Earth-Science Reviews 136 (2014) 21–35

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Earth-Science Reviews
journal homepage: www.elsevier.com/locate/earscirev

New insight into polycrystalline diamond genesis from modern

nanoanalytical techniques
Dorrit E. Jacob a,⁎, Larissa Dobrzhinetskaya b, Richard Wirth c
a
Australian Research Council Centre of Excellence for Core to Crust Fluid Systems and Department of Earth and Planetary Sciences, Macquarie University, North Ryde, NSW 2109, Australia
b
Department of Earth Sciences, University of California at Riverside, Riverside, CA 92521-0412, USA
c
Helmholtz Centre Potsdam, GFZ German Research Center for Geosciences, Telegrafenberg, D-14473 Potsdam, Germany

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

Article history: Technical developments in analytical methods that reach nanometer spatial resolution have enabled the interro-
Received 23 December 2013 gation of smaller, submicron-sized inclusions in diamond that had previously been elusive. This has inspired and
Accepted 11 May 2014 enabled studies of non-classical diamond species from different geological settings, resulting in a strongly faceted
Available online 18 May 2014
and dynamic picture of diamond formation. This article reviews the leap of knowledge achieved by employing
state-of-the-art analytical methods with high spatial resolution to polycrystalline diamonds from different
Keywords:
Diamond
settings, i.e. from kimberlite, from crustal ultra-high pressure metamorphic terranes and alluvial carbonados.
Earth's mantle While crustal metamorphic diamonds are generally formed under oxidizing conditions, polycrystalline diamond
Carbonado from the Earth's mantle and carbonado have inclusion suites reflecting variable, and sometimes extreme, redox
Ultra-high pressure metamorphism conditions. Diamond fluid compositions, however, fall in the same compositional field for worldwide diamond
TEM fluids, regardless of their geodynamic environment.
Subduction On the basis of thermodynamic equilibrium data for C–H–O fluids in the mantle we argue that submicron
inclusions in diamonds are products of local remobilization connected to fluid-fluxed partial melting and
redox freezing. Thus, evidence from these inclusions complements information from classical work on larger
inclusions and allows a unique direct insight into the medium in which diamond formed.
© 2014 Published by Elsevier B.V.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22
2. Modern micro- and nanoanalytical techniques applied to diamond . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22
2.1. X-ray tomography and micro-X-ray computed tomography . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22
2.2. Micro-X-ray fluorescence . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 23
2.3. Focused ion beam (FIB) milling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 23
2.4. Transmission electron microscopy (TEM) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 24
2.5. NanoSIMS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 24
3. Polycrystalline diamonds from kimberlitic sources . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 24
3.1. Mineral intergrowths: macroinclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 24
3.2. Oxidation state and clues to formation mechanisms . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 25
3.3. Insights from nano-inclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 26
4. Carbonado . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 27
5. Polycrystalline diamonds from ultrahigh-pressure terranes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 28
5.1. Nanoinclusions in the Erzgebirge polycrystalline diamonds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 28
5.2. Nanoinclusions in the Kokchetav polycrystalline diamonds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 29
5.2.1. Marbles and calcareous-silicate gneisses . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 29
5.2.2. Feldspathic gneisses . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 29
5.3. Diamond-forming fluid media and oxidation state . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 29
5.4. Source of carbon and nitrogen aggregation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 29
5.5. Evidence from fluids for crust–mantle interaction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 30

⁎ Corresponding author. Tel.: +61 298508428; fax: +61 298508943.

E-mail addresses: dorrit.jacob@mq.edu.au (D.E. Jacob), larissa.dobrzhinetskaya@ucr.edu (L. Dobrzhinetskaya), wirth@gfz-potsdam.de (R. Wirth).

http://dx.doi.org/10.1016/j.earscirev.2014.05.005
0012-8252/© 2014 Published by Elsevier B.V.
22 D.E. Jacob et al. / Earth-Science Reviews 136 (2014) 21–35

6. Discussion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 30
6.1. Diamond fluids in the Earth's mantle . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 30
6.2. Diamond fluids in polycrystalline diamonds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 31
6.3. Oxidation conditions recorded by polycrystalline diamonds: a matter of scale . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 31
6.4. Chemical environments for diamond formation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 32
7. Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 32
Acknowledgments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 33
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 33

