Superdeep Diamonds Research Articles

K- and Na-rich davemaoite inclusion in diamond is not inherited from deeply subducted oceanic crusts

Deep potassium (K) and sodium (Na) cycles can affect the physiochemical properties and geodynamic processes of the Earth's interior, to some extent. Recently reported natural K- and Na-rich davemaoite inclusion in superdeep diamond (Tschauner et al., 2021), which is still controversial (Walter et al. 2022a; Tschauner et al., 2022), motivated us to reinvestigate the recycling and partitioning behaviours of K and Na in the subducting oceanic crust under deep-mantle P-T conditions. In this study, we experimentally determined the partitioning of Na and K, as well as other major elements, in a natural phengite-rich eclogite system under 5–30 GPa and 850–1550 °C, relevant to P-T conditions from the deep upper mantle to the uppermost lower mantle. We found that the produced davemaoite with the perovskite structure contained minimal amounts of other elements, including K and Na. Therefore, we conclude that K- and Na-rich davemaoite inclusion in the superdeep diamond cannot be inherited from deeply subducted oceanic crusts. In addition, our experimental results further support previous arguments overestimating the K and Na, and other elemental contents in natural davemaoite, which may further indicate that the reported diamond “inclusion” with abnormally high heteroatoms (Tschauner et al., 2021) is not a davemaoite from the lower mantle (Walter et al. 2022a). Finally, we combined the high-pressure phase relationship in the upper continental crust, oceanic basalt, and pyrolite systems from previous studies, and constructed a geodynamical model for the deep K and Na cycles along with the subduction of the oceanic slabs into the uppermost lower mantle.

Thermoelastic Properties of Fe3+‐Rich Jeffbenite and Application to Superdeep Diamond Barometry

AbstractJeffbenite (Mg3Al2Si3O12) is a tetragonal phase found in so far only in superdeep diamonds, and its thermoelastic parameters are a prerequisite for determining entrapment pressures as it is regarded as a potential indicator for superdeep diamonds. In this study, the thermoelastic properties of synthetic Fe3+‐jeffbenite were measured up to 33.7 GPa and 750 K. High‐temperature static compression data were fitted, giving (∂KT0/∂T)P = −0.0107 (4) GPa/K and αT = 3.50 (3) × 10−5 K−1. The thermoelastic properties and phase stability are applied to modeling isomekes, or P‐T paths intersecting possible conditions of entrapment in diamond. We calculate that under ideal exhumation, jeffbenite entrapped at mantle transition zone conditions will exhibit a high remnant pressure at 300 K (Pinc) of ∼5.0 GPa. Elastic geobarometry on future finds of jeffbenite inclusions can use the new equation of state to estimate entrapment pressures for this phase with still highly uncertain stability field in the mantle.

The composition and redox state of hydrous partial melts generated at the top of the lower mantle

Seismic low-velocity zones, that are proposed to form through hydrous partial melting, have been observed at the top of the lower mantle. The buoyancy of such melts will depend significantly on their iron content, but little is known about how iron partitions into melts under these conditions. In this study, ferrous and ferric iron partitioning between bridgmanite and melt has been studied at 25 GPa and 1973 K. A model, based on these data, indicates that increasing oxygen fugacity and the Al content of bridgmanite can change the mineral–melt partitioning of iron from incompatible to compatible. Hydrous partial melts at the top of a pyrolitic lower mantle are calculated to have an Fe3+/∑Fe ratio of 0.26–0.5 and a total iron content of 5.9–7.8 wt. % in the fO2 range between IW+2 and IW+4. Such melts would be less dense than the surrounding lower mantle and would migrate upwards into the transition zone. This could facilitate the formation of superdeep diamonds and crystallize an assemblage that also contains ferropericlase as the melts lose water to the surrounding ringwoodite.

Distinct Groups of Low- and High-Fe Ferropericlase Inclusions in Super-Deep Diamonds: An Example from the Juina Area, Brazil

Diamonds from the Rio Sorriso placer in the Juina area, Mato Grosso State, Brazil, contain mineral inclusions of ferropericlase associated with MgSiO3, CaSiO3, magnesite, merrillite, and other minerals. The ferropericlase inclusions in Rio Sorriso diamonds are resolved into two distinct genetic and compositional groups: (1) protogenetic, high-Ni and low-Fe (Ni = 8270–10,660 ppm; mg# = 0.756–0.842) ferropericlases, and (2) syngenetic, low-Ni and high-Fe (Ni = 600–3050 ppm; mg# = 0.477–0.718) ferropericlases. Based on the crystallographic orientation relationships between natural ferropericlase inclusions and host diamonds, high-Ni and low-Fe ferropericlases originate in the upper part of the lower mantle, while low-Ni and high-Fe ferropericlases, most likely, originate in the lithosphere. Mineral inclusions form the ultramafic lower-mantle (MgSiO3, which we suggest as bridgmanite, CaSiO3, which we suggest as CaSi-perovskite, and high-Ni and low-Fe ferropericlase) and lithospheric (CaSiO3, which we suggest as breyite, Ca(Si,Ti)O3, and low-Ni and high-Fe ferropericlase) associations. The presence of magnesite and merrillite inclusions in association with ferropericlase confirmed the existence of a deep-seated carbonatitic association. Diamonds hosting high-Ni and low-Ni ferropericlase have different carbon-isotopic compositions (δ13C = −5.52 ± 0.75‰ versus −7.07 ± 1.23‰ VPDB, respectively). It implies the carbon-isotopic stratification of the mantle: in the lower mantle, the carbon-isotopic composition tends to become isotopically heavier (less depleted in 13C) than in lithospheric diamonds. These regularities may characterize deep-seated diamonds and ferropericlases not only in the Juina area of Brazil but also in other parts of the world.

Mantle convection and diamonds

Research subject. The present evolutionary stage of geodynamic theory is associated with the idea of thermochemical convection of various levels in the Earth's mantle, where the centrifugal branches are represented by plumes, and the centripetal - by subduction zones. Aim. The study of diamonds contributes to an understanding of when, at what level in mantle, under what P-T conditions and geochemical environment particular diamonds originated, which were then transported by centrifugal convection flows to the Earth's surface, thereby permitting characterization of this flow. Materials and methods. Generalization of published materials and characterization of mineral inclusions in diamonds allow the general structure of mantle convection to be clarified in different epochs and different regions. Results. The data obtained on mineral inclusions in diamonds, along with the experimental data on the P-T conditions of their mineral parageneses and geophysical data on mantle properties, indicate that the depth of diamond formation varies from the lower lithosphere in the upper part of the upper mantle (≈150-250 km) to the bottom of the lower mantle. At the same time, the diamonds containing mineral inclusions, characteristic of the lower mantle, account for only the first percents of the general number of diamonds. Conclusions. The transport of diamonds from different depths of their origin is a reliable indication of convection processes (as a plume activity) in the mantle. This information provides evidence to the real existence of plumes, which is important in the context of ongoing discussions on the depth of their origin. However, the study of mineral inclusions in diamonds, particularly in superdeep diamonds, is a challenging task due to the retrograde changes, resorption and sometimes complete dissolution on their way to the surface. These circumstances minimize the probability of occurrence of superdeep diamonds and require consideration when making judgements about the reality of existence of superdeep diamonds.

Dual origin of ferropericlase inclusions within super-deep diamonds

Ferropericlase [(Mg,Fe)O] is one of the major constituents of Earth's lower mantle and the most abundant mineral inclusion in sub-lithospheric diamonds. Although a lower mantle origin for ferropericlase inclusions has often been suggested, some studies have proposed that many of these inclusions may instead form at much shallower depths, in the deep upper mantle or transition zone. No straightforward method exists to discriminate ferropericlase of lower-mantle origin without characteristic mineral associations, such as co-existing former bridgmanite. To explore ferropericlase-diamond growth relationships, we have investigated the crystallographic orientation relationships (CORs), determined by single-crystal X-ray diffraction, between 57 ferropericlase inclusions and 37 diamonds from Juina (Brazil) and Kankan (Guinea). We show that ferropericlase inclusions can develop specific (16 inclusions in 12 diamonds), rotational statistical (9 inclusions in 7 diamonds) and random (32 inclusions in 25 diamond) CORs with respect to their diamond hosts. All measured inclusions showing a specific COR were found to be Fe-rich (XFeO > 0.30). Coexistence of non-randomly and randomly oriented ferropericlase inclusions within the same diamond indicates that their CORs may be variably affected by local growth conditions. However, the occurrence of specific CORs only for Fe-rich inclusions indicates that Fe-rich ferropericlases have a distinct genesis and are syngenetic with their host diamonds. This result provides strong support for a dual origin for ferropericlase in Earth's mantle, with Fe-rich compositions likely indicating redox growth in the upper mantle, while more Mg-rich compositions with random COR mostly representing ambient lower mantle trapped as protogenetic inclusions.

Extreme redox variations in a superdeep diamond from a subducted slab.

The introduction of volatile-rich subducting slabs to the mantle may locally generate large redox gradients, affecting phase stability, element partitioning and volatile speciation1. Here we investigate the redox conditions of the deep mantle recorded in inclusions in a diamond from Kankan, Guinea. Enstatite (former bridgmanite), ferropericlase and a uniquely Mg-rich olivine (Mg# 99.9) inclusion indicate formation in highly variable redox conditions near the 660 km seismic discontinuity. We propose a model involving dehydration, rehydration and dehydration in the underside of a warming slab at the transition zone-lower mantle boundary. Fluid liberated by dehydration in a crumpled slab, driven by heating from the lower mantle, ascends into the cooler interior of the slab, where the H2O is sequestered in new hydrous minerals. Consequent fractionation of the remaining fluid produces extremely reducing conditions, forming Mg-end-member ringwoodite. This fractionating fluid also precipitates the host diamond. With continued heating, ringwoodite in the slab surrounding the diamond forms bridgmanite and ferropericlase, which is trapped as the diamond grows in hydrous fluids produced by dehydration of the warming slab.

Mg3Al2Si3O12 jeffbenite inclusion in super-deep diamonds is thermodynamically stable at very shallow Earth’s depths

Jeffbenite (having the same chemical composition of pyrope, ~ Mg3Al2Si3O12, and also known as TAPP phase) is a mineral inclusion only found in diamonds formed between about 300 and 1000 km depth) and is considered a stable phase in the transition zone (410–660 km depth) and/or in the shallowest regions of the lower mantle (around 660–700 km depth). This rare and enigmatic mineral is considered to be a pressure marker for super-deep diamonds and therefore it has a key role in super-deep diamond research. However, the pressure–temperature stability fields for Mg3Al2Si3O12 jeffbenite is unknown and its actual formation conditions remain unexplored. Here we have determined the thermodynamic pressure–temperature stability field for the jeffbenite Mg-end member and surprisingly discovered that it is stable at low pressure–temperature conditions, i.e., 2–4 GPa at 800 and 500 °C. Thus, Mg3Al2Si3O12 jeffbenite is not the high-pressure polymorph of pyrope and is likely a retrogressed phase formed during the late ascent stages of super-deep diamonds to the surface.

Redox species and oxygen fugacity of slab-derived fluids: Implications for mantle oxidation and deep carbon-sulfur cycling

The generation and migration of slab-derived fluids modulate subduction zone seismicity, arc magmatism, and deep volatile cycling. However, the redox species and oxygen fugacity (fO2) (hereafter expressed as log units relative to the fayalite–magnetite–quartz buffer, △FMQ) of slab-derived fluids are highly debated. Here we conducted phase equilibria modeling on altered oceanic crust (AOC) and serpentinites along typical subduction geotherms in the C-S-bearing system over a pressure range of 0.5–6 GPa. With the averaged compositions of AOC and serpentinite, our calculated results show that oxidized carbon-sulfur species dominate slab-derived fluids during slab subduction. As a result, slab-derived fluids are highly oxidized and at or above the typical △FMQ values of arc magmas at forearc to subarc depths. The predicted oxidized carbon and sulfur species are compatible with natural observations in fluid inclusions from many oceanic HP metamorphic rocks. More importantly, it is revealed that, the redox state of slab-derived fluids is primarily controlled by the redox budget (RB) of the slab prior to subduction. Subduction-zone thermal structure, however, only exerts a minor influence on the slab-derived fluid fO2, which is supported by the similar fO2 ranges in arc lavas from cold and hot subduction zones. Our models further show that, if an open system is assumed, most of carbon (>70%) and sulfur (>50%) in cold subducted AOC and serpentinite would be lost at subarc depths. Small amounts of carbon and sulfur could be transported into the deeper mantle via closed-system subduction and open-system cold subduction, supplying the source materials for volatile-rich intraplate magmas and superdeep diamonds.

Melting of the Fe‐C‐H System and Earth's Deep Carbon‐Hydrogen Cycle

AbstractThe occurrences and cycling of slab‐originated carbon and hydrogen are considered to be controlled by their reactions with metallic iron from mantle disproportionation and slab serpentinization, to form Fe alloys containing carbon and hydrogen. Here we show experimental results on the phase relations and melting of the Fe‐C‐H system using laser‐heated diamond anvil cell and X‐ray diffraction techniques up to 72 GPa. The incorporation of hydrogen was found to lower the eutectic melting temperatures of Fe‐C alloy by ∼50–178 K at 20–70 GPa, facilitating the formation of metallic liquids in the deep mantle and thus enhancing the mobility and deep cycling of subducted carbon and hydrogen. Hydrogen also substitutes with carbon in Fe‐C metal to form hydride and diamond at relatively high‐temperature conditions (e.g., 42.6 GPa, >1885 K and 71.8 GPa, >1798 K). The hydrogen‐carbon‐enriched metallic liquids provide the necessary fluid environment for superdeep diamond growth.

Ringwoodite and zirconia inclusions indicate downward travel of super-deep diamonds

Abstract Natural diamonds and their inclusions provide unique glimpses of mantle processes from as deep as ~800 km and dating back to 3.5 G.y. Once formed, diamonds are commonly interpreted to travel upward, either slowly within mantle upwellings or rapidly within explosive, carbonate-rich magmas erupting at the surface. Although global tectonics induce subduction of material from shallow depths into the deep mantle, mineralogical evidence for downward movements of diamonds has never been reported. We report the finding of an unusual composite inclusion consisting of ringwoodite (the second finding to date), tetragonal zirconia, and coesite within an alluvial super-deep diamond from the Central African Republic. We interpret zirconia + coesite and ringwoodite as prograde transformation products after zircon or reidite (ZrSiO4) and olivine or wadsleyite, respectively. This inclusion assemblage can be explained if the diamond traveled downward after entrapping olivine/wadsleyite + zircon/reidite, dragged down by a subducting slab, before being delivered to the surface. This indicates that the commonly assumed view that diamonds form at, and capture material from, a specific mantle level and then travel upward is probably too simplistic.

Fate of Carbonates in the Earth’s Mantle (10-136 GPa)

Earth carbon cycle shapes the evolution of our planet and our habitats. As a key region of carbon cycle, subduction zone acts as a sole channel transporting supracrustal carbonate rocks down to the mantle, balancing carbon budget between the Earth’s surface and the interior, and regulating CO2 concentration of the atmosphere. How carbonates evolve at depth is thus, a most fundamental issue in understanding carbon flux and carbon sequestration mechanism in the Earth. This study reviews prominent progresses made in the field of crystal chemistry of carbonates along subduction geotherms. It clearly finds that, in addition to common carbonates in the Earth’s crust, several new polymorphs of carbonates have been discovered to be stable under high-pressure and high-temperature conditions. This opens possibilities for oxidized carbon species in the deep Earth. However, metamorphic decarbonatation and reduction reactions restrict subducting carbonates to the top-mid region of the lower mantle. Specifically, subsolidus decarbonatation in the form of carbonates reacting with silicates has been proposed as an efficient process releasing CO2 from slabs to the mantle. Besides, carbonate reduction in the metal-saturated mantle likely results in generation of super-deep diamonds and a considerable degree of carbon isotope fractionation. Review of these novel findings leads us to consider three issues in the further studies, including 1) searching for new chemical forms of carbon in the mantle, 2) determining the reduction efficiency of carbonates to diamonds and the accompanying carbon isotope fractionation and 3) concerning carbon cycle in subduction of continental crust.

Low- and High-Fe Ferropericlase Inclusions in Super-Deep Diamonds and Their Depth of Origin: An Example from the Juina Area, Brazil,

Low- and High-Fe Ferropericlase Inclusions in Super-Deep Diamonds and Their Depth of Origin: An Example from the Juina Area, Brazil,

Ellinaite, CaCr<sub>2</sub>O<sub>4</sub>, a new natural post-spinel oxide from Hatrurim Basin, Israel, and Juína kimberlite field, