et al., 1999b; Stachel
et al., 2000a, 2000b; Tappert et al., 2005; Walter et al., 2011) and hence
can provide only very limited insights into diamond formation and
storage in pyrolitic upper and lower mantle. For this contribution we
will, therefore, focus exclusively on lithospheric diamonds.
Based on their mineral inclusion content, diamonds from the litho-
spheric mantle (N = 2837) are divided into peridotitic (65%), eclogitic
(33%) and websteritic (pyroxenitic) suites (2%). Using garnet composi-
tions (N = 685), the peridotitic inclusion suite can be subdivided into
harzburgitic (56% of all diamonds), lherzolitic (8%) and wehrlitic
(0.7%) parageneses. The 86:13:1 harzburgite:lherzolite:wehrlite split
of the peridotitic suite is virtually unchanged from the original
pioneering work of Gurney (1984). The 2:1 ratio of peridotitic:eclogitic
suite diamonds is based on destructive studies on diamonds generally
b3 mm in size; it has, however, been speculated that among larger
diamonds the relative proportion of the eclogitic suite may increase
(e.g., Gurney, 1989; Stachel and Harris, 2008). In any case, 33% of all di-
amonds hosted in eclogite far exceed the b 1 to 5% estimated volumetric
abundance of eclogite in subcratonic lithospheric mantle (Dawson and
Stephens, 1975; McLean et al., 2007; Schulze, 1989). Equally, the ratio
of harzburgitic:lherzolitic paragenesis diamonds (~ 7:1) reverses the
relative proportions of harzburgite to lherzolite in diamond stable lith-
ospheric mantle (ca. 1:4 for the Western Kaapvaal Craton; Griffin
et al., 2003). This suggests that compared to lherzolite, harzburgite
and eclogite are strongly preferred substrates for diamond (Grütter
et al., 2004; Gurney, 1984).

2. Diamond substrates in Earth's mantle 3. Pressure–temperature conditions of diamond formation

The mineralogy and the mineral compositions of diamond host rocks 3.1. Peridotitic suite
in Earth's mantle are very well characterized through studies on mineral
inclusions in diamond (reviewed in Gurney, 1989; Meyer, 1987; Meyer Diamond represents a closed system, with even the mobility of hydro-
and Boyd, 1972; Shirey et al., 2013; Stachel and Harris, 2008). These gen being very low (Connell et al., 1998; Saguy, 2004). Non-touching
202 T. Stachel, R.W. Luth / Lithos 220–223 (2015) 200–220

inclusions (i.e., isolated single-phase mineral inclusions) in diamond are,
therefore, assumed to have remained unchanged since encapsulation —
rare cases with microscopically visible exsolution features aside (Leost
et al., 2003). Disequilibrium has been documented among non-touching
inclusions incorporated during diamond growth in chemically evolving
environments (e.g., Bulanova, 1995; Griffin et al., 1988; Rickard et al.,
1989; Stachel et al., 1998). Multiple inclusions in single diamonds suitable
for the application of independent geothermometers allow testing for
possible disequilibrium. Worldwide, 13 diamonds have been studied
containing inclusions of garnet + orthopyroxene + olivine (database of
Stachel and Harris, 2008), allowing to derive temperature estimates
based on the Mg–Fe exchange between both garnet–olivine (O'Neill,
1980; O'Neill and Wood, 1979) and garnet–orthopyroxene (Harley,
1984); accounting for the systematic deviations between the two ther-
mometers documented by Brey and Köhler (1990), the two methods
yield temperature estimates agreeing within uncertainty for 12 of the
diamonds (i.e., N 90% show no evidence for internal disequilibrium;
Supplementary Fig. 1). Adding further evidence derived through detailed
examination of tie-lines connecting coexisting mineral pairs (e.g., Otter
diamond transition (Fig. 1a). The regression line indicates a typical
diamond window – representing the thickness of diamond stable
lithospheric mantle bracketed by the intersections of the local
geotherm with the graphite–diamond transition and the mantle
adiabat – of 95 km thickness (110–205 km depth). Linear regression
of the PNT 00–TNT 00 dataset of Grütter (2009) for garnet lherzolite
xenoliths from the Central Slave Craton yields an almost identical
local geotherm, underscoring that the Central Slave Craton represents
a very appropriate choice as a reference geotherm for cratonic regions
with high diamond potential (Grütter, 2009).
T [˚C]
600 800 1000 1200 1400
3.0
Gr

Lherz+CH4+H2O
ap
and Gurney, 1989; Rickard et al., 1989) and observation of common hit
e

Solidus
Dia Harzburgitic
trace element equilibrium between multiple inclusions (e.g., garnet– mo
4.0 nd
clinopyroxene pairs; Stachel et al., 2000a), disequilibrium between non-
touching inclusions is considered the exception rather than the rule
(Gurney, 1989). On this basis, the pressure–temperature conditions of
Lherzolitic

P [GPa]
diamond formation can be derived through mineral exchange 5.0

Harzb+Carb+H2O
geothermobarometry employing silicate inclusions. In its primary sta- b

Solidus
bility field and at temperatures ≥1000 °C, diamond is not a rigid pres-
sure vessel but will transfer changes in ambient pressure to included 6.0
minerals by means of plastic deformation (De Vries, 1975). Touching Solidus
minerals will thus re-equilibrate under changing pressure–temperature Lherz+Carb+H2O

conditions and, therefore, reflect conditions of the final mantle storage. Solidus
7.0
The geothermobarometers applicable to a comparatively large num- Lherz+H2O
ber of inclusions are: (1.) for garnet–orthopyroxene pairs, the Al 3.0
Gr

TP=1300°C
exchange barometer of Brey and Köhler (1990; PBKN) combined with a

Adiabat
Dia phite
the Mg–Fe exchange thermometer of Harley (1984; THarley) and (2.) for mo
nd
clinopyroxene inclusions assumed to be in equilibrium with 4.0
orthopyroxene and garnet, the single crystal geothermobarometer of
Nimis and Taylor (2000; PNT 00 and TNT 00). The former is applicable to
the dominant harzburgitic and the lherzolitic inclusion paragenesis; 45
P [GPa]

5.0 a
the latter can only be applied to comparatively rare diamonds with
lherzolitic inclusions. The combination of PBKN–THarley owes its relatively
large uncertainty (1 sigma of ~100 °C and 0.5 GPa) mainly to systematic PNT 00-PNT 00
errors in the thermometer calibration (above 1000 °C the thermometer 6.0
Lherzolitic 40
increasingly underestimates temperature; Brey and Köhler, 1990). The PBKN-THarley
experimental calibration of the PBKN barometer extends to 6.0 GPa; Lherzolitic
extrapolation to higher pressures adds additional uncertainty. The better 7.0 Harzburgitic
precision of PNT 00–TNT 00 (~50 °C and 0.3 GPa) only holds to pressure of
35

up to ~ 4.5 GPa; at higher pressure the barometer increasingly underesti-
mates pressure (Nimis, 2002). Application of PNT 00–TNT 00 requires rigor-
ous filtering of clinopyroxene analyses (using cation totals as a quality
criterion and then excluding all compositions outside the experimental
ranges; see Grütter, 2009 for details), which for the current study elimi-
nated 40% of the available data (N = 134).
Fig. 1 illustrates P–T estimates (including 26% touching inclusion
pairs) using the two geothermobarometer combinations discussed
above. Based on 157 independent estimates (82 diamonds with
lherzolitic and 75 with harzburgitic inclusions), the average peridotitic
suite diamond derives from 5.3 ± 0.8 GPa and 1130 ± 120 °C.
Lherzolitic and harzburgitic inclusions yield similar means (5.1 ±
0.8 GPa and 1120 ± 140 °C, and 5.6 ± 0.8 GPa and 1140 ± 90 °C, respec-
tively). The lherzolitic data, however, extend to low temperature condi-
tions (640–970 °C) that are not observed for the harzburgitic inclusion
set. A regression line through the combined dataset is slightly oblique
to the continental heat flow geotherms of Hasterok and Chapman
(2011), crossing from a 39 mW/m2 model geotherm at the intersection
with the mantle adiabat to a 36 mW/m2 geotherm at the graphite
600 800 1000 1200 1400
T [˚C]
Fig. 1. (a): Pressure–temperature estimates for peridotitic suite diamonds based on garnet–
orthopyroxene inclusion pairs (PBKN–THarley) and clinopyroxene inclusions (PNT 00 and
TNT 00). The latter combination is only applicable to the lherzolitic inclusion paragenesis.
The filled red circle and surrounding pale red error ellipse represent the average and 1 stan-
dard deviation for the entire dataset (5.3 ± 0.8 GPa and 1130 ± 120 °C; N = 157). A linear
regression through the dataset (r2 = 0.53) is shown as a red line and represents an average
geotherm for global diamondiferous lithospheric mantle. Continental geotherms (blue
dashed lines with surface heat flow values in mW/m2; Hasterok and Chapman, 2011), a
mantle adiabat for a potential temperature of 1300 °C (Hasterok and Chapman, 2011), and
the graphite–diamond transition (Day, 2012) are shown for reference. (b): Fields of P–T
conditions for lherzolitic and harzburgitic inclusions in diamonds compared to a range of
solidus temperatures in the presence of CHO-fluids. The solidus for hydrous melting of
carbonated lherzolite (red short dashed line) is from Wyllie and Ryabchikov (2000). The
solidi of lherzolite in the presence of a hydrous fluid (red long dashed line) and a reduced
CHO fluid (red dotted line) are from Wyllie and Ryabchikov (2000) and Litasov et al.
(2014), respectively. The solidus of harzburgite in the presence of carbonate and H2O (blue
dashed-dotted line) is taken from Wyllie (1987). The error ellipse around the average
value of P–T estimates for peridotitic suite diamonds is shown as a black dashed line.
 T. Stachel, R.W. Luth / Lithos 220–223 (2015) 200–220 203

The significance of the relatively small difference in average P–T con-
ditions for peridotitic suite diamonds of lherzolitic and harzburgitic para-
genesis is difficult to evaluate as it likely results from iterations in two
different geothermobarometer combinations (e.g., Nimis and Grütter,
2010). Assuming an ~5.0 GPa average pressure, the temperature condi-
tions for diamonds hosted by lherzolite and harzburgite can be
compared based only on the garnet–olivine Mg–Fe exchange
geothermometer (O'Neill, 1980; O'Neill and Wood, 1979; T O'Neill).
Based on TO'Neill (Fig. 2a), harzburgitic (N = 144, average = 1170 ±
120 °C, median = 1170 °C) and lherzolitic (N = 23, average =
1150 ± 170 °C, median = 1170 °C) inclusions yield the same median
values and an equality of means cannot be rejected (Student's t-test at
α = 5%). This suggests that harzburgitic and lherzolitic paragenesis
diamonds grew in different substrates but under comparable P–T
conditions.
3.2. Eclogitic suite
The most widely used and tested thermometer for mantle eclogites is
the garnet–clinopyroxene Mg–Fe exchange thermometer of Krogh
(1988; TKrogh 88). Brey and Köhler (1990) found that TKrogh 88 reproduces
their lherzolite system experiments within about 40 °C (1 sigma) over the
TKrogh 88 [°C]
800 900 1000 1100 1200 1300 1400
40
Eclogitic:
N=144
30 Mean=1170
±110 °C
Median=1160 °C
N 20 b 0.5 GPa and 70 °C higher than those for peridotitic suite diamonds.
entire 900–1400 °C experimental range. Purwin et al. (2013) con-
ducted eclogite system experiments specifically designed to evalu-
ate the effect of highly variable Fe3 +/Fe2 + in their starting materials
over an 800–1300 °C temperature range. They found that, if total iron
is used as input for TKrogh 88, their experiments are reproduced over
the entire temperature range within 60 °C, whilst significant systematic
temperature estimation errors occur when measured Fe2+ is employed.
Consequently, results obtained for eclogitic inclusions in diamond using
total Fe measurements via EPMA and the Krogh (1988) thermometer
can be considered both accurate and precise.
A reliable barometer suitable for mantle eclogites and eclogitic inclu-
sions in diamond is currently not available (Nimis and Grütter, 2010).
Assuming that diamonds hosted by eclogite form at similar pressure as
peridotitic suite diamonds, a fixed value of 5.0 GPa is applied for thermo-
metric calculations.
On this basis, 144 eclogitic garnet–clinopyroxene pairs (including
11% touching inclusion pairs) yield an average equilibration tempera-
ture of 1170 ± 110 °C (median = 1160 °C; see Fig. 2b). This compares
very well to temperatures derived from equally abundant (N = 164)
garnet–olivine pairs (TO'Neill) in peridotitic suite diamonds, which
yield a mean of 1160 ± 110 °C (median = 1140 °C; see Fig. 2a) for
the same assumed pressure. This excellent agreement suggests that
diamonds hosted by peridotite and eclogite indeed share a common
origin within diamond stable lithospheric mantle. In the absence of a
reliable barometer, pressure estimates for mantle eclogites are usually
based on projections of calculated temperatures on independently
derived local geotherms. Following a similar approach (Fig. 3), the
average temperature and one sigma range (1170 ± 110 °C) for eclogitic
inclusions in diamond are projected on both the average Precambrian
shield geotherm of Hasterok and Chapman (2011; 40 mW/m2) and
the peridotitic inclusion-based diamond geotherm (Fig. 1a). A depth of
origin for 70% (samples within 1 sigma) of eclogitic suite diamonds
between 135–190 km is obtained for the average shield geotherm, and
145–200 km for the peridotitic inclusion-based diamond “geotherm”
(Fig. 3). The latter projection results in P–T conditions that are about

10 3.0
Solidus

TP=1300°C
Adiabat
Basalt+H2O Graphite-
Diamond
4.0 Transition
0
Peridotitic
Peridotitic: Diamond
Harzburgitic 45
N=164
P [GPa]

5.0 P-T
30
Mean=1160 ±110 °C Regression
Median=1140 °C
Eclogite+CH4+H2O

6.0
40
Solidus

N 20 a 1 sigma

7.0 Solidus
Eclogite+Carbonate
Lherzolitic
35

10 600 800 1000 1200 1400

T [˚C]

0 Fig. 3. Average temperature and 1 sigma range (1170 ± 110 °C; TKrogh 88 at 5 GPa) for 144
800 900 1000 1100 1200 1300 1400 eclogitic garnet–clinopyroxene inclusion pairs shown as solid red circles and bold red lines,
in a pressure corrected projection onto two geotherms: the 40 mW/m2 average Precambrian
TO’Neill [°C] shield geotherm of Hasterok and Chapman (2011; as labeled) and the peridotitic suite
diamond geotherm at slightly higher pressures (from Fig. 1a). The solidi for hydrous eclogite
Fig. 2. Temperature estimates for diamonds with peridotitic (a; garnet–olivine pairs, TO'Neill) (Kessel et al., 2005; solid green line) and carbonated eclogite (Dasgupta et al., 2004; dashed
and eclogitic inclusions (b; garnet–clinopyroxene pairs, TKrogh 88). Calculations assume a fixed green line) occur at lower temperatures, implying melt present conditions for diamond
pressure of 5.0 GPa. Temperatures above 1400 °C were excluded as they exceed the mantle precipitation in eclogite, except under reducing conditions (IW buffer, with CH4–H2O
adiabat (Fig. 1a) by more than 50 °C. For the eclogitic inclusion set (b), all data from the present; Litasov et al., 2014; long dashed blue line). The hydrous solidus terminates at a
Argyle Diamond Mine were excluded as they represent atypically “hot” conditions (Stachel second critical endpoint (star) between 5–6 GPa (Kessel et al., 2005). Mantle adiabat,
et al., in press). conductive geotherms and graphite-diamond transition as in Fig. 1.
204 T. Stachel, R.W. Luth / Lithos 220–223 (2015) 200–220

3.3. Comparison of temperatures derived from non-touching and
touching inclusion pairs: evidence for diamond formation during
transient heating events?
3.3.1. Peridotitic inclusion pairs
An extensive geothermobarometric study to evaluate differences
between the conditions of diamond formation (8 non-touching pairs)
and final mantle residence (27 touching pairs) was conducted on
garnet–orthopyroxene inclusions in diamonds from the De Beers Pool
kimberlite pipes in South Africa (Phillips and Harris, 1995; Phillips
et al., 2004). Based on a combination of PBKN and THarley it was found
that diamond formation (average non-touching inclusion pairs:
6.2 GPa and 1200 °C) was followed by cooling (average touching
pairs: 5.4 GPa and 1080 °C) by about 120 °C (Phillips et al., 2004).
Recalculating the entire dataset of Phillips et al. (2004) at a fixed pressure
of 5.0 GPa, however, strongly reduces the average temperature difference
to about 60 °C (Fig. 4a). The decrease of 0.8 GPa in pressure may indicate
that the residence history of diamonds in the lithospheric mantle be-
neath Kimberley (Western Kaapvaal) was more complicated than
simple cooling and involved differential uplift of almost 30 km as
well (Phillips et al., 2004). This number compares well to the loss
T O’Neill or Harley [˚C]
900 1000 1100 1200 1300
4
Non-
Panda
touching
3
Touching
Frequency
in lithosphere thickness for the Western Kaapvaal Craton of ~20 km oc-
curring between kimberlite emplacement at Finsch (124 Ma) and Kim-
berley (94–86 Ma; Griffin et al., 2003) and may suggest that the uplift
reflected in the inclusion in diamond data was related to extension of
the lithospheric mantle.
For diamonds from the Panda kimberlite in the Central Slave Craton,
Canada, thermometric data obtained from non-touching (4 pairs) and
touching (4 pairs) garnet–olivine (TO'Neill) and garnet–orthopyroxene
(THarley) pairs indicate that diamond formation was followed by cooling
(Stachel et al., 2003) by about 150 °C (Fig. 4b). Nitrogen aggregation
based thermometry (Leahy and Taylor, 1997; assuming 3 Ga mantle
residence) indicates that time averaged mantle residence temperatures
for Panda diamonds with non-touching pairs (giving diamond forma-
tion temperatures) are on average about 30 °C lower than the mineral
exchange temperatures but about 120 °C higher for diamonds contain-
ing touching inclusion pairs (giving final residence temperatures). This
suggests that slow lithosphere-scale cooling (100 s of million to billion
year time scale) rather than a short lived local heating event associated
with diamond formation (million year time scale) may have occurred in
the Central Slave Craton.
Evidence that diamond formation in peridotite is not invariably
followed by cooling can be drawn from two diamonds each containing
a clinopyroxene and a clinopyroxene–orthopyroxene pair (diamonds
MW-80 from Mwadui in Tanzania and Nam-211 from Namibia). Calcu-
lating TNT 00 at 5.0 GPa, in both cases the single clinopyroxene inclusion
records temperatures about 40 °C lower than the touching pair. These
temperature differences are slightly larger than the error on the temper-
ature estimates (1 sigma of ±30 °C) and suggest that thermal regimes
may also slightly increase following diamond formation.
3.3.2. Eclogitic inclusion pairs

For diamonds hosted by eclogite the presence of touching and non-

touching pairs of garnet and clinopyroxene inclusions can only be confi-
2 b dently identified in literature data for the kimberlites at De Beers Pool
(Phillips et al., 2004), George Creek, USA (Chinn, 1995), and Jagersfontein,
South Africa (Tappert et al., 2005). For De Beers Pool and George Creek,
1 touching inclusions record temperatures that are distinctly lower (differ-
ences in average TKrogh 88 of 100 and 180 °C, respectively; Fig. 5a and b)
than obtained from non-touching pairs, suggesting that diamond forma-
tion was followed by cooling. These results are consistent with a
0 ~ 170 °C cooling estimate (recalculated using TKrogh 88) for eclogitic
clinopyroxene and touching garnet–clinopyroxene in an unsourced
De Beers
Touching diamond initially described by Meyer and Tsai (1976), based on analyses
Pool
of Prinz et al. (1975). In the case of Jagersfontein, the temperatures calcu-
15 lated for touching and non-touching pairs agree within error of the ther-
mometer (touching inclusions indicate temperatures that are 20 °C
Frequency

higher; Fig. 5c). Similarly, at Argyle, for a diamond containing one touch-
10 a ing garnet–clinopyroxene pair and two separate garnets, calculated
temperatures (TKrogh 88) agree to within 10 °C (i.e., within error). So
Non- similar to peridotitic suite diamonds, in some cases formation of eclogitic
touching diamonds is followed by 100–180 °C cooling whilst in other cases
5 diamond formation and ultimate storage take place in a thermally stable
mantle environment.

3.4. Pressure–temperature conditions of diamond formation and solidi of

0
900 1000 1100 1200 1300
T Harley [˚C]
Fig. 4. Temperature estimates for non-touching (blue) and touching (red) peridotitic inclu-
sion pairs in diamonds from the De Beers Pool Mines (a) and the Panda kimberlite of the
Ekati Mine (b). Temperatures were calculated assuming a fixed pressure of 5.0 GPa and are
based on garnet–orthopyroxene (THarley; De Beers Pool and Panda) and garnet–olivine
(TO'Neill; only Panda) inclusion pairs. For De Beers Pool diamonds (a), the average tempera-
ture for non-touching inclusions is 1120 °C versus 1060 °C for touching inclusions (implying
cooling by 60 °C from diamond formation to final mantle residence). For Panda diamonds (b),
the average temperature for non-touching inclusions is 1190 °C versus 1040 °C for touching
inclusions (150 °C drop in temperature from diamond formation to final mantle residence).
diamond host rocks
Based on a layer-by-layer growth mode, smooth-surfaced octahe-
dral diamond is presumed to grow into open space (Sunagawa, 1984),
implying the presence of a melt or a high density fluid. This premise
can be tested by comparing inclusion-based temperature estimates to
experimentally determined solidus temperatures for possible diamond
host lithologies.
Diamond forms as a consequence of the influx of carbon-bearing
fluids/melts into pre-existing substrates (e.g., Haggerty, 1986; Stachel
and Harris, 1997; Taylor and Green, 1988). Since carbonation reactions
 T. Stachel, R.W. Luth / Lithos 220–223 (2015) 200–220 205

800 900 1000 1100 1200 1300 1400 peridotite plus a H2O–carbonate fluid and carbonated peridotite plus
3
H2O are equivalent. The solidus for hydrous melting of carbonated
Jagersfontein
lherzolite shown in Fig. 1b is taken from Wyllie and Ryabchikov (2000)
Non- and based on extrapolation of experiments b3.5 GPa. However, there is
touching
excellent agreement between this extrapolation and the hydrous solidus
2 of carbonated lherzolite between 4.0–6.0 GPa experimentally determined
Frequency

by Foley et al. (2009). In the pressure region shown in Fig. 1b, the hydrous
solidus of lherzolite (from Wyllie and Ryabchikov, 2000; principally based
c on Kushiro et al., 1968) is only about 50 °C higher. P–T estimates
for lherzolitic inclusions dominantly fall above the hydrous solidi for
1 lherzolite and carbonated lherzolite. At lower pressures (≤5.0 GPa equiv-
Touching
alent to ≤160 km depth) there is, however, a group of “low temperature”
(b1050 to b1000 °C) lherzolitic inclusions that were encapsulated by
diamond under sub-solidus conditions. Because of the low solubility of
CH4 and H2 in silicate melts, reduced fluids inhibit melting (Green,
0 1990). In mixed CH4–H2O fluids, due to strong non-ideality, with increas-
George Creek ing CH4 the activity of H2O decreases more rapidly than the actual H2O
6 content in the fluid, leading to a rapid increase in CH4 activity and solidus
temperature (Foley, 2011). The solidus for lherzolite in the presence of a
reduced CHO fluid shown in Fig. 1b (Litasov et al., 2014) is for very reduc-
Non- ing conditions (IW buffered), resulting in a methane dominated fluid with
Frequency

touching a water content increasing from 13% at 3 GPa to 25% at 6 GPa. Tempera-
4
tures in conductively equilibrated peridotites are below the solidus of
b lherzolite in the presence of a reduced fluid (Fig. 1b). The solidus temper-
Touching
ature for harzburgite in the presence of carbonate and H2O (Fig. 1b;
estimate of Wyllie, 1987) is also high and exceeded by only a few
2
harzburgitic inclusions pairs derived from deeper portions of lithospheric
mantle (N 6.0 GPa equivalent to N 190 km). We conclude that subsolidus
fluids (H2O–CO2− 3 to H2O–CH4) are the principal diamond forming
agent in harzburgitic substrates but only play a similar role in lherzolites
0 if either they are reducing (CH4-rich) or diamond formation occurs
De Beers Pool below the H2O–carbonate solidus (i.e., at b 5 GPa along model geotherms
6 b40 mW/m2; Fig. 1).
Under diamond stable conditions the solidus of anhydrous and non-
Non- carbonated metabasalt distinctly exceeds the mantle adiabat (Yasuda
touching et al., 1994). However, similar to their peridotitic counterparts, the
Frequency

4 formation of diamonds in eclogite is related to the influx of fluids and/

a or melts (Ickert et al., 2013; Keller et al., 1998; Taylor et al., 1998). Con-
trary to peridotite, in the presence of a hydrous fluid and along typical
Touching
cratonic geotherms CO2 is not buffered in bimineralic eclogite (Knoche
2 et al., 1999; Luth, 1993). The experimentally determined solidi of
metabasalt in the presence of water (Kessel et al., 2005) or carbonate
(Dasgupta et al., 2004) provide the two most relevant end-member
conditions (Fig. 3). Kessel et al. (2005) found that the hydrous eclogite
0 solidus terminates at a second critical end-point at 5–6 GPa, after
800 900 1000 1100 1200 1300 1400 which the onset of melting cannot be defined anymore. Experiments
T Krogh 88 [˚C] on melting of eclogite under strongly reducing conditions (Litasov
et al., 2014; IW buffered), i.e. in the presence of a methane dominated
Fig. 5. Temperature estimates for non-touching (blue) and touching (red) eclogitic inclusion
fluid (b 20% H2O in the pressure range of Fig. 3), document an ~200 °C
pairs in diamonds from the De Beers Pool Mines (a), George Creek, USA (b) and Jagersfontein, increase in solidus temperature relative to hydrous and carbonated
South Africa (c). Temperatures were calculated assuming a fixed pressure of 5.0 GPa and are eclogite at 5.0 GPa. Our thermometric results for diamonds in eclogitic
based on garnet–clinopyroxene (TKrogh 88) inclusion pairs. For De Beers Pool diamonds (a), substrates indicate that in the presence of water or carbonate, their
the average temperature for non-touching inclusions is 1170 °C versus 1070 °C for touching
formation occurred in a source that was partially molten (Fig. 3). In the
inclusions (i.e., a 100 °C drop in temperature from diamond growth to final mantle
residence). For diamonds from George Creek (b), the average temperature for non-touching presence of a reducing fluid, eclogite melting would only occur in the
inclusions is 1110 °C and for touching inclusions pairs 930 °C, implying cooling by 180 °C. For deeper portions of subcratonic lithospheric mantle (N 5.5 GPa equivalent
Jagersfontein diamonds (c), the average temperature for non-touching inclusions is 1140 °C to N175 km).
versus 1160 °C for touching inclusions (implying an increase in temperature by 20 °C from
diamond genesis to final mantle residence). Excluding the one touching pair yielding a
very high temperature estimate (1380 °C), cooling by 30 °C is derived. Both temperature
3.5. Evidence from trace elements in support of melt-present and melt-
differences for Jagersfontein are within error of the thermometer. absent diamond formation

Fluid and melt metasomatism have distinctive trace element

prevent the migration of CO2 through olivine-bearing rocks at high
pressure (Wyllie and Huang, 1976), the spectrum of oxidized to reduced
fluid species during peridotite melting ranges from H2O–carbonate
through pure H2O and H2O–CH4 to H2O–CH4–H2 (Foley, 2011; French,
1966; Taylor and Green, 1989). With respect to solidus temperature,
signatures, with the ratios of highly to mildly incompatible elements
(e.g., LREE/HREE or Zr/Y) decreasing strongly from fluids to melts
(e.g., Griffin and Ryan, 1995; Stachel et al., 2004; Stosch and Lugmair,
1986). Griffin and Ryan (1995) empirically devised fields in a diagram
of Y versus Zr content in garnet that permit discrimination between
206 T. Stachel, R.W. Luth / Lithos 220–223 (2015) 200–220

low temperature (fluid) metasomatism and melt metasomatism (Fig. 6a).
The majority (about 75%) of garnet inclusions analyzed for these elements
fall into the “depleted” field (Fig. 6a), where no clear distinction of meta-
somatic style can be made below Y b5 ppm and Zr b20 ppm. Plotting the
HREE content (YbN, with N = C1-chondrite normalized) versus the
degree of sinuosity of REEN patterns (NdN/ErN; Fig. 6b), nevertheless
allows to derive evidence for ubiquitous metasomatic overprint for the
strongly depleted group of garnets (as predicted by Frey and Green,
1974). This implies that formation of diamond is typically associated
with mild metasomatic events reflecting low fluid–rock or melt–rock
ratios. For HREE depleted garnets, LREEN–HREEN ratios near or greater
than one imply overprint by a strongly LREE enriched fluid (e.g., Stachel
et al., 2004). For depleted garnets showing some re-enrichment in
HREE, sinuosity of REE patterns is comparatively low (NdN/ErN b 10;
Fig. 6b), suggestive of overall mild metasomatism involving a melt. If all
depleted garnets with NdN/ErN N 20 are interpreted to relate to fluid
metasomatism and all garnets with YbN N 2 to indicate mild melt metaso-
matism, then (with one exception) depleted lherzolitic garnets reflect
melt metasomatism whilst depleted harzburgitic garnets reflect both
mild fluid and mild melt metasomatism (Fig. 6b). About half the depleted
garnets (with YbN b 2 and NdN/ErN b 20), although clearly derived from a
metasomatized source (otherwise NdN/ErN should be ≪1), cannot be
assigned to a particular style of overprint. For the more strongly
metasomatized inclusions (falling outside the “depleted” field in Fig. 6a)
it is evident that lherzolitic garnets have high Y/Zr, typical of melt infiltra-
tion into their host rocks, whereas harzburgitic garnets predominantly
show low Y/Zr (typical for low-temperature metasomatism) but with a
number of exceptions (as predicted from the position of the hydrous
solidus; Fig. 1b). Overall, the trace element evidence hence supports the
conclusions made in Section 3.4. The low-temperature (fluid) metasoma-
tism evident in Fig. 6a is, however, not a simple extension of the fluid
metasomatic trend visible in Fig. 6b, since sinuosity of garnet REEN
patterns actually decreases towards high Zr contents (e.g., all garnets
with Zr N 50 ppm have NdN/ErN b 5). This suggests that increasing Zr
contents are accompanied by decreasing LREE–HREE fractionation in
metasomatic fluids.
It should, however, be noted that such an approach will only identify
the dominant re-enrichment event affecting a diamond source region,
which may not necessarily be the diamond forming event; e.g., during
a thermal pulse a harzburgitic diamond substrate may have been affected
by melt metasomatism, but diamond only formed later, after thermal
relaxation, during a mild fluid metasomatic event that essentially remains
invisible in the trace element signature of inclusions. In fact, Richardson
et al. (1984) concluded that a melt metasomatic event must have preced-
ed diamond formation in the lithospheric mantle beneath Kimberley and
Finsch (Western Kaapvaal) by about 300 Ma, based on unsupported high-
ly radiogenic Sr in harzburgitic garnet inclusions.
4. Timing of diamond growth
Cathodoluminescence imaging reveals that diamonds often have
complex internal growth structures, including oscillatory zoning or
the presence of sharp boundaries that may show evidence for intermit-
tent periods of diamond resorption (e.g., Harte et al., 1999a; Wiggers de
Vries et al., 2013a). In situ studies of micron scale variations in nitrogen
content and carbon isotopic composition demonstrate that such sharp
internal boundaries are often associated with abrupt compositional
changes, which may include switches in the redox character (carbonate
versus methane bearing) of the precipitating fluid/melt (Palot et al.,
2013; Peats et al., 2012; Wiggers de Vries et al., 2013a). Grouping sul-
fides from Mir and 23rd Party Congress (Yakutia) based on their compo-
sition, the nitrogen characteristics and carbon isotopic compositions of
the associated growth zones in their host diamonds, and coexisting
silicate inclusions, Wiggers de Vries et al. (2013b) inferred that these
sulfide groupings likely document protracted diamond growth span-
ning up to ~1 Ga. In this context, diamond formation ages that are not
based on the dating of single inclusions have to be viewed with some
caution. However, the consistency of certain diamond formation ages
within and across cratons (see below) and, in particular, the observed
close agreement of Re–Os sulfide and Sm–Nd silicate isochron ages for
diamonds from individual occurrences (reviewed in Stachel and Harris,
2008) cannot be coincidental and suggest that the temporal extent of
individual diamond growth events is usually well contained within the
uncertainty of the age dates.
Isotopic dating using garnet, clinopyroxene and sulfide inclusions
(reviewed in Gurney et al., 2010; Pearson and Shirey, 1999; Stachel

40 6
Undepleted Lherzolitic
Garnets a Only garnets with b
Harzburgitic Y<5 and Zr<20 ppm
30
Melt

m 4
is
at
om
Y 20 as Yb N
et
M
e lt
M
2
e)
is pit

10
go
m
lo

h
(P
at

Low-T om Fluid
s
Meta
0 0
0 Depleted 50 100 150 0 20 40 60 80
Zr NdN/ErN

Fig. 6. (a): Y versus Zr (wt. ppm) content in peridotitic garnet inclusions in diamond from worldwide sources. Empirical compositional fields and trends are from Griffin and Ryan (1995). The
formation of subcratonic lithospheric mantle (SCLM) involved intense melt extraction and consequently, if no major re-enrichment event occurred, garnets from SCLM plot in the depleted field
(Y b7 ppm and Zr b30 ppm). Low temperature (fluid) metasomatism involves preferential re-enrichment in Zr and is restricted to harzburgitic garnet inclusions. Simultaneous addition of Zr
and Y, attributed to melt metasomatism, is observed for lherzolitic and some harzburgitic garnet inclusions. This is consistent with the observation (see Fig. 1b) that diamond formation mostly
occurs above the solidus of lherzolite (in the presence of a CHO fluid) but below the solidus of harzburgite. The majority of garnet inclusions, however, plot into the depleted field, and for garnets
with Y b5 ppm and Zr b20 ppm assignment to extrapolated metasomatic trends is no longer practical. For such strongly “depleted” garnets (b, right), ubiquitous metasomatic overprint is
nevertheless documented by LREE–HREE ratios (NdN/ErN) invariably near or greater than one. Modest HREE enrichment at low NdN/ErN is interpreted to represent mild melt metasomatism
(trend along the Y-axis) whilst strongly sinusoidal REEN at low HREE (trend along X-axis) document overprint by a strongly fractionated fluid Normalization to C1-chondrite (N) after
McDonough and Sun (1995).
 T. Stachel, R.W. Luth / Lithos 220–223 (2015) 200–220
and Harris, 2008) documents that formation of diamonds occurred
through most of Earth's history (from the Paleoarchean to at least the
Mesozoic). Diamond forming episodes in subcratonic lithospheric mantle
occur on regional to global scales in response to tectonothermal events
such as suturing, subduction and plume impact (e.g., Aulbach et al.,
2009; Gurney et al., 2010; Shirey et al., 2002). Individual diamond
forming episodes may be associated with particular substrates, with
harzburgitic paragenesis diamonds generally yielding Paleoarchean
(3.6–3.2 Ga) ages and lherzolitic paragenesis diamonds forming mostly
in the Paleoproterozoic at about 2 Ga (see references in Gurney et al.,
2010; Stachel and Harris, 2008). Harzburgitic garnet inclusions from
Udachnaya, however, yield a 2 Ga isochron age (Richardson and Harris,
1997), coinciding with the worldwide peak in lherzolitic diamond forma-
tion and younger episodes of peridotitic diamond growth are established
through Mesoproterozoic isochron ages for lherzolitic sulfide inclusions
in diamonds from Ellendale (Western Australia, 1.4 Ga; Smit et al.,
2010), Mir and 23rd Party Congress (the second diamond growth event
in Yakutia, 1.0–0.9 Ga; Wiggers de Vries et al., 2013b), a Mesozoic
isochron age obtained from two peridotitic sulfide inclusions in a single
diamond from Koffiefontein (within error of kimberlite emplacement at
90 Ma; Pearson et al., 1998), and an inferred similar age for a peridotitic
sulfide inclusion from Jagersfontein (Aulbach et al., 2009). Formation of
diamonds hosted by eclogite is documented from the Mesoarchean to
the Neoproterozoic (2.9 and 0.6 Ga) and may well continue up to the
present.
For fibrous coats (overgrowths over pre-existing monocrystalline
diamonds) from Aikhal, Siberia, an Ar–Ar study suggested that the
coat-forming event occurred close to the time of host kimberlite erup-
tion (Burgess et al., 2002). This is consistent with infrared spectroscopic
studies on fibrous diamonds (coats and cuboids) from southern and
western Africa, Siberia and Australia, documenting low nitrogen aggre-
gation states (pure Type IaA; Boyd et al., 1987, 1992) and thereby indi-
cating that their formation likely occurred penecontemporaneously
with and probably initiated by host kimberlite activity (Boyd et al.,
1987, 1992; Gurney et al., 2010). Fibrous coats on diamonds from tertia-
ry kimberlites at Lac de Gras, Canada (Gurney et al., 2004), consequently,
may represent the youngest diamond samples available.
5. Diamond forming reactions
5.1. Diamond formation
Diamond may form in Earth's mantle by a variety of processes:
recrystallization of the low-pressure graphite polymorph, precipitation
from a fluid or melt saturated with carbon, or by oxidation–reduction
reactions involving carbonate or methane.
The direct conversion of graphite to diamond is a reconstructive
phase transition, and in the absence of a flux or solvent requires consid-
erable overstepping of the reaction boundary; Irifune et al. (2004) found
that 15 GPa and 1800 °C, or 12 GPa and 2000 °C were required for this
reaction to proceed in the laboratory in a static compression mode. On
the other hand, graphite is commonly used as a carbon source in exper-
iments that grow diamond in the presence of metal, carbonate, and
silicate melts, as well as CHO fluids at pressure–temperature conditions
much closer to the graphite–diamond reaction curve. The operative
mechanism in these cases would be one of dissolution of graphite into
the melt or fluid, and re-precipitation as diamond resulting from the
higher solubility of the metastable polymorph relative to the stable
one at the experimental P–T conditions.
Industrial syntheses of diamond at high P and T use metallic melts as
growth media. Similar metallic melts may be responsible for diamond
growth in the mantle at depths greater than ~250 km where conditions
become sufficiently reduced to stabilize metal (Frost and McCammon,
2008; Rohrbach et al., 2007, 2011). In the shallower lithospheric mantle,
conditions are typically too oxidized for metal stability. There is no
evidence at present for dissolution of elemental carbon in either silicate
207
or carbonate melts, so precipitation of diamond from such melts would
require an oxidation or reduction reaction. In general, such reactions
could involve reduction of oxidized species such as CO23 − or CO2, or
oxidation of reduced species such as CH 4 . In addition to being
dissolved in silicate or carbonate melts, oxidized species could also
be present as crystalline carbonate or in a fluid. Reduced carbon
could be present in a melt, a fluid, or under very reduced conditions
in phases such as moissanite (SiC; see Di Pierro et al., 2003; Shiryaev
et al., 2011; Ulmer et al., 1998).
Fluids at mantle conditions may contain oxidized carbon-bearing
species such as CO 2 or reduced species such as CH4, depending on
the oxidation state. There is a constraint on CO2 -bearing fluids in
peridotitic lithologies, however. Since the landmark work of a num-
ber of research groups in the 1970s, it has been clear that CO2-rich
fluids would not be stable in oxidized peridotitic mantle, but
would react to form carbonates such as dolomite or magnesite by
reactions such as forsterite + diopside + CO2 → enstatite + dolomite
and forsterite + CO2 → enstatite + magnesite (Fig. 7). Another reaction
relevant to peridotitic mantle is the exchange reaction by which
enstatite and dolomite react to form the higher-pressure assemblage
magnesite and diopside. Comparing these reactions with possible
geotherms for lithospheric mantle (Fig. 7), it is apparent that magnesite
would be the stable carbonate under most circumstances in oxidized
lithospheric peridotitic mantle, and thus carbon would be present in
magnesite rather than in a CO2-rich fluid. At more reduced conditions,
magnesite becomes unstable relative to graphite or diamond via the
reaction enstatite + magnesite → forsterite + graphite/diamond + O2
(the EMOG/EMOD reactions of Eggler and Baker, 1982). Whether the
mantle is sufficiently oxidized to stabilize carbonate requires evaluation
of the evidence that constrains the oxidation state of diamond substrates
in the upper mantle.
5.2. Oxidized and reduced mineral inclusions in diamond
Mineral inclusions in diamond place constraints on the range of redox
conditions associated with natural diamond formation. The upper limit of
1
2
3
100
Gr
Dia
adiabat
4 3
Depth [km]
140
P [GPa]
45
5
180
6
40
7 220
35
700 900 1100 1300 1500
T [°C]
Fig. 7. Pressure–temperature diagram showing the location of the carbonation/
decarbonation reactions (1) enstatite + dolomite = forsterite + diopside + CO2 (Wyllie
et al., 1983) and (2) enstatite + magnesite = forsterite + CO2 (Newton and Sharp, 1975).
In both cases, CO2 is present on the high-temperature, low-pressure side of the reaction
boundary. (3) is the exchange reaction diopside + magnesite = enstatite + dolomite
(Brey et al., 1983) that stabilizes magnesite on the high-pressure side of the reaction. The
35, 40, and 45 mW/m2 geotherms for lithospheric mantle and the 1300 °C mantle adiabat
are from Hasterok and Chapman (2011). Gr–Dia is the graphite–diamond transition from
Day (2012). Magnesite would be the stable carbonate in peridotitic lithospheric mantle
along most geotherms.
208 T. Stachel, R.W. Luth / Lithos 220–223 (2015) 200–220
diamond stability with respect to oxygen fugacity is defined by the pres-
ence of carbonates. Primary inclusions of carbonate (versus secondary
precipitates from original fluid or melt inclusions) are rare but have
been observed in diamonds hosted by both peridotite (magnesite:
Harris et al., 2004; Phillips et al., 2004; Wang et al., 1996) and eclogite
(calcite and dolomite: Meyer and McCallum, 1986; Sobolev et al.,
2009). On the reducing side, diamond stability in mantle peridotite is
limited through metal saturation (Frost and McCammon, 2008; Wood,
1993). Ni-free to Ni-poor native iron inclusions have been observed in
diamonds from Yakutia (coexisting with silicates of harzburgitic para-
genesis; Sobolev et al., 1981), Sloan (Meyer and McCallum, 1986) and
Mwadui (rimmed by wüstite; Stachel et al., 1998). Oxygen fugacities
distinctly below the iron–wüstite buffer (Ulmer et al., 1998) are docu-
mented by the occurrence of moissanite as inclusion in diamonds from
Monastery (Moore and Gurney, 1989), Argyle (Jaques et al., 1989), and
George Creek (Chinn, 1995). In the latter two cases, moissanite co-
existed with silicate inclusions of the eclogitic suite.
Attempts to constrain the fO2 conditions associated with common
inclusions in diamond have so far been limited to the application
of the olivine–orthopyroxene–spinel oxybarometer to diamonds of
peridotitic paragenesis from several kimberlites on the Kaapvaal Craton
(Daniels and Gurney, 1991) and the Limpopo Belt (Kopylova et al.,
1997). Considering all uncertainties, including significant differences
between the various existing calibrations (Ballhaus et al., 1991; O'Neill
and Wall, 1987), the results provide no additional constraints
beyond the limitation of diamond stability to fO2 conditions bounded
by carbonate and Fe–metal forming reactions.
5.3. Oxidation state of Earth's upper mantle
Discussion of the oxidation state of natural samples is usually couched
in terms of their oxygen fugacity, which stems from the use of oxygen
buffers in experimental petrology pioneered by Eugster (1957). These
buffers are assemblages that control the chemical potential of oxygen by
reactions such as:
::
2x Fe þ O2 ¼ 2 Fex O ðiron–wustite; IWÞ
2Ni þ O2 ¼ 2NiO ðnickel–nickel oxide; NNOÞ
:
3 Fe2 SiO4 þ O2 ¼ 2Fe3 O4 þ 3SiO2 ðfayalite–magnetite–quartz; FMQ Þ
4 Fe3 O4 þ O2 ¼ 6 Fe2 O3 ðmagnetite−hematite; MHÞ
For each of these reactions, an equilibrium expression of the form
a6Fe2 O3
KMH ¼
4
a Fe3 O4 f O2
may be written. Combining this equation with that relating the equilib-
rium constant to the standard free energy for this reaction
o
RT lnK MH ¼ −Δr G
produces an expression for fO2 (by convention expressed as log10 fO2) of
the form:
Δr Go
log f O2 ðMH Þ ¼ þ 6 log a Fe2 O3 −4 log a Fe3 O4 ;
2:303RT
which in the case of pure magnetite and hematite reduces to:
o
Δr G
log f O2 ðMH Þ ¼ : et al., 2009, 2010) that yield fascinating insights into the oxidation state
2:303RT
The calculated locations of these reactions in T-log fO2 space at 4 GPa
are shown in Supplementary Fig. 2a. Because these reactions are nearly
parallel in this diagram, much of the relative temperature dependence is
removed by expressing the values of fO2 relative to a reference reaction.
The most common reference in use is the FMQ reaction, such that Δlog
fO2 (FMQ) = log fO2 (sample) − log fO2 (FMQ), changing the T-log fO2
diagram to one expressing T versus Δlog fO2 (FMQ) one (Supplementary
Fig. 2b). These buffer reactions also depend on pressure to varying extents
(Supplementary Fig. 3), so using values of Δlog fO2 (FMQ) to compare
samples from different pressures should be done with the awareness
that such values do not normalize out the pressure dependencies as
effectively as the temperature dependencies.
Turning to the oxidation state of the mantle in the diamond stability
field, the most direct evidence comes from garnet-bearing peridotites.
All four minerals in a garnet peridotite (olivine, orthopyroxene,
clinopyroxene, and garnet) contain Fe2 +; the pyroxenes and garnet
can accommodate Fe3+ to variable extents as well. Various reactions
have been proposed as “oxybarometers” for garnet peridotites; Luth
et al. (1990) outlined five:
2þ 3þ 2þ 2þ
Fe3 Fe2 Si3 O12 ¼ 2 Fe2 SiO4 þ Fe SiO3 þ 0:5O2 ð1Þ
3þ 2þ
Mg3 Fe2 Si3 O12 ¼ MgSiO3 þ Mg2 SiO4 þ Fe2 SiO4 þ 0:5O2 ð2Þ
3þ
2Ca3 Fe2 Si3 O12 þ 6MgSiO3 þ 4Fe
2þ
SiO3
2þ
¼ 6CaMgSi2 O6 þ 4 Fe2 SiO4 þ O2 ð3Þ
3þ 2þ
2 Ca3 Fe2 Si3 O12 þ 2 Fe3 Al2 Si3 O12
¼ 2 Ca3 Al2 Si3 O12 þ 4 Fe2 SiO4 þ 2 FeSiO3 þ O2 ð4Þ
3þ
2Ca3 Fe2 Si3 O12 þ 2Mg3 Al2 Si3 O12 þ 4FeSiO3
¼ 2Ca3 Al2 Si3 O12 þ 4Fe2 SiO4 þ 6MgSiO3 þ O2 : ð5Þ
The thermochemical data available to Luth et al. (1990) restrict-
ed their analysis to the reactions involving the Ca 3 Fe 2 Si 3 O12 end-
member. Following the determination of the free energy of forma-
tion of the Fe3Fe2Si3O12 end-member by Woodland and O'Neill
(1993), Gudmundsson and Wood (1995) experimentally constrained
reactions (1) and (5) at 1300 °C and 2.5–3.5 GPa. They found (1) to be
more precise, and until recently all subsequent studies have used their
calibration for Δlog fO2 (FMQ) based on reaction (1), with the correc-
tion to a typographical error as noted by Woodland and Peltonen
(1999). Oxybarometry of garnet peridotites was revisited recently by
Stagno et al. (2013), who did experiments at 3, 6, and 7 GPa at temper-
atures between 1300 and 1600 °C. They proposed a new calibration
based on reaction (5), which reproduced their data to better precision
than the previous calibration of Gudmundsson and Wood (1995).
There have been a number of studies on the oxidation state of
cratonic garnet peridotites from various localities (Canil and O'Neill,
1996; Creighton et al., 2009, 2010; Goncharov and Ionov, 2012;
Goncharov et al., 2012; Lazarov et al., 2009; Luth et al., 1990;
McCammon and Kopylova, 2004; Woodland, 2009; Woodland and
Koch, 2003; Woodland and Peltonen, 1999; Yaxley et al., 2012). These
studies have produced a dataset of 225 samples from cratons world-
wide, with almost half of the data coming from the Kaapvaal Craton in
southern Africa. Of the samples studied, very few have been document-
ed to contain diamond or graphite. The one graphite-bearing sample
studied by Canil and O'Neill (1996) is a low-pressure sample (2.1 GPa,
710 °C). Two diamond-bearing samples from Finsch have been studied;
one (865) by both Canil and O'Neill (1996) and Lazarov et al. (2009). The
other (F556) is from the Canil and O'Neill (1996) study.
There have also been recent studies of ultrahigh-pressure orogenic
peridotites interpreted to be samples of mantle wedges (Malaspina
in these environments. However, given the focus of this review on
diamond formation in cratonic lithospheric mantle, space prohibits a full
exploration of variations in oxidation state with tectonic environment.
To place the available data on cratonic samples in context in terms of
their depths of origin and the geothermal conditions recorded by their
mineral compositions, they are shown on a P–T diagram (Fig. 8) along
 T. Stachel, R.W. Luth / Lithos 220–223 (2015) 200–220
with conductive reference geotherms and the mantle adiabat from
Hasterok and Chapman (2011). The samples from the Slave Craton
mostly plot between the 35 and 40 mW/m2 geotherms, with a
few recording hotter conditions. The Siberia samples scatter more
widely, whereas those from the Kaapvaal record conditions near the
40 mW/m2 geotherm, with the deepest samples actually plotting
along the extrapolation of that geotherm beyond the mantle adiabat
of Hasterok and Chapman (2011).
To show the oxidation state of these samples, we can plot them on a
depth/pressure versus Δlog fO2 (FMQ) diagram, on which the samples
are placed at the pressure derived from their mineral thermobarometry
(Fig. 9). Temperature would also be increasing with depth (cf. Fig. 8). For
comparative purposes, we also plot the iron–wüstite (IW), EMOG/D,
and graphite–diamond reactions on these diagrams. These reactions
are all calculated for the P–T conditions along a 40 mW/m2 model
geotherm (Hasterok and Chapman, 2011).
The IW curve approximates the fO2 at which metal becomes stable;
as shown by Frost and McCammon (2008), for example, the fO2 at
which Ni-rich metal becomes stable is very close to the location of the
end-member IW reaction (after Ballhaus et al., 1991). The EMOG/D
reactions represent the upper fO2 bound for the stability of graphite or
diamond in olivine-bearing mantle relative to crystalline carbonate.
The “SF10” curves shown in Fig. 9 represent the upper bound when
the carbonate is present as a carbonatitic melt (Stagno and Frost, 2010).
Comparing the oxidation states of these samples calculated using the
calibration of Stagno et al. (2013; “S13”) with those from the calibration
of Gudmundsson and Wood (1995; “GW95”) (Fig. 9a and b), there is
reasonable agreement at low pressure (b 5 GPa), but increasing differ-
ences at higher pressure (Fig. 10), with S13 yielding more oxidized
values. S13 also yields a wider range of values at a given pressure than
GW95 (Fig. 9a and b). For both oxybarometers, calculated Δlog fO2
(FMQ) for a given Fe3 +/ΣFe in garnet becomes more reduced with
increasing depth (Supplementary Fig. 4).
Separating the global dataset allows us to understand better what is
happening on a regional basis. We will consider the two cratons with
the most data: the Kaapvaal and Slave Cratons. The results are illustrated
in Fig. 9c and d, which show the trend to more reduced values with
45
3
100
40
35
adiabat
4 depletion – which would be reflected in both modal mineralogy and
140
Depth (km)
P [GPa]
5 Δlog fO2 (FMQ) to addition or removal of oxygen by interactions with
Gr
Dia
180
6
Kaapvaal
Siberia
Slave
Tanzania
7
Fennoscan 220
700 900 1100 1300 1500
T [°C]
Fig. 8. Global dataset of garnet peridotites with measured Fe3+/ΣFe (garnet). Data at less
than 2.5 GPa (mostly Vitim, southern Siberia data from Goncharov and Ionov, 2012) are
not plotted. The 35, 40, and 45 mW/m2 model conductive geotherms for lithospheric man-
tle and the 1300 °C mantle adiabat are from Hasterok and Chapman (2011). Temperatures
and pressures were taken from the original papers except for those of Luth et al. (1990)
and Canil and O'Neill (1996), which were re-calculated as per Creighton et al. (2009),
i.e., using PBKN (Brey and Köhler, 1990) in combination with TO'Neill (O'Neill, 1980; O'Neill
and Wood, 1979). Blue circles are diamond-bearing peridotites (Canil and O’Neill, 1996;
Lazarov et al., 2009).
209
increasing depth. Some localities show trends with less scatter than
others (e.g., the Early Cretaceous Group II kimberlite at Finsch versus
the Late Cretaceous Group I kimberlites of Kimberley). For the Kaapvaal
Craton, there is also a correlation with texture; the “sheared” peridotites
(open symbols) tend to be more oxidized than the “coarse” ones (filled
symbols).
A first order observation is that there is considerable variability in
the relative oxidation states recorded even by samples from the same
locality. The Kimberley samples from the Kaapvaal Craton and both
the Diavik and Jericho suites from the Slave Craton are excellent exam-
ples of this variability, in that these samples present ranges in Δlog fO2
(FMQ) on the same order as that of the global dataset. This variability
begs the question as to whether these values reflect the differences in
oxidation state(s) at the time of diamond formation, or processes that
post-date diamond formation. If the latter is the case, then the signifi-
cance of the current values is as a record of whether the lithospheric
mantle was “diamond-friendly” or “diamond-hostile”, at least at the
time of sampling by the kimberlite host magma.
What causes the variability observed in either the global dataset or
in individual suites? To address this question, we first need to under-
stand how a peridotite of a given fixed composition, including its FeO
and Fe2O3 contents, would change in relative oxidation state with pres-
sure and temperature along the geotherm. Then, to explain the variation
at a given depth, we need to determine how robust the relative oxida-
tion state values are to modification by interactions with fluids or melts.
Wood et al. (1990) showed that in an isochemical mantle, the rela-
tive oxidation state of garnet peridotite should decrease with depth
along the geotherm because of the change in volume for reactions
that stabilize Fe3+-bearing garnet. This result has been confirmed by
subsequent modeling by a number of workers (Ballhaus and Frost,
1994; Creighton et al., 2009; Frost and McCammon, 2008; Luth and
Stachel, 2014) (Supplementary Fig. 5).
Superimposing the results of the “Luth/Stachel” calculations for
pyrolite with different bulk Fe3+/ΣFe on the global xenolith dataset
(Fig. 11), it is noted that a bulk Fe3+/ΣFe greater than 0.05 would stabilize
carbonate rather than diamond in a pyrolite mantle composition, and that
most samples lie in a field bounded on the low-fO2 side by the 0.02 curve.
It is also clear in Fig. 11 that the variability in Δlog fO2 (FMQ) at a given
depth can be explained by changing the bulk Fe3+/ΣFe of a peridotite —
by adding or removing oxygen, in other words, without requiring any
other compositional change. Confounding this straightforward interpre-
tation of the dataset, however, is the fact that many of the natural samples
are more depleted than pyrolite (and variably so), and thus the effects of
mineral composition – need to be evaluated. How will the more deplet-
ed nature of cratonic peridotite affect the sensitivity of the calculated
fluids or melts? It is reasonable to suppose that decreasing the modal
abundance of Fe3 +-bearing minerals – clinopyroxene and garnet in
particular – should decrease the amount of oxygen required to shift
the fO2 of the rock.
To quantify this, Luth and Stachel (2014) calculated the Δlog fO2
(FMQ) of a peridotite of an arbitrary bulk composition as a function of
bulk Fe3 +/ΣFe, P, and T. Their model, conceptually based on those of
Frost and McCammon (2008) and Stagno et al. (2013), allowed explora-
tion of the effects of changing bulk composition on the relationship
between bulk Fe3+/ΣFe and the calculated Δlog fO2 (FMQ). Using the
pyrolite mantle composition of McDonough and Sun (1995) as a
starting point, they varied the modal mineralogy (and hence the
bulk composition) and found – as anticipated – decreasing the
amount of clinopyroxene and garnet decreased the change in
Fe3 +/ΣFe required to move the fO 2 of a sample from IW to EMOD.
For example, at ~200 km depth (approximating the base of the litho-
sphere), the Fe3+/ΣFe of pyrolite increases from 0.017 at IW to 0.065 at
EMOD (i.e., 382%). For comparison, the Fe3+/ΣFe of a peridotite with 5%
garnet and 5% clinopyroxene would change from 0.009 to 0.026 (289%)
210 T. Stachel, R.W. Luth / Lithos 220–223 (2015) 200–220

a b

EMOG
IW IW
3 100

120
4

Gr Gr 140

Depth [km]
P [GPa]

Dia Dia
5 160

GW95 180
6 Calibration
Kaapvaal
200

EMOD

EMOD
Siberia

SF10
SF10
Slave
S13 Tanzania
7 220
Calibration Fennoscan

c d
EMOG

EMOG
IW IW
3 100

120
4
SF10

SF10
Gr Gr 140

Depth [km]
P [GPa]

Dia Dia
EMOD

5 160

Kimberley 180
Lesotho
6 Frank Smith
EMOD

Monastery
200

EMOD
Cullinan
(Premier)
Gibeon Diavik
7 Finsch Gahcho Kue 220
(Group II) Jericho

-6 -4 -2 0 -6 -4 -2 0
Δlog fO2 (FMQ) Δlog fO2 (FMQ)

Fig. 9. Top figures: Comparison of the oxidation states of 225 garnet peridotites calculated with the Stagno et al. (2013) calibration (a) and with the Gudmundsson and Wood (1995)
calibration (b). Data for samples with pressures b2.5 GPa are omitted. The curves shown are calculated at the pressure–temperature conditions along a 40 mW/m2 geotherm
(Hasterok and Chapman, 2011). Blue circles in (a) are diamond-bearing peridotites (see text). Bottom figures: Comparison of the oxidation states of garnet peridotites from the Kaapvaal
(c) and Slave (d) cratons, both calculated with the Stagno et al. (2013) oxybarometer calibration. In (c), the solid symbols are “coarse” textured samples, open symbols are “sheared”
samples. Darker blue symbols are diamond-bearing samples from Finsch. Abbreviations: IW is the iron–wüstite buffer reaction, Gr–Dia is the graphite–diamond reaction; EMOG/
EMOD is the enstatite + magnesite = olivine + graphite or diamond reaction; SF10 is the calculated location of the analogous reaction involving carbonate melt rather than crystalline
carbonate. IW from Ballhaus et al. (1991). Gr-Dia, EMOG, EMOD reactions calculated from the thermodynamic dataset of Holland and Powell (2011). SF10 curve from Stagno and Frost
(2010).

over the same range in fO2, and that of a peridotite with 2% garnet and 2%
clinopyroxene would increase from 0.007 to 0.016 (228%). They then
modeled some real samples for which modal mineralogy, mineral compo-
sitions, and Fe3+/ΣFe for garnet are available. Their results are shown for
three natural samples and for the model pyrolite composition in Fig. 12.
All three of the natural samples contain less garnet and clinopyroxene
than pyrolite, which shifts their curves on the Δlog fO2 (FMQ)–Fe3+/ΣFe
diagram to the left. The curves for the natural samples are also steeper
than pyrolite, so that they require less increase in Fe3+/ΣFe (and therefore
less O2 added to the sample) to change their fO2 from IW to EMOD.
Applying their model to a larger set of samples, Luth and Stachel
(2014) addressed a simple question: how much O2 is required to shift
the fO2 of cratonic peridotites from IW to EMOD? Luth and Stachel
(2014) demonstrated that only ~ 400 ppm O2 is required to shift the
oxidation state of primitive mantle pyrolite from IW to EMOD. For
depleted peridotites, less than 200 ppm is needed — and for four samples
from Finsch from the study of Lazarov et al. (2009), less than 50 ppm O2 is
needed (Fig. 13).
The study of Luth and Stachel (2014) quantified the extreme sensi-
tivity of the fO2 of depleted lithospheric peridotites to changes in bulk
Fe3+/ΣFe — and therefore to changes in oxygen content that could be
produced by interaction with a melt or fluid, either during the formation
of diamond or subsequently. In order to evaluate the effectiveness of
such an interaction, however, we need to turn our attention to what
we know about possible fluids and melts.
5.4. Fluids in the upper mantle
Fluids in Earth's upper mantle can be modeled in the CHO system,
although evidence from natural samples suggests that chlorine, sulfur,
and nitrogen need to be included in a comprehensive model of mantle
fluids. In addition, the solubility of silicates in fluids, especially those
that are water-rich, increases with increasing pressure to the extent
that a second critical endpoint on the (hydrous) fluid-saturated solidus
of model eclogite has been found at ~6 GPa (Kessel et al., 2005; Fig. 3).
The second critical endpoint is where there can no longer be any distinc-
tion between a solute-rich fluid and a fluid-rich melt — so the solidus
would terminate at this point. The existence of a second critical end-
point on the fluid-saturated solidus of either harzburgite or lherzolite
 T. Stachel, R.W. Luth / Lithos 220–223 (2015) 200–220 211

EMOD
2
-2

Δlog fO2 (FMQ)

P [GPa]

4 -3

5
Kaapvaal MS95 pyrolite
Siberia PHN 5267
-4
6 Slave Finsch F-15
Tanzania Finsch 695
Fennoscan
7 IW
0.00 0.02 0.04 0.06 0.08
-1.0 -0.5 0.0 0.5 1.0 1.5
Δlog fO2 (FMQ)S13 - Δlog fO2 (FMQ)GW95 Fe3+/ΣFe (bulk)

Fig. 10. Differences between the values of Δlog fO2 (FMQ) calculated with the Stagno et al.
(2013) and the Gudmundsson and Wood (1995) oxybarometers plotted as a function of
pressure for the global dataset.
Fig. 12. Δlog fO2 (FMQ) versus Fe3+/ΣFe trends calculated for samples from Finsch and
Cullinan (Premier) compared to the trend for primitive mantle pyrolite. Data sources:
MS95 pyrolite composition of McDonough and Sun (1995), PHN 5267 (Cullinan)
data from Boyd and Mertzman (1987) and Canil and O'Neill (1996), and Finsch data
from Lazarov et al. (2009).

has proven to be more difficult to constrain (indeed, as has the location

of solidi in either lithology — see discussion in Luth, 2014).
As a starting point for our discussion, we will use the CHO system,
given that there are quantitative models for fluids in this system that
allow calculation of composition and speciation under both C-saturated
and C-undersaturated conditions (e.g., Huizenga et al., 2012). The most
recent thermodynamic model for CHO fluids is that of Zhang and Duan
(2009, 2010). The compositions of these fluids are usually depicted in
the CHO ternary (Fig. 14), and the speciation in the fluid can be plotted
as a function of fO2 (Supplementary Fig. 6). In both cases, pressure and
temperature are fixed; these two example figures show the results for
conditions at the base of the lithosphere along a 40 mW/m2 geotherm.
From these diagrams, we see that fluids coexisting with diamond would
be CH4-rich at reduced conditions (IW), nearly pure H2O at the water
maximum (labeled “m” on Supplementary Fig. 6), and water-rich
H2O + CO2 at the maximum fO2 at which diamond would be stable in
olivine-bearing mantle (EMOD). In the absence of olivine, diamond
could coexist with more CO2-rich fluids (dominantly H2O–CO2 mixtures)
example, a fluid at IW contains ~8 mol% oxygen, whereas one at EMOD
contains ~34 mol% O. Because H and C have much lower molar weights
than O, the change is more dramatic in mass units; if the fluids are
expressed in terms of wt. % (of C, H2, and O2), the composition of the
IW fluid is 33 wt.% O2 versus 87 wt.% O2 in the EMOD fluid.
The shape of the carbon–saturation curve also shows how the carbon
content of the fluid changes, and hence how the saturation in diamond
changes, with oxidation state. With increasing fO2, the carbon content
decreases from 20 mol% C in pure CH4 to its minimum value near the
O–H sideline at the composition of H2O. Further oxidation increases the
carbon content to its maximum value of 33 mol% at pure CO2. The impli-
cations for diamond formation are straightforward: oxidation of a
reduced fluid with a starting fO2 at IW will precipitate diamond until con-
ditions of the water maximum are reached. Conceptually, this precipita-
tion can be represented by the reaction CH4 + O2 → C + 2 H2O
O2 required for IW to EMOD shift (ppm)

at higher fO2. 200

The carbon–saturation curve (red curve in Fig. 14) shows the change

carats diamond per metric ton

in fluid composition from CH4-rich to CO2-rich with increasing fO2. For
60 300
150 ppm C
2

4
5
0.06
7

IW
3
0.0

0.0

0.0
0.0
0.0

100 40 200
100

120
Depth [km]

4
P [GPa]

50 20 100
Gr 140
Dia PHN 5267
5 Finsch samples
160
0 0 0
0 2 4 6 8 10 12 14
180
EMOD

6 Modal garnet (wt.%)

200 Fig. 13. Amount of O2 required to shift a sample from IW to EMOD, plotted against the modal
-6 -4 -2 0 garnet in the sample. The right hand axis indicates the amount of elemental carbon (diamond
Δlog fO2 (FMQ) or graphite in ppm and carats per ton) that is precipitated during reduction of CO2 (C:O =
1:2) in the fluid. Finsch samples are cpx-bearing peridotites from Lazarov et al. (2009)
(their samples 695, F-1, F-3, F-5, F-6, F-8, F-11, F-12, F-14, F-15, F-16). Calculated at stated
Fig. 11. Calculated oxygen fugacities for a primitive mantle composition (McDonough and P–T of equilibration for each sample. For comparison to the curves in Fig. 12, samples 695
Sun, 1995) as a function of bulk Fe3+/ΣFe along a 40 mW/m2 geotherm (Hasterok and and F-15 are the most garnet-poor and most garnet-rich points, respectively, of the “Finsch
Chapman, 2011). Numbers at top of curves are the bulk Fe3+/ΣFe of the mantle composition. sample” on this diagram. MS95 pyrolite requires ~400 ppm O2 to shift from IW to EMOD
Oxygen fugacities are calculated with the Stagno et al. (2013) oxybarometer. For reference, (Luth and Stachel, 2014), causing ~150 ppm C (equivalent to 750 carats diamond per metric
the global xenolith database and reaction boundaries from Fig. 9 are shown as well. ton) to precipitate.
212 T. Stachel, R.W. Luth / Lithos 220–223 (2015) 200–220

C The location of the carbon saturation curve in the CHO ternary

Diamond
+ (Fig. 15a). At the water maximum, the solubility of carbon (as CO2 and
Fluid -0.31 CO2
CH4 -5 IW
-4
-3 -1
-2
EMOD
H H2O
Fig. 14. Molar ternary diagram showing the compositions of fluids (red curves) in equilibri-
um with diamond at the base of the lithosphere along a 40 mW/m2 geotherm (192 km,
6.1 GPa, 1356 °C; see Huizenga et al. (2012) for the composition of fluids in equilibrium
with diamond at 5.0 GPa, 1227 °C). The numbers along the curve are values of Δlog fO2
(FMQ). For reference, the location of the Δlog fO2 (FMQ) values for IW and EMOD are
shown as well. Calculated with GFluid (Zhang and Duan, 2010).
(Huizenga et al., 2012; Taylor and Green, 1989). With further oxidation,
the fluid will consume diamond rather than precipitate it. Conversely,
an oxidized fluid coexisting with diamond would have a starting fO2 no
higher than EMOD in a peridotitic mantle, and could only precipitate
diamond upon reduction via CO2 → C + O2 until reaching the water max-
imum. Further reduction of such a fluid would resorb diamond as the fluid
became more C-rich.
The amounts of oxygen involved are not trivial; 119 g O2 have to
be added to 100 g starting IW fluid, and 45 g diamond has to precip-
itate for the fluid to evolve to the water maximum composition at the
P and T conditions of Fig. 14. The amounts of oxygen and carbon
removed from the fluid in reducing an EMOD fluid to the water max-
imum composition are smaller (5.7 g O2 and 1.0 g C per 100 g original
EMOD fluid), because of the compositional proximity of the two
fluids.
moves with changing pressure and temperature (as shown earlier by
Huizenga et al., 2012). It is difficult to show these changes at the scale
of the whole ternary diagram; a more useful approach is to zoom in
by plotting the concentration of carbon in the fluid directly. The concen-
tration of carbon in a carbon-saturated fluid is a strong function of bulk
composition, which can be expressed as molar O/(O + H), equivalent to
the O–H base of the CHO ternary (Fig. 14). Changing temperature has
the largest influence on composition near the water maximum
CH4) increases most strongly with increasing temperature, almost
doubling in amount with a 200 °C increase in temperature. At higher
and lower O/(O + H) than those shown in Fig. 15a, the changes in C
content of the fluid are negligible. The effect of pressure is greatest at
the water maximum as well, with the content of C decreasing with
increasing pressure. In reducing fluids, however, the C content increases
O with increasing pressure.
Because both pressure and temperature increase with depth along
a geotherm, the opposing pressure and temperature effects on the
solubility of C in fluids near the water maximum means that we cannot
predict a priori how the C-saturation surface near the water maximum
will change. Calculating the compositions of the fluids with changing
O/(O + H) at two depths along a 40 mW/m2 geotherm, however,
shows that the carbon content decreases with decreasing depth in
both the water maximum fluid and reduced fluids (Fig. 15b). The effect
drops off rapidly as the fluids become more oxidized than the water
maximum, such that the two curves are coincident by EMOD-like
conditions (O/(O + H) ~ 0.35). The decrease in maximum C content
with ascent in reduced fluids reflects a pressure effect.
Another way to view the change in composition of the fluid along
the geotherm is to look specifically at the water-maximum fluid, and
to see how the solubility of carbon species in that fluid changes. This
fluid has O/(O + H) = 0.333, but the C content in the fluid increases
dramatically, from 0.32 mol% at 3 GPa to 0.91 mol% at 6 GPa. This change
in the C content of the fluid essentially results from the oxygen-
conservative reaction CO2 + CH4 → C + 2H2O.
As well as composition, the speciation in the fluid will change with
depth along the geotherm (Fig. 16). Comparing the curves for X(H2O)
and X(CH4) in the fluid with the global xenolith dataset, most of the
samples plot to the reduced side of the water maximum, and would
coexist with water-rich H2O–CH4 fluids.

10 20
a b
mole % C in C-saturated fluid

8
15

6
10
4

5
2 1556°C
1456°C 192 km
1356°C 120 km
0
0.20 0.25 0.30 0.35 0.40 0.1 0.2 0.3 0.4
O/(O + H) (molar) O/(O + H) (molar)

Fig. 15. (a) Change in the carbon content of diamond-saturated fluid with temperature at 192 km depth as a function of the O/(O + H) of the fluid. The black curve shows the composition of the
fluid at the temperature appropriate for a 40 mW/m2 geotherm at that depth. The other two curves illustrate the increasing solubility of C with increasing temperature. (b) Change in the carbon
content of C-saturated fluid with depth along a 40 mW/m2 geotherm as a function of the O/(O + H) of the fluid. For reference, the O/(O + H) for a C-saturated fluid with fO2 equal to IW is
0.10 at 192 km and 0.03 at 120 km depth. The O/(O + H) for a C-saturated fluid with fO2 equal to EMOD is 0.35 at 192 km and 0.34 at 120 km depth. Calculated with GFluid (Zhang and
Duan, 2010).
 T. Stachel, R.W. Luth / Lithos 220–223 (2015) 200–220 213

0 .0 1

0 .0 5
Because the fluid has to change composition to maintain equilibrium
with a constant-composition mantle as it ascends along the geotherm, a
3 IW source of oxygen (or sink for hydrogen) would be required, in addition
100
to the precipitation of carbon that takes place. If the surrounding mantle
were to act as this source or sink, it follows that the “isochemical
120
4 mantle” assumption would no longer hold, and the mantle would
have to become more reduced with decreasing depth. The ability of
0.8

140 the mantle to do so will be addressed presently, but we will first consid-

Depth [km]
Gr
P [GPa]

Dia
er the case of a fluid cooling isobarically or ascending along the
5 160 geotherm without exchanging O (or H) with the surrounding mantle.

180 5.6. “Isochemical” ascent or isobaric cooling of fluids

0.6

6
0.4

200 What happens to a C-saturated CHO fluid that ascends along the
EMOD
0.2

geotherm “isochemically” — that is, without exchanging either oxygen

7 220 or hydrogen with the surrounding mantle? Given the expansion of the
max

0.8
0.2

0.4

0.2
0.6

0.8

C-saturation curve with ascent along a geotherm (Fig. 15b), an ascent

-6 -4 -2
Δlog fO2 (FMQ)
Fig. 16. Pressure-Δlog fO2 (FMQ) diagram calculated along a 40 mW/m2 geotherm illustrat-
ing how the speciation of CHO fluids changes along the geotherm. Solid gray lines show the
mole fraction of H2O, long dashed gray lines show the mole fraction of CH4, and short dashed
black lines are the mole fraction of CO2 for 1 and 5 mol% CO2; at more oxidized conditions, the
fluid lacks CH4 and is essentially H2O + CO2, so the X(CO2) = 0.2 curve coincides with the
curve for X(H2O) = 0.8. Calculated with GFluid (Zhang and Duan, 2010). For reference, the
global xenolith database and reaction boundaries from Fig. 9 are shown as well.
5.5. Ascent along lithospheric PT–fO2 path
By comparing the change in fO2 of an isochemical mantle composi-
tion and the fluid speciation along the geotherm (Figs. 11 and 16), it is
apparent that a fluid in equilibrium with an isochemical mantle would
become more oxidized at shallower depths. This effect can be illustrated
quantitatively for two values of bulk Fe3+/ΣFe of the primitive mantle
(0.02 and 0.03). In both cases, the fluids coexisting with the mantle
become more oxidized and lower in carbon content with decreasing
depth as they shift to higher O/(O + H) and move along the C-
saturation surface towards the water maximum (Fig. 17).
14
200
12
mole % C in C-saturated fluid
0 in which the O/(O + H) of the fluid remains constant would oversatu-
rate a C-saturated fluid and cause precipitation of diamond. This effect
can be seen from the relative locations of the two C-saturation surfaces
in Fig. 15b — a fluid composition that is C-saturated at 192 km depth
would contain more C than would be stable in the fluid with the same
O/(O + H) at 120 km depth (at least for O/(O + H) ≲ 0.35; that is, for
fluids with fO2 of EMOD or lower).
Along with precipitating diamond, CHO fluids ascending along the
geotherm at constant O/(O + H) will shift to more oxidized values
relative to FMQ (Fig. 18a). Fig. 18a also shows the amount of carbon
that would precipitate from four distinct fluids as a percentage of the
amount of carbon in the original fluid. Arguably, expressing the carbon
precipitation in this fashion fails to account for the effect of the decreas-
ing carbon content in the fluid with increasing O/(O + H). In terms of
the mass of carbon precipitated, more reduced fluids precipitate more
carbon (Fig. 18b), but at a lower percentage simply because they are
more carbon-rich.
The change in carbon content of a diamond saturated fluid with tem-
perature only (i.e., isobaric cooling) suggests an alternative mode of
diamond formation. Fig. 15a shows that the decrease in maximum car-
bon content with temperature is particularly prominent for fluids near
the water maximum. This implies that even fluids that initially were
not saturated in carbon may begin to precipitate diamond during
cooling. A possible scenario for the infiltration of CHO fluids hotter
than ambient mantle is the release of fluid from crystallizing magmas
or mantle plumes. As shown in Section 3.4, diamond formation general-
ly takes place below the wet solidus of harzburgite but above the wet
solidi of lherzolite and eclogite. This effectively limits diamond precipi-
tation from cooling water-rich CHO fluids to harzburgitic substrates as

150
fluid dilution through a melt component would occur in lherzolitic
10
and eclogitic lithologies (except along conductive model geotherms
b40 mW/m2 at pressures b5 GPa; see Fig. 1). This may explain the
8
observed close relationship between harzburgitic (“G10”) garnets and
6 diamond (Gurney, 1984) employed as the principal tool of indicator
200 mineral based diamond exploration. More reducing fluids may also
4 penetrate lherzolitic and eclogitic lithologies due to the higher solidus
temperature associated with such fluids, but as seen in Fig. 15a, the
100 150 change in maximum carbon content of such fluids with temperature is
2
Fe3+/ΣFe = 0.02 negligible.
0 Fe3+/ΣFe = 0.03 100
5.7. Diamond precipitation from ascending or isobarically cooling melts
0.10 0.15 0.20 0.25 0.30 0.35
In the presence of methane-rich fluids, the high solidus temperature
O/(O + H) (molar) of peridotite and to a lesser degree eclogite largely precludes percola-
tion of strongly reducing melts through the lithospheric mantle. There-
Fig. 17. Change in carbon content of a C-saturated fluid in equilibrium with primitive mantle
fore, for melt associated diamond precipitation, likely to dominate in
compositions with constant bulk Fe3+/ΣFe of 0.02 and 0.03 (compare Fig. 11). Numbers by
symbols are depth in km. In both cases, the fluids become more oxidized with decreasing eclogitic and lherzolitic substrates (see Section 3.4), only carbonate-
depth and consequently liberate elemental carbon upon ascent. Calculated with GFluid bearing melts need to be considered. With decreasing carbonate con-
(Zhang and Duan, 2010). tent such melts become stable to fO2 conditions far below the EMOD
214
a
4% 6%
4
IW
Gr
P [GPa]
Dia
5 Dia
6
-4
Δlog fO2 (FMQ)
2.5
g C precipitated per 100 g original fluid
b Δlog fO2 (FMQ)
2.0
1.5
1.0
0.5
0.0
0.1 0.2
O/(O + H) (molar)
Fig. 18. (a) Pressure-Δlog fO2 (FMQ) diagram calculated along a 40 mW/m2 geotherm.
Yellow-orange lines show the trajectory of four CHO fluid compositions ascending along
the geotherm at constant O/(O + H). The numbers at the top of each arrow provide the
percentage of carbon in the original fluid that precipitates during the ascent of each
fluid from 192 to 120 km. The trajectory for the most oxidized fluid, as it is entirely
above the fO2 of EMOD, could only occur in an olivine-free lithology. Curves calculated
with GFluid (Zhang and Duan, 2010). For reference, the global xenolith database
(gray symbols) and reaction boundaries from Fig. 9 are shown as well. (b) Amount of car-
bon precipitated from fluids during ascent along a 40 mW/m2 geotherm, as a function of
O/(O + H). The amount of carbon is expressed as the mass of carbon precipitated from
100 g of the fluid that was present at 192 km. Calculated with GFluid (Zhang and Duan,
2010).
buffer (Fig. 19) and consequently, precipitation of diamond from the
melt is possible. The precipitation of diamond directly from carbonate-
bearing melts would involve an internal redistribution of oxygen and
thus have an oxidizing effect on the residual melt, which ultimately
may stall further diamond precipitation. Percolating carbonate-bearing
melts are in equilibrium with the surrounding peridotitic mantle
(e.g., Hiraga and Kohlstedt, 2009; Watson et al., 1990) and, consequent-
ly, have the full peridotitic mineral assemblage as liquidus phases. In the
absence of adequate thermodynamic data for carbonate-bearing melts
we cannot evaluate if they would experience a similar decrease in max-
imum carbon content as CHO fluids during cooling or ascent along a
geotherm. The possible appearance of diamond on the liquidus of
cooling and evolving carbonate-bearing melts at fO2 conditions below
the EMOD buffer has not been investigated experimentally and, there-
fore, is speculative. The absence of a clear association between diamond
and lherzolitic garnets, however, suggests that this either is not the case
or only rarely occurs.
T. Stachel, R.W. Luth / Lithos 220–223 (2015) 200–220
100
01
0
0 .0
0 .0
0 .1
0 .5
49% 2% 3 IW
120 100
EMOG
120
140 4
Depth [km]
140
Depth [km]
Gr
P [GPa]
160
5 160
180 180
max
EMOD 6
200
EMOD
200
-2 0 7 220
max
-6 -4 -2 0
Fig. 19. Pressure-Δlog fO2 (FMQ) diagram calculated along a 40 mW/m2 geotherm. Light blue
curves show the maximum-fO2 stability of carbonate-bearing melts according to the model
of Stagno and Frost (2010). Numbers at the top of the curves indicate the molar fraction of
CO2 (Xmelt(CO2)) in the melt (pure carbonate melt has Xmelt(CO2) = 0.5). Unlabeled curves
(from left to right) are for Xmelt(CO2) = 0.005, 0.05, 0.2, 0.3, and 0.4.
The high abundance of eclogitic suite diamonds (1/3 of all inclusion-
bearing diamonds) derived from a volumetrically very minor component
of lithospheric mantle (b1% to 5%; Dawson and Stephens, 1975; Schulze,
1989; McLean et al., 2007) implies that a fundamental difference exists
between diamond precipitation in lherzolite and eclogite. The extension
of diamond stability in eclogite, compared to peridotite, by at least one
0.3 0.4 log unit to more oxidizing conditions (shift from EMOD to the DCDD
[dolomite + coesite = diopside + diamond] equilibrium; Luth, 1993)
potentially establishes such a key difference. Relative to pure diopside,
the omphacitic nature of eclogitic clinopyroxene shifts the DCDD equilib-
rium even further to more oxidizing conditions (see Fig. 2 in Luth, 1993).
This expansion of diamond stability to higher fO2 values may strongly
enhance diamond precipitation directly from cooling or upward migrat-
ing carbonate-bearing melts. Alternatively, the redox buffering capacity
of eclogite, which is much more Fe-rich than peridotite, far exceeds that
of cratonic peridotites and, consequently, the possible extent of diamond
precipitation during carbonate reduction is greatly enhanced. Olivine-
free garnet pyroxenite layers with original diamond contents of up to
15 vol.% (preserved as graphite pseudomorphs) embedded in non-
diamondiferous peridotite at Beni Bousera (Pearson et al., 1989) strong-
ly support localized diamond precipitation from melts more oxidizing
than EMOD in olivine-free lithologies. Extreme diamond contents,
such as in the Beni Bousera websterites but also in diamondiferous
eclogite xenoliths (e.g., up to 20% diamond in eclogite xenoliths
from the Jericho kimberlite; Smart et al., 2009) cannot conceivably
result from wall rock buffered redox reactions and, thus, support
an “isochemical” mode of diamond precipitation from cooling or
ascending carbonate-bearing melts. The redistribution of oxygen
within the melt and consequent increase in fO 2 associated with
this “isochemical” mode of diamond precipitation may be alleviated
when continuous flow of percolating melt into eclogite/pyroxenite
involving incremental diamond growth is considered. When such
melts cross from ubiquitous peridotitic lithologies into eclogite,
they will also be out of equilibrium with their new eclogitic wall
rocks, which at fO 2 conditions below the DCDD equilibrium may
enhance diamond precipitation. In any case, that diamond is so
much more abundant in eclogite compared to lherzolite must relate to
the more oxidizing conditions permissive of diamond precipitation in
olivine-free lithologies (Luth, 1993).
 T. Stachel, R.W. Luth / Lithos 220–223 (2015) 200–220
5.8. The redox buffering capacity of cratonic peridotite
As outlined above, redox reactions such as the oxidation of methane
or the reduction of carbonate are thought to be essential aspects of
diamond formation in Earth's upper mantle. Expressing these two
mechanisms by the simple reactions CH4 + O2 = C + 2 H2O and
CO23 − = C + O2 − + O2 demonstrates the fundamental role of O2 in
mass-balancing this process as either a reactant or product. That is not
to say that molecular oxygen per se is involved, but there has to be
another coupled reaction to either produce or consume oxygen to
allow redox precipitation of diamond to occur. A logical candidate for
such a coupled reaction is the iron redox couple, in which reduced
ferrous iron reacts with oxygen to produce oxidized ferric iron. This
reaction, expressed as 4FeO + O2 = 2Fe2O3, could proceed in this
form in iron-bearing melts, but in the assemblage of solid silicates that
make up peridotitic mantle, charge-balance and crystal–chemical con-
straints require more complex reactions to provide or consume oxygen.
These reactions are actually the same reactions previously discussed as
the basis for oxybarometry in mantle peridotites (Eqs. (1)–(5) above).
A key issue, therefore, is the ability of these reactions in the litho-
spheric mantle to act as the necessary source or sink of oxygen to
allow redox precipitation of diamond to occur. In order to address this
question, it is necessary to quantify both the amount of oxygen required
for the redox precipitation of diamond, and the capacity of the mantle to
act as a source or sink for oxygen. The former is reasonably straightfor-
ward, in that the oxygen required can be scaled to the amount of dia-
mond precipitated, assuming that the redox reactions involve either
methane or carbonate. In either case, the molar ratio of O2 to C is 1:1,
which translates into a mass ratio of 2.67 g of O2 per gram of C.
As seen from the previous discussion of the study of Luth and Stachel
(2014), the capacity of mantle peridotite to act as an effective source or
sink of O2 is limited by the sensitivity of its redox state to small changes
in O2 content, at least relative to the much larger amount of O2 required
to change the oxidation state of a CHO fluid. As shown above, b50 ppm
O2 is needed to move the oxidation state of a strongly depleted perido-
tite from IW to EMOD (i.e., b5 mg O2 per 100 g rock) compared to the
119 g O2 that must be added to 100 g IW fluid to move it to the water
maximum composition.
It is also worth noting that the amount of diamond that would precip-
itate as a result of the shift of the oxidation state of even primitive mantle
from IW to EMOD is relatively small (~150 ppm — see Fig. 13). For
comparison, diamond-bearing peridotite xenoliths can have 5500 ppm
diamond (Viljoen et al., 2004).
Luth and Stachel (2014) modeled various scenarios of oxidized
fluids interacting with reduced peridotite and vice versa; their conclu-
sion was that b50 ppm fluid would be required to reset the oxidation
state of depleted peridotite to that of the fluid. Thus, relative to a CHO
fluid, the oxygen buffering capacity of cratonic (depleted) peridotites
is very small, and the ability of such mantle to act as the sink or source
for oxygen necessary for redox precipitation of diamond is quite low.
To allow for the growth of common commercial sized diamonds
through wall rock buffered redox reactions, diffusive transport of
oxygen would need to occur over large distances (10s of cm); diffuse
exchange over such length scales during metasomatic events is incon-
sistent with common evidence for mineral compositional and isotopic
heterogeneity observed on the hand-sample scale in cratonic peridotite
xenoliths (e.g., Burgess and Harte, 1999; Schmidberger et al., 2003 and
references therein).
From the degree of secondary LREE enrichment in cratonic garnet
peridotites, Luth and Stachel (2014) estimated bulk addition of metaso-
matic fluid/melt approximately in the range of 0.1–5 wt.% — that is 20 to
1000 times the maximum amount of fluid required to reset the oxida-
tion state of these rocks. This implies that redox profiles through
subcratonic lithospheric mantle (Fig. 9) have no bearing on Archean
mantle fO2 but merely are a reflection of the redox state of the last
metasomatic fluid/melt passing through a section of lithosphere.
215
Consequently, diamond stable lithospheric mantle sampled, e.g., by
Mesoproterozoic to Cretaceous kimberlites on the Kaapvaal Craton
last interacted with fluids that invariably were more reducing than
the EMOD buffer (Fig. 9c). In contrast, peridotite xenoliths in the Eocene
A154 kimberlite at Diavik (Central Slave Craton) show metasomatic
overprint by fluids/melts that are more variable in character, ranging
from highly reducing to oxidizing (Fig. 9d).
6. Diamond forming processes based on co-variations in δ13C–N and
on fluid inclusions
The isotopic fractionation factor of carbon (ΔCdiamond-fluid) for
precipitation of diamond from reduced (methane-bearing) and oxidized
(carbonate- or CO2-bearing) fluids or melts has opposite signs and, on
this basis, it should be relatively straightforward to derive the
mode(s) of natural diamond formation based on population density
plots of diamond carbon isotopic compositions (Deines, 1980) and
through evaluation of co-variations between δ13C and the compati-
ble trace element nitrogen (Stachel et al., 2009; Thomassot et al.,
2007). Diamonds in a typical kimberlite deposit, however, originate
over a depth range that in some cases encompasses the entire diamond
stable lithospheric mantle and reflect multiple growth episodes (Harte
et al., 1999a; Palot et al., 2013; Wiggers de Vries et al., 2013a, 2013b) rath-
er than single diamond forming events. Variation in the bulk distribution
coefficients for carbon and nitrogen (e.g., through co-precipitation of
other phases) combined with large differences in the concentration of
carbon (major element) and nitrogen (trace element) in the diamond
forming fluids/melts introduce further complexity and may lead to an
apparently decoupled behavior of δ13C and nitrogen concentration. On
this background, discernible correlations between carbon isotopic com-
position and nitrogen content, indicative of a particular mode of forma-
tion, are unlikely to be observed based on bulk diamond analyses even
on the level of individual deposits. The character of diamond forming
fluids/melts, therefore, is difficult to constrain.
Thomassot et al. (2007) presented evidence for diamond formation
from a reduced, methane-bearing fluid, based on a suite of diamonds
recovered from a single garnet–lherzolite xenolith from the Cullinan
(Premier) mine. Nitrogen concentration and aggregation state charac-
teristics suggested that the diamonds in this xenolith are cogenetic; a
linear positive correlation between log N and δ13C for these diamonds,
therefore, appeared to indicate operation of a single diamond forming
process that could be modeled as precipitation from a methane-
bearing fluid or melt. Thomassot et al. (2007) also presented nitrogen
isotopic data (δ15N) for this suite of diamonds and documented a posi-
tive linear correlation with δ13C, implying (based on a methane precip-
itation model) a positive nitrogen isotope fractionation factor. The
subsequent determination of a negative sign of ΔNdiamond-fluid (Petts
et al., 2014, submitted for publication) is incompatible with the model
of Thomassot et al. (2007) and indicates that a more complex growth
event (e.g., fluid mixing or co-precipitation of nitrogen free phases)
occurred. Consequently, to date there is no compelling case of diamond
precipitation from a reducing fluid documented in the literature that is
built on the stable isotope and nitrogen characteristics of diamond itself.
Indirect evidence for diamond precipitation from highly reducing fluids
is, however, provided by reduced inclusions in diamond (e.g., native
iron; see Section 5.2).
Ion microprobes – for high precision analyses equipped with a large
magnetic sector and a multi-collection system – enable the study of
possible co-variations between δ13C and nitrogen content on the level
of individual diamond growth zones. On this spatially highly resolved
level, strongly correlated variations in δ13C and N-content are occasion-
ally observed. To date, the best documented example is diamond 25-S1
recovered from a low-Mg eclogite xenolith from the Jericho kimberlite
(Smart et al., 2011): in its outer core zone, characterized by homogenous
blue CL response, this diamond shows an outward increase in δ13C (and
δ15N; Petts et al., 2014; Petts et al., submitted for publication) coupled
216 T. Stachel, R.W. Luth / Lithos 220–223 (2015) 200–220
with a decrease in nitrogen content. Such a relationship can only be
modeled based on precipitation from an oxidized (carbonate- or
CO2-bearing) fluid or melt (Smart et al., 2011). This conclusion is sup-
ported by the occurrence of (rare) carbonate inclusions in smooth-
surfaced monocrystalline diamond (see Section 5.2). For non-gem fi-
brous diamonds, a clear link to carbonatitic melts (“high density fluids”)
has been established through the study of finely dispersed, micrometer
to nanometer-sized original melt inclusions (e.g., Klein-BenDavid et al.,
2009; Kopylova et al., 2010; Navon et al., 1988). Similar carbonatitic
melt inclusions have now also been documented within smooth-
surfaced gem-type diamonds (Weiss et al., 2014), providing strong
evidence that carbonate-bearing melts are an important diamond
forming medium. With decreasing carbonate content, such melts may
represent a spectrum of fO2 conditions from oxidizing (carbonatites)
to reducing (possible for carbonated silicate melts; Fig. 19). In view of
the currently very limited number of in situ studies documenting inter-
nal variations in stable isotope composition and nitrogen content dur-
ing gem-diamond growth, the current absence of clear evidence for
methane-driven diamond precipitation can, however, not be used to
discount its operation in nature. Given the limited buffering capacity
of cratonic peridotites (see Section 5.8), their overall reduced character
(Fig. 9a) clearly implies that they last interacted with a reduced fluid or
melt, documenting upward migration of chiefly reduced fluids through
diamond stable lithospheric mantle. Whilst in the case of CHO fluids this
implies methane as an important component, in melts the carbon
speciation is less straightforward to predict and even at the reducing
conditions of typical diamond stable mantle may still involve carbonate
(see Fig. 19).
Based on these results, natural diamond formation involving
methane- and carbonate-bearing fluids/melts are both possible although
actual diamond based evidence so far points to a strong predominance of
carbonate-bearing diamond forming media.
7. Conclusions
Inclusion based geothermobarometry indicates that peridotitic suite
diamonds typically (1 sigma range about the average) originate from a
140–190 km depth at temperatures between 1040–1250 °C. Regression
of the entire dataset results in a “diamond geotherm” that is slightly
oblique to the model geotherms of Hasterok and Chapman (2011),
increasing from 36 mW/m2 at the graphite–diamond transition to
39 mW/m2 at the intersection with the mantle adiabat (base of the
lithosphere). The resulting “diamond window” (diamond stable region
of the lithospheric mantle) extends from 110–205 km depth. In the ab-
sence of a reliable barometer for garnet–clinopyroxene assemblages,
projection of thermometric data for diamonds hosted by eclogite on
the peridotitic suite “diamond geotherm” indicates derivation mainly
(1 sigma range about the average) from 155–200 km depth and
1060–1340 °C. Projection on the 40 mW/m2 Precambrian shield
geotherm of Hasterok and Chapman (2011) results in a 1 sigma range
of 135–190 km depth at temperatures of 1040–1330 °C. Compared to
the peridotitic suite, typical eclogitic suite diamonds thus show a larger
spread in temperatures extending to higher values.
A detailed comparison of temperature estimates based on non-
touching (diamond formation) and touching (final residence tempera-
ture) inclusion pairs of peridotitic and eclogitic paragenesis indicates
that diamond formation in some cases is associated with elevated tem-
peratures (by about 100–180 °C), whilst in other cases temperatures of
formation and final residence are comparable or final residence may
even occur at slightly elevated (40 °C) temperatures. For peridotitic
suite diamonds from the Panda kimberlite (Central Slave Craton), com-
parison with nitrogen-in-diamond based mantle residence temperature
estimates indicates that cooling after diamond formation was slow
(100 s of millions to billion year time scale), suggesting lithosphere-
scale thermal relaxation (e.g., after impact of a plume) rather than
cooling following a local advective heating event.
Comparison of the geothermobarometric data with hydrous
(-carbonated) solidi indicates that diamond formation in lherzolitic
and eclogitic substrates typically occurs in the presence of a melt, whilst
harzburgitic paragenesis diamonds generally form under sub-solidus
conditions. The increase in solidus temperature associated with reduced
fluids is permissive of melt-absent diamond formation in lherzolite and
eclogite under such conditions. Consequently, for the dominant
harzburgitic paragenesis, diamond formation can only relate to CHO
fluids (without geothermobarometric constraints on fO2, i.e., within
the range from H2O–carbonate to H2O–CH4–H2) whilst for diamonds
hosted by lherzolite and eclogite both melts (carbonatites or silicate
melts with dissolved OH− and CO23 −; e.g., Green and Falloon, 1998)
and reducing fluids need to be considered.
Diamond formation is generally believed to relate to redox reactions
involving either oxidized (carbonate- or CO2-bearing) fluids/melts
interacting with reduced wall rocks or reduced (methane-bearing)
fluids/melts in contact with more oxidized wall rocks. Modeling the
interaction of fluids with depleted cratonic peridotites indicates, how-
ever, that only less than 50 ppm fluid are required to completely reset
the oxidation state of depleted peridotite to that of the fluid. This
extremely limited buffering capacity of cratonic peridotites implies
that redox reactions between fluid and wall rock are not an efficient
way to precipitate diamond and extremely unlikely to produce large
macro-diamonds. An additional implication of the limited buffering
capacity of cratonic peridotites is that fO2 studies on garnet peridotite
xenoliths generally only determine the redox state of the last metaso-
matic fluid/melt that interacted with these rocks. The observation that
the bulk of peridotite xenoliths derived from the diamond stability
field yields fO2 conditions more reducing than the EMOD buffer, conse-
quently, implies that the last metasomatic event in most sections of
deep cratonic lithosphere was reducing in character.
We propose that a much more efficient mode of diamond precipita-
tion is “isochemical” (not involving oxygen exchange with the wall
rock) cooling of CHO fluids or their “isochemical” ascent along a geo-
thermal gradient. In particular for fluids with compositions close to
the water maximum both scenarios are associated with a distinct
decrease in the solubility of carbon species (CH4, CO2 or CO2−3 ), leading
to diamond precipitation in peridotite from fluids more reducing than
the EMOD buffer and in eclogite from fluids more reducing than the
DCDD equilibrium. Incorporating the derived relationships between
diamond forming conditions and hydrous solidi, this mode of diamond
formation will be largely restricted to harzburgitic substrates and thus
may explain the strong association between diamond and harzburgitic
garnets observed worldwide. For melt-associated diamond precipita-
tion, likely to dominate in eclogitic and lherzolitic substrates, the effect
of cooling or ascent along a geotherm cannot be assessed in the absence
of adequate thermodynamic data. The extreme overabundance of
eclogitic suite diamonds (1/3 of all inclusion bearing diamonds belong
to the eclogitic suite but eclogite constitutes only a very minor portion
of lithospheric mantle) indicates, however, that the extension of dia-
mond stability by at least one log unit to more oxidizing conditions
(shift from EMOD to DCDD for olivine-free lithologies) plays a critical
role. This expansion of diamond stability in fO2 space may strongly
enhance diamond precipitation either during redox reactions with such
far more Fe-rich bulk rock compositions or directly from “isochemically”
cooling or upward migrating carbonate-bearing melts. The occurrence
of originally highly diamondiferous garnet pyroxenite layers surrounded
by carbon-free orogenic peridotites (Pearson et al., 1989) strongly
supports preferential carbon capture in olivine-free pyroxenite or
eclogite, specifically in settings more oxidized than EMOD. Extreme
(15–20 vol.%) diamond contents in these garnet websterite layers and
in some kimberlite born eclogite xenoliths, and the occurrence of very
large (cm-sized) diamonds hosted by eclogite appear to be incompatible
with formation during wall rock buffered redox reactions and again favor
an “isochemical” mode of precipitation directly from a fluid or melt more
reducing than DCDD.
 T. Stachel, R.W. Luth / Lithos 220–223 (2015) 200–220
Stable isotope and nitrogen content studies on diamond itself so far
have not provided a conclusive answer as to what the redox state of the
dominant diamond forming fluid/melt may be. Combining the currently
available data from in situ (ion microprobe) studies with the recent
finding of broadly carbonatitic high density fluids (melt inclusions) in
gem diamonds, then diamond formation from carbonate-bearing fluids/
melts can be considered as being well established, but given the current
paucity of conclusive datasets, diamond formation from reducing,
methane-bearing fluids cannot be discounted.
Supplementary data to this article can be found online at http://dx.
doi.org/10.1016/j.lithos.2015.01.028.
Acknowledgments
Marco Scambeluri is thanked for inviting this review paper and
showing both persistence and patience over the two years of writing.
The new concepts presented here matured during fruitful discussions
in particular with Herman Grütter, Jeff Harris, Gerhard Brey and Tom
Chacko. Herman Grütter and Fanus Viljoen are also thanked for their
detailed input during formal reviews. George Read is thanked for show-
ing TS a diamond vein cutting through an eclogite xenolith from Fort a la
Corne, changing TS' thinking about diamond forming processes. TS and
RL both acknowledge funding of their research programs through the
Natural Sciences and Engineering Research Council of Canada (NSERC)
Discovery grants. TS receives additional funding through the Canada
Research Chairs program.
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