1. Introduction 2–3 Ma, six of them with well-documented microdiamond occurrences

The study of mineral inclusions in diamonds from kimberlites has
been critical in shaping our current understanding of the formation of
diamond in the Earth's mantle (Navon, 1999; Stachel and Harris,
2008). However, instrumental limitations have, until recently, restricted
studies to micrometer-sized inclusions in larger, monocrystalline
diamonds. Smaller inclusions and inclusions in small diamonds from
kimberlitic and non-kimberlitic settings remained elusive.
Progress in instrumental development now enables accurate chem-
ical and structural analyses at unprecedented spatial resolution, which
has resulted in a leap in our understanding of small-scale, even atom-
scale processes in minerals. These new microanalytical methods have
allowed diamond inclusion studies to be carried to the next level,
as submicron inclusions are now accessible, thus building on a solid
foundation from studies of large inclusions. This has inspired a new
generation of innovative studies of smaller and rarer diamond species,
whose inclusion content had not been accessible before. Here we review
recently developed microanalytical techniques that are not yet routinely
applied in the Geosciences and illustrate the leap in knowledge in the
study of smaller diamonds and their inclusions that these methods
have enabled and will continue to support. We compare and contrast
evidence from classical studies of micrometer-sized inclusion suites
(here referred to as “macroinclusions”) with recent results for submi-
cron inclusions suites (“microinclusions”) focussing on TEM investiga-
tions of focused ion beam (FIB) prepared samples and evaluate the
contribution of these to our current view of diamond formation.
Polycrystalline diamonds are aggregates of diamond crystals with
heterogeneous grain sizes and random orientation. An unusual feature
is that these diamond aggregates can have a highly porous structure
with up to 30% porosity (Heaney et al., 2005), which indicates that
they formed from a volatile-rich medium strongly oversaturated in
carbon (Sunagawa, 1990). Monocrystalline diamonds can contain a
long history of growth and dissolution resulting in complex zonation
patterns (Howell et al., 2012). In contrast, polycrystalline diamonds
form rapidly (Orlov, 1977; Sunagawa, 2005), presenting snapshots of
diamond formation conditions that complement the information from
slowly grown monocrystalline diamond.
Polycrystalline diamonds are found worldwide in rather contrasting
settings. They occur in typical crustal rocks in ultra-high pressure meta-
morphic (UHPM) terranes as well as in kimberlites, the main source of
diamonds from the Earth's mantle, and also in alluvial deposits with
unknown sources.
Kimberlites are volatile-rich exotic magmatic rocks that contain
diamond and mantle xenoliths originating from depths of 150–
N450 km. Polycrystalline diamond is found in Group I kimberlites in
Africa and Siberia where it can locally amount to ca. 20% of the total
diamond production (K. de Corte, pers. comm. 2012). UHPM terranes
occur along continental margins delineating a wide spectrum of
Phanerozoic collisions of continental lithospheric plates (Ernst, 2006;
Ernst and Liou, 2008; Dobrzhinetskaya, 2012; Schertl and Sobolev,
2013). They are composed of metasedimentary and meta-igneous rocks
with continental affinities that were subjected to deep subduction up to
N250 km followed by exhumation. Microdiamonds have been reported
from almost a dozen of UHPM terranes ranging in age from 640 Ma to
(Dobrzhinetskaya, 2012; Schertl and Sobolev, 2013) and two of these
contain polycrystalline diamonds. Lastly, polycrystalline diamond is
found in alluvial deposits, most famous perhaps are the carbonado
diamonds from Brazil and Central Africa, whose sources are as yet
unknown and for which a number of contrasting and mutually exclu-
sive models have been proposed (McCall, 2009).
2. Modern micro- and nanoanalytical techniques applied to diamond
2.1. X-ray tomography and micro-X-ray computed tomography
X-ray tomography provides information about the occurrence and
spatial distribution of fluid and solid-state inclusions in diamond
(Jacob et al., 2011). Amongst the solid inclusions, mineral phases can
be identified by applying techniques such as Raman spectroscopy,
FTIR spectroscopy, X-ray diffraction analysis (Kopylova et al., 2010)
and transmission electron microscopy (TEM), particularly electron
diffraction (Wirth et al., 2009). Their chemical composition can be mea-
sured by electron microprobe analysis, μ-X-ray fluorescence analysis,
TEM energy dispersive analysis and/or electron energy-loss spectroscopy
(EELS), and nanometer resolution secondary ion mass spectrometry
(Nano-SIMS) analysis. The chemical composition of fluids included in
diamond can be determined by infrared spectroscopy (IR, FTIR, Weiss
et al., 2010, 2013) and synchrotron-based μ-X-ray fluorescence analysis
(Klein-BenDavid et al., 2004; Sitepu et al., 2005).
However, if the grain size of the individual phases inside the inclu-
sions is significantly smaller than 100 nm and/or the inclusions are
polycrystalline, then most of these techniques render insufficient spatial
resolution. Nanometer-sized phases can be reliably determined only by
applying TEM techniques (electron diffraction, high-resolution imaging,
analytical electron microscopy (AEM)) on site-specific foils prepared by
focused ion beam (FIB) milling (Wirth, 2004, 2009; Dobrzhinetskaya
et al., 2010). This is why we emphasize FIB/TEM techniques in the
following section.
The application of various appropriate techniques mentioned above
provides answers to important questions, such as: How many inclusions
are present in a particular volume? Where are they located in that
particular stone? What is the chemical composition of the inclusions
and which phases are present? What is the size of the inclusions and
that of the constituting phases? How can they be made accessible for
analysis, and by which analytical method?
Micro-computed X-ray tomography (μCT) is a non-destructive
technique that allows identification of inclusions larger than 1 μm per
voxel (volume pixel), depending on the original sample size. CT unveils
the internal structure of a sample (inclusions, porosity) down to a
micrometer scale based on X-ray absorption, which depends on density
variations and differences in chemical composition of the sample. A
series of two-dimensional X-ray absorption images are acquired and
then assembled into a 3D image. X-ray sources are usually synchrotron
radiation facilities or high-brilliance rotating anodes. The resolution is
basically defined by the original focal spot size and the sample size.
The larger the sample the more beam broadening due to scattering
effects results, thus reducing spatial resolution. Micro-computed X-ray
tomography works well as long as there is a large contrast in X-ray
 D.E. Jacob et al. / Earth-Science Reviews 136 (2014) 21–35
attenuation between the host and the inclusions. To date, a number of
applications of X-ray computed tomography in Earth Sciences have
been published (Mees et al., 2003; Jacob et al., 2011; Cnudde et al.,
2012; Ketcham and Koeberl, 2013 and references therein).
2.2. Micro-X-ray fluorescence
Micro-X-ray fluorescence analysis is a method that excites X-ray
photons in a specific volume defined by the diameter of the primary
synchrotron beam and records the X-ray photons exited from atoms
present in that particular volume. The penetration depth of the synchro-
tron beam is limited by the absorption of the incident beam by the
target material. The absorption of the excited X-ray photons by the
target material defines the detection limit for individual elements.
The use of X-ray-fluorescence techniques on micrometer-sized inclu-
sions in minerals requires a focused X-ray beam with very high intensity.
Synchrotron radiation provides the intense source and has been used
for μ-X-ray fluorescence analysis of inclusions in minerals since the
nineteen eighties (Frantz et al., 1988). It is a non-destructive method
that leaves the diamond sample unaffected for further investigations.
This method allows the collection of spectra with excellent detection
limits for individual elements (e.g. 10 ppm for Ti and b1 ppm for Zn;
Sitepu et al., 2005). The spectra can also be used for creating elemental
distribution maps. Further details of the technique are presented in one
of the first studies of that kind on diamond inclusions by Sitepu et al.
(2005), and references therein.
With μ-X-ray fluorescence analysis the chemical composition of an
inclusion in diamond can be determined as well as its location inside
the stone. However, to identify the phase and the crystal structure of
inclusions another method such as μ-X-ray diffraction analysis can be
applied. Identification of micrometer-sized inclusions in diamond
using this method is described in detail in recent articles (Kopylova
et al., 2010; Smith et al., 2011). The major advantage of this method is
that many solid-state inclusions can be identified simultaneously, thus
providing an indication of the frequency of individual phases in a single
stone. Together with μ-X-ray fluorescence analysis described above it is
possible to obtain information on the number of inclusions, their phase
compositions and chemical compositions in a comparatively large
volume of several hundred μm3. Micro-X-ray diffraction analysis does
not require the use of synchrotron radiation. Modern rotating anode
X-ray generators can be considered as high-brilliance X-ray sources
suitable for this kind of diffraction analysis.
2.3. Focused ion beam (FIB) milling
While the X-ray based techniques described above are state of
the art methods, they are not appropriate to study nanometer-sized
inclusions because of their limited spatial resolution. The leading tool
to study the “nano-world” inside inclusions is the focused ion beam
(FIB) technique for site-specific TEM sample preparation combined
with TEM. Thanks to the advent of this method in the Earth Sciences,
we know today that many inclusions with a grain size well below
100 nm exist in diamond. Before FIB sample preparation was available
to prepare electron transparent foils from diamond (starting from
approximately 2000), there were only two options to produce speci-
mens applicable for TEM studies.
One of these is crushing of the sample and placing the crushed
material onto a carbon covered TEM grid. This method has many disad-
vantages, particularly loss of spatial information and inhomogeneous
thickness, the latter excluding application of line scans and element
mapping. The second method is the argon-ion milling technique that
was usually applied in the past to prepare electron transparent foils.
However, this method has the tremendous drawback that due to the
incident angle of the ions (a few degrees) preferential thinning occurs
with the result that the weakest material is always sputtered first.
Momentum transfer from Ar ions onto the target atoms is comparatively
23
low because of the lower atomic number of Ar ions compared with Ga
ions used in FIB milling, and the lower acceleration voltage in argon
ion milling devices. For argon ion milling of diamond, this translates
into very long milling times, because bond strength in diamond exceeds
that of all of its inclusions and consequently will be sputtered first.
In contrast, the FIB technique allows preparation of electron trans-
parent foils or membranes from diamond from the location of interest
(site-specific) leaving the inclusions untouched. However, because of
the extreme hardness of diamond the sputtering yield is significantly
smaller than with silicates. To overcome this disadvantage a gas injec-
tion system (GIS) is usually employed that injects water vapor close to
the target surface to be sputtered thus facilitating the sputtering
process.
In a FIB device Ga ions are extracted from a liquid gallium source by
applying an extraction voltage (6–14 keV) to it. An appropriate suppres-
sor voltage prevents extraction of electrons from the liquid metal ion
source (LMIS). Variation of the suppressor voltage adjusts the beam
current to a preset value (e.g. 2.2 μA) maintaining the extractor voltage
at constant value. A constant ion current is required for reproducible
sputtering conditions and automation of the sputtering process. The
extracted Ga ions are accelerated to 30 keV and focused onto the target,
which they hit with sufficient momentum to sputter atoms from the
target surface. Inserting appropriate apertures into the path of the ion
beam controls the beam diameter. The sputtering rate depends on the
acceleration voltage (momentum of the Ga ions), the target material
(bond strength) and the angle of incidence (penetration depth). At
high angles such as 90° – the ion beam is normal to the target surface –
the sputtering rate is low because the Ga ions penetrate deep into the
sample and interact with the sample atoms deep in the sample, but
sputtering of target atoms occurs predominantly at the surface. At
very low incident angles (1–2°), with the Ga ion beam approximately
parallel to the foil surface, sputtering rate is high because the Ga ions
do not penetrate deep into the target and sputtering of surface atoms
occurs much more frequently. Further details of the FIB technique and
the FIB sample preparation of TEM foils with application of a gas
injection system can be found elsewhere (Wirth, 2004; Giannuzzi and
Stevie, 2005; Desbois et al., 2008; Wirth, 2009, 2010).
A typical FIB prepared TEM foil has the dimensions 15 μm × 10 μm ×
0.15 μm and takes approximately 4 hours to produce in a fully automated
process. Significantly thinner membranes with around 35 nm thickness
can be produced in a SEM–FIB combined DualBeam equipment with
in-situ lift out technique (Wirth, 2009). However, for the study of
inclusions in diamond, it is sometimes more favorable to work with
thicker foils to increase the chance of finding nanoinclusions that are
still intact. If the diameter of the inclusion is well below 100 nm and
the total foil thickness is 200–300 nm, intact inclusions can be observed,
while the foil is thin enough to allow electron transparency in diamond.
In these cases, the inclusion's chemical composition can be measured
with EDX and/or electron energy-loss spectroscopy (EELS) analysis.
Subsequently, the electron beam is focused at the inclusion directly,
thereby opening it by intensive electron sputtering and releasing the
liquid content into the system's vacuum. A second EDX analysis after
opening the inclusion can demonstrate which elements were present
in a solid crystalline or quench phase, which were dissolved in the
fluid or gas phase and, by mass balance, which escaped into the vacuum.
FIB-prepared TEM foils have several advantages over other specimen
preparation techniques. (1) FIB prepared foils can be prepared at
uniform thickness. This allows the acquisition of elemental maps of
the inclusions because the recorded X-ray intensities depend only on
the concentration of the individual elements and not on sample thick-
ness. Line scan analyses are also possible but are restricted to inclusions
that are not sensitive to electron irradiation damage and electron
sputtering (sulfides, garnet, olivine). (2) The location of the foil in the
sample can be easily reconstructed because the sputtering site is visible
on the sample surface under an optical microscope at moderate magni-
fication. (3) No preferential sputtering of the inclusions occurs. (4) No
24 D.E. Jacob et al. / Earth-Science Reviews 136 (2014) 21–35
further carbon coating of the foil is required, which is essential when
investigating carbon-based materials.
Because of the limited sputtering depth (10–15 μm) inclusions
must be located close to the surface to be accessible by FIB otherwise
mechanical polishing is required.
2.4. Transmission electron microscopy (TEM)
FIB-prepared foils or membranes are studied with TEM methods.
TEM is an ideal tool to investigate nanometer-sized inclusions in
diamond or any other minerals (Lee, 2010), because it allows the acqui-
sition of chemical, microstructural and structure information from the
same object even at nanometer-scale. The chemical information is
derived from energy dispersive spectra (EDS) of collected X-ray
photons escaping from the sample. Another more qualitative method
is the acquisition of Z-contrast sensitive images with a high-angle
annular dark field (HAADF) detector in the scanning transmission
(STEM) mode. The HAADF images display differences in chemical com-
position in an inclusion composed of different phases. In some special
cases EELS can be used for qualitative chemical analysis. For example,
if iron is present in an inclusion there is an overlap of the Fe-L peak in
the EDX spectrum with the F-K peak. If we want to prove the presence
of fluorine in a particular phase, the fluorine F-L edge in the EEL spec-
trum can be used because there is no interference with the iron Fe-L
edges. The chemical composition of Fe-carbides can be measured with
EEL spectroscopy by calculating the Fe/C ratio (Kaminsky and Wirth,
2011).
In addition to the chemical composition, grain size, grain shape
and defect structure (dislocations, stacking faults, nitrogen platelets)
of the inclusion are of interest. This information can be obtained by
bright-field and dark-field imaging. Usually, the crystal structure, which
unambiguously identifies a solid-state inclusion, is derived from
electron diffraction patterns or convergent beam electron diffraction
(CBED) patterns. However, for selected area electron diffraction the
nanometer-sized crystals are too small and CBED usually cannot be
applied because the focused electron beam immediately destroys
the crystal structure rendering the inclusion amorphous. The best
applicable approach in this case to derive structural information is
high-resolution lattice fringe imaging. Due to very short exposure
times necessary to acquire images with lattice fringes with a CCD
camera (b 1 s) the crystal will not be destroyed before the image is
acquired. After acquisition the lattice fringe image is Fourier trans-
formed (FFT), calculating a diffraction pattern. From the diffraction
pattern in reciprocal space it is possible to measure the length of several
diffraction vectors and angles between them. Transformation of the
length of the vectors into real space (d-spacing) allows a comparison
of the measured d-spacing with calculated d-spacing of the phase we
expect to be present from chemical data. A comparison of the measured
d-spacing with the calculated d-spacing and a comparison of the angles
between adjacent vectors allow an identification of the phase. Thus,
TEM methods enable the identification of nanometer-sized phases
inside inclusions in diamond and minerals in general.
2.5. NanoSIMS
In addition, FIB-prepared TEM foils can also be used for NanoSIMS
studies, which can deliver isotopic information at high spatial resolu-
tion. This has been demonstrated with carbonate inclusions in diamond
(Wirth et al., 2007), nitride inclusions in coesite (Dobrzhinetskaya et al.,
2010) and determinations of the isotopic composition of oxygen and
carbon in lower mantle carbonate and silicate inclusions in diamond
(Kaminsky et al., 2012). NanoSIMS uses an ion beam (Cs+ or O−
depending on the target material to be sputtered) usually b100 nm in
diameter that is scanned over a preselected area e.g. 4 × 4 μm. The
secondary ions sputtered from the target material are collected and
guided into a mass spectrometer for isotopic analysis. Details of this
method are given elsewhere (Stadermann et al., 2005; Floss et al.,
2006; Hoppe et al., 2013 and references therein).
Many recent applications of these methods focused on polycrystal-
line diamonds from such contrasting settings as UHP metamorphic
terranes, alluvial sources and kimberlites. Metamorphic diamonds
from crustal UHP rock are typically in the micron range, thus an ideal
target for these methods. Carbonados and polycrystalline diamonds
from kimberlites are porous and contain minerals intergrown with the
diamond grains in the pores. These minerals have been studied exten-
sively to enlighten the origin of their hosts, but because of the intercon-
nectivity of the pore space, the intergrown minerals are not shielded
against alteration and the evidence they bring has to be critically
interpreted. Studying submicron minerals and fluids actually included
in the diamonds delivers unambiguous evidence and has proved very
beneficial, as reviewed in detail below.
3. Polycrystalline diamonds from kimberlitic sources
Polycrystalline diamond (PCD) is classified by grain size as framesite
(finer; Gurney et al., 1984) or bort (coarser; Orlov, 1977) and typically
has a porous structure. Gray to silver in color, these diamond aggregates
are often intimately intergrown with silicates, oxides and/or sulfides.
Diamond crystals are randomly oriented and range over at least five
orders of magnitude in size (Sobolev et al., 2009). PCD is also referred
to as “diamondite”, which emphasizes the perspective that these
aggregates are rocks, however small, with diamond as the rock-forming
mineral while silicates and other phases are minor and accessory
components.
Polycrystalline diamond is a regular member of the diamond suite in
a number of kimberlite pipes worldwide, where it is believed to amount
to about 20% of the total production (K. de Corte, pers. comm., 2012).
Kimberlite pipes in Africa (Venetia, Premier, Jwaneng, Orapa) yield
polycrystalline diamonds, as do some diamond mines in Siberia (Mir,
Aikhal; Sobolev, 1977).
This variety of diamond is only lately beginning to receive increased
attention and sheds light on another facet of diamond formation in the
Earth's mantle, namely formation by rapid crystallization from a fluid
supersaturated in carbon (Orlov, 1977; Gurney and Boyd, 1982; Jacob
et al., 2000, 2011). Much of what we know about them comes from
study of phases intergrown with, rather than actually being included
in, the diamond crystals. These phases range from several tens to
hundreds of micrometers in size and are termed here “macroinclusions”
to set them apart from the submicron-sized phases included in the
diamond crystals that have only been accessible in recent times.
3.1. Mineral intergrowths: macroinclusions
High-pressure minerals intergrown with the diamond aggregates
are commonly interpreted as syngenetic to the diamonds, based on
the fact that they include small diamond crystals (Kurat and Dobosi,
2000) or display chemical correlations with the diamonds (Jacob et al.,
2000, 2004). However, it is noteworthy that unlike inclusions in
diamond these intergrown phases are not shielded from later metaso-
matic overprint.
The aggregates contain mostly silicates and oxides of eclogitic,
websteritic and peridotitic affinity, broadly similar to the macro-
inclusion suite found in monocrystalline diamonds, although character-
istic differences exist. Chromium-poor (non-peridotitic) garnets in
polycrystalline diamonds have a more restricted compositional range
than inclusions in monocrystalline diamonds, containing typically less
than 6 wt.% CaO (Fig. 1). Thus, most classify as websteritic (Aulbach
et al., 2002), and don't reflect the large variation in grossular component
seen in eclogitic garnets from mantle xenoliths. Nevertheless, some
phases can clearly be classified as eclogitic, for example omphacitic
clinopyroxene and rutile in an Orapa sample (Jacob et al., 2011).
 D.E. Jacob et al. / Earth-Science Reviews 136 (2014) 21–35 25

Fig. 1. Major element compositions of garnets intergrown with diamond in polycrystalline

diamonds from kimberlites compared to garnets from eclogitic xenoliths (Roberts Victor
Mine, RSA, large gray field; Jacob, 2004). Gray field labeled A = peridotitic–websteritic
garnets; dark gray field B = websteritic–eclogitic compositions. Note the more restricted
grossular component compared to typical eclogitic xenoliths.
Data from Dobosi and Kurat (2002, 2010), Jacob et al. (2011) and Kurat and Dobosi (2000).

While restricted in their grossular contents, the garnets show a large

variation in almandine contents (13–46%), covering nearly the whole
variation reported for eclogite xenoliths (Fig. 1). In this respect, their
major element composition is similar to low Cr garnet megacrysts
found in kimberlites (Gurney et al., 1979). Magnetite, while rarely
reported from monocrystalline diamonds (Harris, 1968; Sobolev et al.,
1989) coexists with almandine-rich garnet in a sample from Orapa
(Jacob et al., 2011) and many other polycrystalline diamond aggregates
are magnetic suggesting the presence of magnetite or even native iron
(Jacob et al., 2004). Thus, compared to macroinclusions in diamonds,
magnetite is overrepresented in polycrystalline diamond aggregates.

3.2. Oxidation state and clues to formation mechanisms

Phases intergrown with polycrystalline diamonds show a similarly
large range of redox conditions to macroinclusions in monocrystalline
diamonds of over ca. 10 log units fO2. Inclusions consisting of native
iron and iron carbide, for example, provide evidence for reducing condi-
tions well below the iron–wüstite oxygen buffer (Jacob et al., 2004). The
majority of polycrystalline diamonds, however, are compatible with
more oxidizing conditions involving carbonates.
The origin of the carbon-bearing fluid is debated. Some authors have
argued for an entirely mantle-derived carbon fluid, which subsequently
undergoes Rayleigh fractionation (Deines, 1980; Maruoka et al., 2004),
while others infer a subducted carbon source (Mikhail et al., 2013).
The δ13C values (n = 115) overlap with those for eclogitic and meta-
morphic diamonds and show a broad bimodal distribution from −1.3
to − 29‰ with major frequencies of occurrence at − 5‰ and at
− 19‰ (Fig. 2; Table 1). The first peak at the typical mantle value of
− 5‰ (Cartigny, 2005) argues for at least partial involvement of
mantle-derived carbon. The second peak at −19‰, however, is distinct
and typical only for polycrystalline diamond aggregates (Cartigny,
2005). Whether this mean value is indicative of the formation processes
or source of carbon or if it is connected to biased sampling of the small
database remains to be seen.
Nitrogen concentrations and nitrogen isotope ratios in these
diamonds cover a large range of 8 to 3635 ppm and δ15N − 6.1 to
+ 22.6‰ (Gautheron et al., 2005; Mikhail et al., 2013), but neither
nitrogen concentrations nor δ15N values are coupled with δ13C values,
apparently discounting coupled fractionation processes operating
during diamond growth (Deines, 1980; Maruoka et al., 2004; Cartigny,
2005). Nitrogen aggregation states are across the whole spectrum
from pure IaA to pure IaB (Mikhail et al., in press).
Fig. 2. Carbon isotopic compositions of polycrystalline diamonds from kimberlites (a),
from UHPM terranes ((b): white = Kokchetav, gray = Erzgebirge) and of carbonado
diamonds (c) compared to the typical range of monocrystalline diamonds with peridotitic
inclusions (light gray band) and fibrous diamonds (dark gray band). Data for polycrystalline
diamonds from Jacob et al. (2000), Maruoka et al. (2004), and Mikhail et al. (2013), for
UHPM diamonds from Cartigny et al. (2001), Imamura et al. (2013), and Dobrzhinetskaya
et al. (2010), for carbonado from Cartigny (2010) and for fibrous diamonds Cartigny
(2005) and references therein.
The only study to date on radiogenic isotope systems of minerals
included in polycrystalline diamonds reported unradiogenic Nd isotopic
ratios of −15.9 to − 21.7 εNd, typical for ancient lithospheric material
and argued for recent remobilization of this material to form polycrys-
talline diamonds (Jacob et al., 2000). The authors based their arguments
on coupled chemical characteristics of diamonds and intergrown
garnets as well as on trace element zonation in the garnets, which
would have been erased by diffusion during expanded storage at mantle
temperatures and pressures. Contrasting with this apparently recent
formation of polycrystalline diamonds at the Venetia Mine are findings
that some samples from an unknown South African locality show high-
temperature deformation and annealing structures in Electron
Backscattered Diffraction (EBSD) that apparently require long mantle
residence times (Rubanova et al., 2012).
In summary, polycrystalline diamonds form episodically by small-
scale, rapidly occurring fluid-dominated redox processes within the
subcratonic lithosphere. Intergrown micron-sized phases are most
often hybrids, carrying evidence for a mixed derivation involving fluids
and peridotite or eclogite solids and preserving inhomogeneity as a
result of their rapid formation. Their trace element patterns often
show strong enrichment in elements indicative for carbonatite metaso-
matism, thus arguing for a role for mainly oxidized fluids. However, very
 26
Table 1
Summary of some major characteristics of diamonds discussed in this study compared to fibrous and monocrystalline diamonds.

Geological setting Macro-inclusions Micro-inclusions Carbon isotopes Nitrogen characteristics P and T fO2 range of
(5–200 μm) (b1 μm) (δ13C values) inclusions

Polycrystalline Subcratonic lithosphere Intergrowths mostly websteritic, Silicates, oxides, sulfides, −2 to −28‰, bimodal with means 0–4000 ppm, δ15N = −5.7 to +22.5‰ Diamond stability Mostly FMQ to IW
aggregates (Group I kimberlites) but also eclogitic and peridotitic metals, fluids. Carbonate at −5‰ and −18‰ (see Fig. 2 for (Mikhail et al., 2013) IaA–IaB (Mikhail et al., field buffers, some be-
suites present but rare references) in press) yond
UHPM terranes Continental collisions None (due to the small size of the Silicates, carbonates, halides, −10 to −27‰ 0–11, 150 ppm, δ15N = −1.8 to +14‰ 6–9 GPa, 900– Around FMQ/CCO
diamonds) metals, fluids (Cartigny et al., 2001) Ib–IaA (De Corte et al., 1100°C buffers
1999)
Carbonado Alluvial, inferred to be Rare, mostly intergrown phases Silicates, carbonates, halides, −5 to −30‰, most −22 to −30‰ 100–300 ppm (Cartigny, 2010) δ15N = −17 Unknown Mostly FMQ to IW
from the Earth's mantle metals, fluids (Cartigny, 2010) to +8‰ (Heaney et al., 2005), Ib–IaA
(Cartigny, 2010)
Fibrous Subcratonic lithosphere None Fluids, silicates, carbonates, −4 to −8‰ (Boyd et al., 1994) 0–3000 ppm, δ15N = −2 to −9‰, IaA, some Diamond stability Around FMQ
halides. All K-bearing Ib–IaA (Cartigny, 2010) field

D.E. Jacob et al. / Earth-Science Reviews 136 (2014) 21–35

Monocrystalline Mostly subcratonic Peridotitic, eclogitic, websteritic Unstudied +1 to −40‰, mean for peridotitic 0–3000 ppm, δ15N = +5 to −10‰ 4.5–7.5 GPa, 950– FMQ to IW but
lithosphere, some suites at −5‰ and wide distribution for (Cartigny, 2005), all aggregation states, but 1350°°C (and mostly around
asthenospheric eclogitic (Stachel et al., 2009) mostly IaA–IaB (Shirey et al., 2013) above) FMQ
version). Scale bars 200 nm.
inclusion in a polycrystalline diamond (see Jacob et al., 2011 for an online animated
magnetite included in polycrystalline diamond with porous structure, (b) intact fluid
Fig. 3. TEM HAADF images of inclusions in polycrystalline diamond grains. (a) shows a

were not observed in the magnetites, this may be due to the fact that
the diamond-forming fluid. Although cavities still containing fluid
which was interpreted as evidence for formation in the presence of
displayed a distinctive polycrystalline and porous texture (Fig. 3a),
mond. Magnetite, volumetrically the most prominent inclusion phase,
inclusions, thus confirming that this paragenesis is syngenetic to dia-
pyrrhotite, omphacite and rutile were found as both nano- and micro-
crystals, the latter were considerably altered at a late stage. Magnetite,
identical to the micro-sized phases intergrown with the diamond
although major nano-phases included in the diamond were largely

tion of the diamonds.

overprinted or even formed later and are thus unrelated to the forma-
shielded by diamond to evaluate whether the former were chemically
micrometer-sized intergrowth phases could be compared to those
inclusions and, most importantly, of coexisting fluids. Furthermore,
TEM enabled a more complete and direct characterization of nano-

3.3. Insights from nano-inclusions

possible scenario.
pronounced heterogeneity in their source regions upon formation as a
reducing inclusions can also be found in these rocks and underline
A sample from the Orapa kimberlite (Jacob et al., 2011) showed that

Taking these earlier studies to the nano-scale with the aid of FIB–
 D.E. Jacob et al. / Earth-Science Reviews 136 (2014) 21–35
a typical TEM foil represents only a very small volume of the total crystal
or an approximate 2D section.
Similarly, several open cavities were encountered in the diamonds,
which were interpreted to have lost their fluid content upon FIB sec-
tioning. These cavities contained rutile and/or pyrrhotite and omphacite
and often non-stoichiometric phases that were interpreted as quench
phases. One occurrence of an intact inclusion enabled identification of
a fluid by its characteristic continuous changes in diffraction contrast
due to density fluctuations caused by the electron beam (Fig. 3b). This
fluid was associated with fine-grained pyrrhotite, a silicate phase rich
in Fe, P, Mg, Al, Ca and K and a quench phase rich in non-stoichiometric
amounts of Fe, P and Si. Amongst all inclusions only one ca. 10 nm
large inclusion was found whose chemical composition suggested it to
be a carbonate, although phase identification was not possible. The
fluid found in the polycrystalline diamonds from Orapa is thus charac-
terized by silicate rich in Fe, Mg, Al, Ca, K and P, while carbonate is
rare and halide phases are absent (Fig. 4).
The majority of polycrystalline diamonds bear evidence for having
precipitated from an oxidized C–H–O medium, while only a minor pro-
portion contain very reduced inclusions. Experimental studies suggest
Fig. 4. Demonstrates the characteristic microstructure of carbonado inside a diamond
grain from the Central African Republic (CAR2#1414, Kaminsky et al., 2013). (a) TEM
bright field image of several diamond grains with irregular grain boundaries. Some grains
show straight dislocation lines. (b) and (c) TEM dark field images taken at the 111 reflex
and displaying three individual diamond grains (copy of a film negative, therefore, 111
crystal faces are dark in the image). Note the irregular grain boundaries and the locally
changing inclination of the grain boundary planes.
27
that at typical upper mantle pressures and temperatures the C–H–O
medium from which these diamonds formed is subcritical, being either
a carbonatitic melt under oxidizing conditions (Dasgupta et al., 2004) or
a CH4-rich fluid at low oxygen fugacity (Stalder et al., 2001). A halide
component that represents one of the end-members identified in
diamond fluids worldwide (Klein-BenDavid et al., 2004) has not yet
been encountered.
4. Carbonado
Carbonado is a smooth-surfaced fine-crystalline (1–10 μm) and
highly porous diamond aggregate, mostly black in color, which lacks
most of the typical macroinclusions found in monocrystalline diamonds
(Heaney et al., 2005; McCall, 2009). Their origin is still under debate
with models ranging between crustal derivation, genesis in the
upper Earth's mantle and an extraterrestrial origin (see Heaney et al.,
2005; McCall, 2009; Cartigny, 2010; Haggerty, 2014 for detailed
summaries).
Characteristic features of carbonado are inclusions of crustal
minerals, such as graphite, quartz, rutile, florencite (a water-bearing
aluminium phosphate), and clay minerals that occur along partially
open grain boundaries and in pores. Carbonado (sensu stricto) is found
in alluvial deposits in Brazil and in Central Africa, and its primary source
is unknown; there is a high chance that some of the inclusions in carbo-
nado are in fact epigenetic, and are thus unable to provide any insights
into the origin of this enigmatic diamond (Heaney et al., 2005). Modern
submicron methods now provide the means to test this by comparing
the nanoinclusion suite in the carbonado with the chemistry of the
macrocinclusions.
Carbonado is similar to polycrystalline diamond aggregates from
kimberlites and the latter are sometimes mistakenly classified as carbo-
nados. Both have a porous structure and random crystallographic orien-
tation of the individual diamond grains within their polycrystalline
aggregates (Ishibashi et al., 2012; Rubanova et al., 2012; Kaminsky
et al., 2013). Furthermore, some polycrystalline diamond aggregates
can show equally small grain sizes and the microporphyritic textures
that are typical of carbonado (see Heaney et al., 2005; Haggerty, 2014
for reviews), and carbonado in turn can display coarse-grained
microtexture (e.g. Trueb and Butterman, 1969). However, carbonado
has much higher porosity (Vicenzi et al., 2003) and displays a very dis-
tinct and unusual nanostructure recognized with TEM, displaying
column-like diamond grains that form linear and zigzag patterns with
low-angle and even partially open grain boundaries. A characteristic
feature of individual diamond grains in carbonado is the presence
of uneven and rough grain boundary planes as displayed in Fig. 4
(Rondeau et al., 2008), very unlike the microstructure of polycrystalline
diamonds from kimberlites. In addition, carbonado occurs in remark-
ably large sizes, much bigger than those reported for polycrystalline
diamond aggregates from kimberlites. Svisero (1995) pointed out that
ten of the eleven largest diamonds reported from Brazil are carbonados,
the largest weighing 3167 carats.
Isotopic dating using Pb isotopes of bulk diamonds (Ozima and
Tatsumoto, 1997) and Pb–Pb SHRIMP dating of quartz and rutile inclu-
sions (Sano et al., 2002) of both Brazilian and Central African carbona-
dos yielded Archean ages, which served as a basis to hypothesize that
both populations are derived from the same eroded source (McCall,
2009). Carbon isotopes define a distinct range of δ13C = − 23.5 to
−33‰ (Table 1; but note two outliers at higher, typical mantle values,
Fig. 2) which led a number of authors to argue for a crustal origin involv-
ing organic carbon (Smith and Dawson, 1985) or irradiated carburanium
(Kaminsky, 1987, 1991; Ozima et al., 1991). Carbonados are rich in
hydrogen (Garai et al., 2006), contain single nitrogen impurities (type
Ib–IaA; Garai, 2012) and polycyclic aromatic hydrocarbons (Garai
et al., 2006), which are otherwise rarely encountered in terrestrial
diamond, but do occur in presolar diamond grains from meteorites.
These characteristics and the apparent lack of primary terrestrial silicate
28 D.E. Jacob et al. / Earth-Science Reviews 136 (2014) 21–35

inclusions led to speculations of an extraterrestrial origin of these

enigmatic diamonds (Haggerty, 1999, 2014).
FIB–TEM analyses provided the means to search for smaller silicate
or oxide inclusions inside individual diamond crystals in order to
exclude any potentially epigenetic material (De Souza Martins, 2006;
Sautter et al., 2011; Kaminsky et al., 2013). The inclusions found with
this method were generally relatively small (in the hundred nanometer
range). Phases comprised almandine–pyrope garnet, augite, apatite
(including fluorapatite), phlogopite, SiO2, Ca–Mg–Sr–and Ca–Ba-
carbonates, halides (sylvite and bismocolite BiOCl), native Ni and
metal alloys (Fe–Ni, Cr–Fe–Mn, and Pb–As–Mo), oxides (FeO, Fe–Sn–
O, TiO2, SnO2, FeTiO3 and PbO2), and Fe–sulfides, as well as fluid inclu-
sions. These results are similar to an earlier TEM study of syngenetic
inclusions in carbonado by De et al. (1998) who reported native metals
and alloys in addition to SiC, sylvite, calcite, smithsonite (ZnCO3) and
Mg–Al silicates. The fluid inclusions are predominantly silicate–carbonate
compositions; halide-rich fluids were also observed, but more rarely.
Molecular H2O, detected by FTIR, was found in a carbonado from Central
Africa (Ishibashi et al., 2012).
The nanoinclusion suites of carbonados thus show much more
similarity to findings in mantle-derived diamonds (Klein-BenDavid
et al., 2007; Cartigny, 2010; Jacob et al., 2011) and metamorphic
diamonds from ultrahigh pressure terranes (e.g. Dobrzhinetskaya,
2012; Dobrzhinetskaya et al., 2013) than the larger inclusions. In con-
trast, low-pressure crustal phases identified in earlier studies, such as
florencite, were not encountered, pointing to an epigenetic origin of
these minerals. Therefore, the solid phase inclusions reported from
carbonados so far (while maybe not yet being representative) do not
support the extraterrestrial origin suggested by Haggerty (1999, 2014)
and Garai et al. (2006).

5. Polycrystalline diamonds from ultrahigh-pressure terranes

Polycrystalline diamonds (Fig. 5) were identified recently within

felsic quartz–feldspathic gneisses of the Erzgebirge massif, Germany
(Dobrzhinetskaya et al., 2013) where they occur in addition to abundant
monocrystalline microdiamonds. Massonne (2003, 2006) showed that
these rocks were subjected to UHP metamorphism during continent–
continent collision at T = 1100 °C and P = 7–8 GPa, which corresponds
to depths of ~200–210 km.
While these represent one of the most recent finds, polycrystalline
diamonds have been known for more than a decade from rocks of the
Kokchetav massif as so-called “S- and R-type” diamonds (Ishida et al.,
2003; Ogasawara and Aoki, 2005) or “overgrown” diamonds (Sitnikova
and Shatsky, 2009). These diamond-bearing metasedimentary rocks of
the Kokchetav UHP massif are thought to have formed under similar
conditions as those in the Erzgebirge, namely in a deep subduction
zone at T = 980–1200 °C and P = 6–9 GPa, corresponding to depths
of ca. 160–250 km (Dobrzhinetskaya et al., 2005; Ogasawara and Aoki,
2005).
5.1. Nanoinclusions in the Erzgebirge polycrystalline diamonds
The diamonds included in felsic gneisses contain abundant
nanoinclusions of 10–200 nm in size. These can be differentiated into
two suites, based on their occurrence within the diamonds: along the
grain boundaries of microcrystalline diamond aggregates (suite 1), or
on the dislocations that are widely developed inside diamond crystals
(suite 2). Suite 1 includes crystalline and amorphous nanoinclusions of
SiO2, rare CaCO3, BaCO3 and KAlSi3O8 as well as abundant amorphous
quench phases of an approximate composition of NaSO4 and KCl. All
phases contain traces of Pb, K, Ca, Cr, Fe, Al, P, Cl, S, Ti, and Zr in different
combinations. Structures of crystalline phases of SiO2, CaCO3 and KAlSiO8
could not be determined due to their very small size (~10 nm). Suite 2 is
composed of rare crystalline nanoinclusions of ZrSiO4, NaSO4, BaSO4
and countless b 1–10 nm amorphous inclusions, mostly SiO2 and
Fig. 5. Typical diamonds from ultrahigh pressure metamorphic terranes: (A) diamond
inclusion in zircon from the Erzgebirge massif, Germany (modified from Dobrzhinetskaya
et al., 2007), (B) diamond from the garnet–biotite gneisses of Kokchetav massif,
Kazakhstan (collection Dobrzhinetskaya).
KAlSi3O8 that are associated with perforated cavities. The amorphous
matter is assumed to be the residue of evaporated remnants of former
fluid inclusions that were perforated by either the FIB sputtering during
foil preparation or the TEM electron-beam sputtering upon focussing
the beam to form a very small probe of only several nanometers in
diameter. The process of fluid bubble penetration by electron sputtering
has been observed several times during numerous TEM study sessions
and detailed descriptions of this effect can be found elsewhere
(e.g. Dobrzhinetskaya et al., 2005). EDX analysis combined with TEM
observations showed that the suite of amorphous inclusions contains
traces of Cl, S, P, Al, K, Fe, As, Hg, Mo, Co and Ti mixed in different
proportions and combinations (Dobrzhinetskaya et al., 2013).
The histogram in Fig. 6a comprises the combined compositional
data for all suites of fluid inclusions in the Erzgebirge gneisses (for
details on the data reduction see Dobrzhinetskaya et al., 2013). Data
analysis suggests that the integral composition of the Erzgebirge
diamond-forming fluids correspond to a high-density C–O–H fluid, a
hydrous-silicic fluid rich in Al and K and a hydrous-saline fluid rich in
Cl, K and Na. The overall composition of these fluids is similar to that
of fluids in fibrous diamonds plotted in Fig. 9. Traces of carbonate,
sulfate, phosphate and metallic cations such as Fe, Mg, Ti, Cr, Co, Mo,
Zn, Zr, Pb, As and Hg reflect the local geochemical diversity of the
metasedimentary rocks which host these diamonds.
 D.E. Jacob et al. / Earth-Science Reviews 136 (2014) 21–35
Fig. 6. Histograms showing average (n) elemental composition of fluids in diamonds
measured as raw counts per second TEM-EDX data: (a) garnet–quartz–feldspathic
gneisses of the Erzgebirge massif, Germany (n = 40 inclusions), (b) garnet–biotite
gneisses of the Kokchetav massif, Kazakhstan (n = 50 inclusions), (c) marbles of the
Kokchetav massif, Kazakhstan (n = 45 inclusions).
5.2. Nanoinclusions in the Kokchetav polycrystalline diamonds
In the UHP Kokchetav massif, polycrystalline diamonds are found
as inclusions in diopside and phlogopite from metacarbonate rocks
(marbles and calcareous rocks) and in feldspathic gneisses.
5.2.1. Marbles and calcareous-silicate gneisses
Diamonds from these carbonaceous rocks contain abundant crystal-
line and amorphous nanoinclusions, and their chemical composition
clearly indicates that the source for the diamonds is locally derived.
They have distinct morphologies and are known as “S- and R”-type
diamonds (Ishida et al., 2003). The nanoinclusions are aragonite, mag-
nesite and rarely also TiO2. No SiO2 inclusions nor any Al–Si-bearing
minerals nor their quench products have been observed. The crystalline
nanophases and the amorphous matter lining the walls of small cavities
(remnants of decrepitated fluid inclusions) contain a diverse spectrum
of lithophile and siderophile trace elements such as Co, Cu, Zn, Mn, Pb,
K, Ba, Fe, Sr, Th, Zn, Cl, S and P (Fig. 6c).
5.2.2. Feldspathic gneisses
Monocrystalline and polycrystalline diamonds from feldspathic
gneisses of the Kokchetav massif are similar to those from felsic gneisses
of the Erzgebirge massif in that they also contain two suites of
nanoinclusions of which one is crystalline while the other is amorphous.
29
The nanoinclusions are situated in cavities along diamond–diamond
interfaces or even create films of amorphous matter between individual
grains of the polycrystalline aggregates, but they are also observed inside
individual diamond crystals. Most of these crystalline nanoinclusions
are oxides (SiO2, TiO2, FexOy, Cr2O3, ThxOy), or silicates, e.g. KAlSi3O8,
and rare inclusions of ZrSiO4, BaSO4, and CaCO3–aragonite occur as
well (Fig. 6b).
The inclusions contain variable amounts of K, Na, P, S, Pb, Zn, Nb, Al,
Co, Mo, P, and Cl (e.g. de Corte et al., 1999; Dobrzhinetskaya et al., 2005).
Amorphous nanoinclusions associated with cavities have similarly
diverse compositions and exhibit large variations of trace elements.
They are considered to be non-stoichiometric “quench” products of
fluid inclusions that were opened during preparation or analysis.
Diamonds hosted by felsic rocks have abundant Si- and Al-bearing
inclusions and contain rare carbonate inclusions, whereas diamonds
from marble and calcareous-silicate gneisses are mostly rich in carbon-
ate inclusions and only rarely contain Si-, or Al-bearing minerals. This
compositional diversity of the crystalline and amorphous nanoinclusions
shown by the Kokchetav polycrystalline diamonds in all rock types
clearly indicates that in general the fluid from which diamonds crystal-
lized has a local origin in UHP terranes.
5.3. Diamond-forming fluid media and oxidation state
The concept of UHPM diamond crystallization from a supercritical
C–O–H fluid in the diamond stability field is agreed upon by a majority
of researchers (see review papers: Dobrzhinetskaya, 2012; Schertl and
Sobolev, 2013). This has received considerable support from detailed
analytical studies of nanoinclusions in natural UHPM diamonds and
from experiments, which successfully synthesized diamond from differ-
ent carbon species in the presence of H2O at pressures and temperatures
corresponding to the diamond stability field (e.g. Dobrzhinetskaya et al.,
2009).
The diamond-hosting sedimentary rocks are rich in H2O and
diamonds themselves contain nanoinclusions that are enriched with
almost all elements available in the host rocks. These observations
show that the origin of the diamond-forming fluid is local.
The presence of carbonate inclusions in polycrystalline diamonds
and in single diamond crystals from both the Erzgebirge and the
Kokchetav UHPM terranes showed that the oxygen fugacity must have
been close to the CCO and the FMQ oxygen buffers (logfO2 = − 6 in
Fig. 7; e.g. Dobrzhinetskaya, 2012; Dobrzhinetskaya et al., 2013).
5.4. Source of carbon and nitrogen aggregation
Polycrystalline and single crystal diamonds from UHPM terranes
originate from the same fluid source (e.g., Dobrzhinetskaya, 2012;
Dobrzhinetskaya et al., 2013). The diamonds from the Kokchetav massif,
Kazakhstan have δ13C = −10.57‰ and N contents of up to 11,385 ppm
(Cartigny et al., 2001), whereas diamonds from dolomitic marble are
characterized by δ13C = − 10.19‰ and N = 2,762 ppm (Table 1,
Fig. 8). These δ13C values are interpreted to be a mixture between crustal
and mantle carbon reservoirs (Cartigny et al., 2001; Ogasawara and
Aoki, 2005), which is supported by He and Ne isotope studies in these
diamonds (Sumino et al., 2011).
The Erzgebirge microdiamonds (Fig. 8) are characterized by
significantly lighter carbon in comparison with the Kokchetav terrane,
ranging in δ13C between − 17 to − 27‰ and N = 100–4,647 ppm
(Dobrzhinetskaya et al., 2010). This carbon isotopic variation suggests
that the Erzgebirge diamonds, in contrast to the Kokchetav suite, crys-
tallized from an entirely crustal carbon reservoir, although whether
that carbon was organic or inorganic may be debated. The wide varia-
tion of nitrogen abundances was explained by an inhomogeneous
distribution of N-bearing fluid inclusions, or by the presence of N-
bearing mica such as phengite, which is observed in association
with microdiamonds or as inclusions (e.g. Stöckhert et al., 2001;
30 D.E. Jacob et al. / Earth-Science Reviews 136 (2014) 21–35
Fig. 7. Composition and oxidation state of C–O–H fluids in equilibrium with diamond for
P = 5 GPa, T = 1400 K (modified after Taylor, 1990; Odling, 1989). The heavy curve
labeled “diamond saturation line” delineates the stability field of diamond and coexisting
fluid at this P and T. The oxidized fluid-only region lies above, and the reduced fluid-only
region is to the lower left of the saturation curve. They are separated by a diamond + fluid
field that extends to very water-rich fluid compositions labeled “water maximum”.
Positions of the magnetite–wüstite (MW) and the iron–wüstite (IW) oxygen buffers are
indicated by dashed lines. Reducing fluids coexisting with diamond at fO2 = IW and
below consist of mixtures of CH4 N H2O N H2 and C2H6 progressing to mixtures of CH4 N
C2H6 N H2 at fO2 well below IW.
Dobrzhinetskaya et al., 2010). Kinetic effects upon diamond crystalliza-
tion may also have played a role.
Nitrogen aggregation characteristics show that all known diamonds
from UHPM terranes belong to the type 1b–1aA, suggesting a short
residence time (ca. 5 Ma) at high temperature conditions (~ 900–
1100 °C) (e.g. Cartigny et al., 2001; Dobrzhinetskaya et al., 2006). This
distinguishes them from many kimberlitic monocrystalline diamonds,
which belong to type 1aAB and are interpreted to have had longer
Fig. 8. Comparative diagram of nitrogen content versus δ13C in diamonds from ultrahigh
pressure metamorphic terranes, polycrystalline diamonds from kimberlite (black spots,
Jacob et al. unpublished SIMS data, open circles, Mikhail et al., 2013) and worldwide
monocrystalline diamonds from kimberlitic and lamproitic sources (Field 3). Fields 1–3
represent Kokchetav massif, Kazakhstan and are adopted from Cartigny et al. (2001,
2003). Field 1 (black squares): diamonds from grt pyroxenites; Field 2 (gray squares):
alluvial microdiamonds, and diamonds from marbles (open squares). Field 4 is from
Dobrzhinetskaya et al. (2010) and represents Erzgebirge microdiamonds included in
garnets from quartz–feldspathic gneisses.
residence times in the mantle (e.g. Jones et al., 1992; Cartigny et al.,
2001).
5.5. Evidence from fluids for crust–mantle interaction
Though most observations have pointed to a crustal origin there are
several lines of evidence that the diamond-bearing fluid in at least some
UHPM terranes is a product of crust–mantle interaction. One of them is
the presence of eskolaite (Cr2O3) inclusions that contain traces of Al, Si, P,
Ni, and Fe in Kokchetav diamonds from felsic gneisses (Dobrzhinetskaya
et al., 2003). Dobrzhinetskaya and Wirth (2009) postulated that Ni- and
Fe-contents as well as the Cr-content of eskolaite were probably derived
from a mantle wedge reservoir. Noble gas studies (Sumino et al., 2011)
supported this proposition. These authors found that the Kokchetav
diamonds contain primordial He and Ne, suggesting that a deep mantle
plume affected the subducted continental slab. Though no evidence
of crust–mantle interaction has yet been found in the Erzgebirge
diamonds (potentially mostly because of the lack of He–Ne isotopes
studies), the mechanism of diamond formation from both UHPM
terranes is characterized by active “crustal” fluid migration through
the subduction zones. In Kokchetav, the process was complicated by
the interaction of this local, crust-derived fluid with mantle fluids.
6. Discussion
6.1. Diamond fluids in the Earth's mantle
While mantle and crustal environments for the formation of poly-
crystalline diamonds appear strikingly different, all of these diamond
crystals contain fluid inclusions, thus emphasizing the prominent role
of fluids in diamond formation in general (Navon et al., 1988).
Much of what we know about diamond-forming fluids comes
from intensive studies of fibrous and cloudy diamonds from the Earth's
mantle (Schrauder and Navon, 1994; Izraeli et al., 2001; Klein-BenDavid
et al., 2004; Zegdenizov et al., 2004; Rege et al., 2005; Tomlinson et al.,
2006, 2009; Logvinova et al., 2008; Weiss et al., 2009). Fibrous
diamonds form in the same environments in the Earth's mantle as
“normal” monocrystalline diamonds, but represent an extreme end of
this process, providing a different perspective. Although they are only
a minor component of the diamond population in Group I kimberlites
(Boyd et al., 1994), fibrous stones are ideal study objects for nano-
methods, because they can contain thousands of fluid inclusions.
For the first time, direct observation of diamond fluids was possible
and these studies significantly extended our knowledge, which had
previously been based solely upon indirect evidence from carbon and
nitrogen and their isotopes within the diamond itself.
Many studies worldwide revealed that the fluids trapped in these
stones range compositionally between three end-members, namely a
carbonatitic end-member rich in Ca, Mg, Fe, K and CO2, a hydrous-
silicic end-member rich in Si, Al, K and H2O, and a hydrous-saline fluid
rich in Cl, K, Na and H2O (Fig. 9; Klein-BenDavid et al., 2004). Most
recently, high Mg/Ca carbonatitic fluid inclusions were reported
(Klein-BenDavid et al., 2008; Kopylova et al., 2010; Weiss et al., 2011),
which perhaps represent an additional end-member for these fluids,
situated deeper in the lithosphere.
A characteristic feature of these fluids is a pronounced miscibility
gap between the silicate-dominated and the halide-rich end-members
at pressures and temperatures relevant to diamond formation in the
Earth's mantle, described from case studies (Izraeli et al., 2001; Klein-
BenDavid et al., 2004, 2006, 2007) and substantiated experimentally
(Safonov et al., 2007). Most fibrous diamond fluid compositions fall
along mixing lines between either the carbonatitic-hydrous saline or
the carbonatitic-hydrous silicic end-members for which contradictory
explanations exist. Silicates are the liquidus phases in carbonatite
melts (Safonov et al., 2007; Litasov and Ohtani, 2009); therefore
diamond crystallization upon successive cooling should produce a
 D.E. Jacob et al. / Earth-Science Reviews 136 (2014) 21–35
Fig. 9. Fluid end-member compositions derived from studies on fibrous diamonds (bold
dashed line: Izraeli et al., 2001; Klein-BenDavid et al., 2004) and experimental results of
Safonov et al. (2007, solid line — 1600 °C, dashed line — 1500 °C, stippled line —
1400 °C) showing the compositional range of fluid inclusions in diamonds. Note the
large miscibility gap between the saline and the siliceous end-member in this system.
Overlain are the general range of inclusion compositions for UHP metamorphic diamond
inclusions from metacarbonate rocks (Kokchetav Massif — light gray field) and feldspathic
gneisses (Kokchetav Massif and Erzgebirge — dark gray fields) and the approximate
composition for the polycrystalline diamond aggregate from Orapa (silicate inclusions as
dark gray field connected with a tie line to the single carbonatic inclusion (star)).
progression from silicate-rich to carbonate-rich inclusions. However,
this contradicts other models (Schrauder and Navon, 1994) that argued
for fractional crystallization of a carbonatitic liquid, which would result
in an opposite trend in inclusion chemistry.
6.2. Diamond fluids in polycrystalline diamonds
The fluid compositions from polycrystalline diamonds from Orapa
plot towards the hydrous-silicic end-member of these compositions
and lack the halide component (Fig. 4). Potassium is present in many
of the nano-inclusions in this sample, but also Ca, Mg and particularly
Fe, which are more typical for the carbonate-dominated fluids in fibrous
and cloudy diamonds. Although it is too early to draw general conclu-
sions for the polycrystalline diamonds from kimberlites, these observa-
tions show that this particular fluid bears general similarities with those
described from the fibrous and cloudy diamonds in representing a
composition close to the silicate-dominated end-member, although
different in divalent cation composition.
In contrast, fluid inclusions in the carbonado suite studied here (not
shown) cover the broad spectrum of fluid compositions depicted in
Fig. 9, including the apparent lack of compositions plotting into the
miscibility gap.
The hypothesis that worldwide diamond fluids comprise silicates,
water, carbonate and halogens also holds for polycrystalline diamonds
from crustal rocks. Diamonds from metacarbonates of the Kokchetav
UHP terrane contain hydrous-saline and carbonatic inclusions, while
silicate-bearing fluid inclusions are rare. Felsic gneisses from the
Kokchetav and Erzgebirge massifs, on the other hand, have inclusions
in diamond that are of hydrous-silicic or hydrous-saline compositions.
The exact composition for each individual nano-inclusion in diamond
from the felsic gneisses was difficult to assess, and the exact composi-
tional range distribution between the individual end-members remains
unclear as of yet. The large miscibility gap at 5 GPa in Fig. 9 persists
towards lower temperatures and pressures (Suk, 2001); however, the
relevant experimental studies did not include water. Safonov et al.
(2007) and Litasov and Ohtani (2009) suggested that the presence of
water would significantly increase the miscibility of Si- and Cl-bearing
liquids.
31
6.3. Oxidation conditions recorded by polycrystalline diamonds: a matter
of scale
Macro-inclusions indicate that diamond has a large stability field
stretching over more than 10 log units in oxygen fugacity (fO2), from
conditions of about six units below the iron–wüstite oxygen buffer,
where moissanite (SiC) is stable (Moore and Gurney, 1989; Ulmer
et al., 1998) to distinctly oxidized conditions where carbonate inclu-
sions are present, at an oxygen fugacity of about 4 log units above the
iron–wüstite equilibrium (Fig. 7). Depending on the exact bulk compo-
sition, even higher fO2 is suggested by rare pure CO2 inclusions in
diamond (Schrauder and Navon, 1994; Chinn, 1995). An important
insight from the application of FIB–TEM methods to diamond was that
in some cases the nano- and micro-inclusion suite within a single
diamond can trace fO2 conditions covering the entire 10 log units fO2
of the diamond stability field (Klein-BenDavid et al., 2007).
Most microinclusions (fluid and solid alike) record oxidized condi-
tions; however, there is also a pronounced record of heterogeneous of
fO2 conditions from microinclusions. Similarly, macro-inclusion suites
also suggest that most of their host diamonds formed by reduction of
an oxidized medium (Stachel and Harris, 2008), but inclusion evidence
for very reducing conditions can be found, too. However, this skewed
distribution towards oxidized carbon sources is not reflected by
the inclusions in polycrystalline diamonds from the Earth's mantle.
Here, inclusions that reflect very reducing conditions appear to be
just as common as those formed under oxidizing conditions. Native
metals and alloys (e.g. Fe-Ni alloy, Sn) are found in carbonados but
so are carbonates (Kaminsky et al., 2013). Carbonates and magnetite
or cohenite and native iron occur in polycrystalline diamonds from
kimberlites (Jacob et al., 2004, 2011). The large range of oxygen fugacity
recorded by polycrystalline diamonds suggests a prominent role
of redox gradients and transient, small-scale equilibria in their
formation.
Compositions of mantle volatiles in equilibrium with diamond
vary at the relevant pressures and temperatures depending on oxygen
fugacity. While they consist of pure CO2 at oxidizing conditions, they
comprise mixtures of CH4, H2O and H2 close to the iron–wüstite buffer
and below (Fig. 7; Saxena, 1989; Taylor, 1990; Sokol et al., 2009;
Zhang and Duan, 2009). Under oxidizing conditions the CO2-rich
volatiles form very mobile carbonatitic melts that provide efficient
transport media for carbon in the mantle (Green and Wallace, 1988).
In a reducing environment, the main carriers of carbon are methane-
rich fluids (Jakobsson and Holloway, 1986; Sokol et al., 2009; Foley,
2011), because reducing silicic melts dissolve b100 to 2000 ppm carbon
(Taylor and Green, 1987; Ardia et al., 2013). Reduction of carbonatitic
melts or oxidation of methane-bearing fluids results in the formation
of carbon-saturated aqueous fluids (Fig. 7) from which diamond can
precipitate across a wide pressure and temperature range.
For reducing conditions more than 3 orders of magnitude below the
water maximum in Fig. 7, fO2 changes upon diamond precipitation
occur from a fluid with near-constant C/H ratio, which facilitates the
precipitation of suites of inclusions with variable oxidation states.
Here, rapid diamond crystallization may occur with essentially
unchanging fluid composition if the fluid throughput is high. The
rapid change in fluid composition 2 orders of magnitude below the
water maximum would be associated with rapid diamond crystalliza-
tion and entrapment of inclusions slightly above iron–wüstite. The
situation is different for oxidizing conditions above the water maxi-
mum, where a fluid in equilibrium with diamond has quite constant
fO2, but evolves from CO2- to H2O-rich compositions. Thus, inclusion
suites in diamonds formed on the oxidized side of this diagram will
show a more uniform oxidation state.
Particularly these latter conditions apply to UHPM polycrystalline
diamonds. Neither native metals nor alloys and carbides have been
found in these diamonds; instead, they are dominated by inclusions
that indicate high oxygen fugacity (e.g. carbonates), close to the FMQ
32 D.E. Jacob et al. / Earth-Science Reviews 136 (2014) 21–35
oxygen buffer. As predicted by the C–H–O speciation diagram in Fig. 7,
fO2 variability is minimal in inclusion suites from these environments.
The recent discovery by Bali et al. (2013) that water and hydrogen
are likely to be immiscible under the conditions of the mantle geotherm
may help to provide an explanation for the extreme small-scale hetero-
geneities in fO2 conditions represented by the inclusions in polycrystal-
line diamonds. During precipitation of diamond along the saturation
curve (Fig. 7), fluids become enriched in H2O, so that hydrogen is likely
to be released: the differential mobility of water and hydrogen (Bali
et al., 2013) will lead to the production of very reducing environments
on the scale of nanometers to centimeters, promoting the crystallization
of nanophases such as metals, carbides and nitrides.
6.4. Chemical environments for diamond formation
Decades of studies of carbon and nitrogen in diamond have
underlined the complications associated with deciphering the origins
of its ingredients (for recent reviews see Stachel and Harris, 2008;
Shirey et al., 2013 and references therein). As carbon is subjected to
efficient deep recycling on Earth (Javoy et al., 1982), there is no question
that sources of carbon in diamond are multiple, comprising both mantle
and subducted crustal components. Source characteristics for carbon
and nitrogen, however, are often encrypted by mixing and fractionation
processes upon subduction and at mantle temperatures (Deines, 1980).
It is likely that the silicic, carbonatitic and saline compositions of fluids
included in diamonds are subjected to similarly complex processes,
which complicate interpretations. Silicate and carbonatitic liquids
have long been recognized as major metasomatic agents in the mantle.
In comparison, the roles of halides and halogens in the Earth's mantle
are much more enigmatic and as of yet data on the deep halogen
cycle is virtually non-existent (Izraeli et al., 2001; Kamenetsky et al.,
2004; Litasov and Ohtani, 2009).
Volatiles, even when present in only small amounts, have large
effects on the melting points of peridotite and ultramafic rocks in the
mantle (Green, 1973; Eggler, 1976; Wyllie, 1978; Taylor and Green,
1988; Dasgupta and Hirschmann, 2006; Foley, 2011). Precipitation of
diamond from a C–H–O fluid via redox reaction rapidly increases the
water activity of the fluid (Fig. 7), which may promote melting of the
surrounding mantle material. This process couples the precipitation of
diamond with melting caused by the increase in water activity of the
fluid. It occurs in both reduced and oxidized conditions, but will be
particularly effective in oxidized conditions where the depression of
melting temperatures in the presence of both H2O and CO2 is stronger
(Foley et al., 2009). This process results in the generation of silicate
partial melts simultaneous with diamond precipitation that mix with
the diamond fluid and, thus, are likely to be included into the growing
diamonds. It is therefore hypothesized here that syngenetic solid
phase inclusions in diamonds generally represent mixtures of compo-
nents carried in the fluid and material produced by partial melting of
surrounding rocks at the site of diamond precipitation on a very local
scale.
The composition of a given inclusion suite would then depend on
both the chemical load of the carbon-bearing fluid which may vary
depending on its oxidation state and on the degree of partial melting
of the local rock. Higher degrees of melting lead to inclusion suites
dominated by silicate material typical for the local environment, thus
with compositions representing the Earth's mantle (eclogitic–peridotitic).
Lower degrees of melting of local rock generate inclusions that are more
representative for the chemical composition of the original C–H–O fluid
and its solutes. However, in either case, the redox conditions recorded
by the syngenetic inclusion suite are a result of the diamond precipita-
tion process and bear little information on the original oxygen fugacity
of the diamond's environment.
For the UHPM polycrystalline diamonds, the marble host rocks
present potential near-infinite reservoirs of carbon. Indeed, the major
and trace element chemistry of the solid nano-inclusions precipitated
from the carbon-bearing fluids, in both the marbles and the felsic
gneisses corresponds closely to those of their respective hosts. Major
fluid species identified by FTIR spectroscopy are carbonate and water in
inclusions from marbles and felsic gneisses alike (de Corte et al., 1999;
Kikuchi et al., 2005; Dobrzhinetskaya et al., 2006; Dobrzhinetskaya and
Wirth, 2009; Sitnikova and Shatsky, 2009). In order to explain the
differences in diamond grade between directly neighboring lithologies,
however, cm-scale heterogeneities in fluid species, e.g. in XCO2, must
have existed during peak metamorphism (Ogasawara et al., 2000;
Ogasawara and Aoki, 2005).
Nevertheless, despite the majority of evidence pointing to local
sources for the carbon-bearing fluids in these UHP terranes, noble gas
isotopic studies (Sumino et al., 2011) suggested the involvement of an
exotic, mantle-derived component at least for the Kokchetav massif,
which is the only UHPM locality for which a noble gas study was carried
out to date. A major challenge for the future will be to carefully decipher
these sources of mixed information.
7. Conclusions
State-of-the-art analytical techniques with high spatial resolution
have deepened our understanding of natural diamond and its inclu-
sions, while at the same time they highlight the complexity of the pro-
cesses at work. Taking microanalysis to the submicron scale in diamond
research up to now benefited in particular from TEM analysis using FIB
prepared electron-transparent samples. Its application to carbonado
and to polycrystalline diamond from kimberlite allowed syngenetic
inclusions to be differentiated from epigenetic material, which proved
particularly critical to test models for the origin of carbonado, finally
resolving the Earth's mantle as its origin.
In situ sampling of diamond fluids revealed a large heterogeneity in
redox-conditions and fluid chemical compositions at small scale, which
is not reflected in the macro-inclusion suite.
However, despite originating from such chemically different
environments as the mantle and the crust, fluids from polycrystalline
diamonds have compositions that conform with the fluid end-
members established by studies on fibrous diamonds, thus suggesting
a universally important role of a limited number of basic ingredients,
namely carbonates, silicates, halides and water.
Strong redox gradients reflected by the micro-inclusions indicate
diamond precipitation via small-scale, ephemeral redox processes driven
by the contrasting oxidation states of fluids and their depositional
environment. The susceptibility of the melting point of Earth's mantle
rocks to the presence of even small amounts of volatiles promotes
melting simultaneous to diamond precipitation, further enhanced by
the changing of fluid composition towards higher water activity. This
creates a chemically heterogeneous environment, in which diamonds
and their inclusions are precipitated via redox-freezing processes.
Recent experimental work implies that the generation of ephemeral
small-scale redox gradients may be even further enhanced by the
immiscibility of water and hydrogen in the diamond fluids at these
pressures and temperatures (Bali et al., 2013).
The submicron inclusion suites are therefore products of redox reac-
tions and mixing of components from the C–H–O fluid, which can be
foreign, and those derived locally from the surrounding mantle rocks.
Simple mass balance considerations predict that in instances where
partial melting of the host rock dominates, the fluid component is
occluded in the resulting inclusion chemistry. In these cases the partic-
ular inclusion only bears information on the depositional environment
rather than on the carbon-bearing medium.
In contrast to polycrystalline diamonds from the mantle, those from
UHPM terranes carry evidence for homogeneously oxidizing formation
conditions and carry a strong local signature in their submicron
inclusion suite. Still, rare gas isotopes suggest the seemingly occluded
involvement of a mantle fluid in their formation, suggesting that a
 D.E. Jacob et al. / Earth-Science Reviews 136 (2014) 21–35
foreign fluid component may merely be masked by dilution in the major
and trace element compositions.
Development in modern microanalytical techniques allows in situ
analysis of diamonds and their inclusions spanning roughly five orders
of magnitude in spatial resolution. Information derived from inclusion
suites at either end of the size range complements each other. Macro-
inclusions, for once, give critical insight into the chemical environment
of diamond formation as well as the pressure and temperature range
of diamond growth. On the other hand, micro-inclusions at the lower
end of the size distribution deliver direct information on the diamond
growth medium represented by included minerals, quench phases
and fluid, which cannot be derived from macroinclusions alone.
Acknowledgments
DJ gratefully acknowledges financial support from DFG grant JA781/
9-1 (Heisenberg Professur), the Earth System Science Research Centre
at Johannes-Gutenberg University, Mainz and Macquarie University,
Sydney. De Beers is thanked for the accessibility of suitable sample
material. LD acknowledges support from US National Science Foundation
(grants EAR-0408505, EAR-1118796) and the Lab Fee Research
Award (No. 09-LR-05-116946-DOBL). Anja Schreiber (GFZ Potsdam) is
thanked for skilful FIB sample preparation. We are grateful to Oded
Navon and Andy Moore who reviewed an earlier version of this ms.
This is contribution 460 from the ARC Centre of Excellence for Core to
Crust Fluid Systems (http://www.ccfs.mq.edu.au).
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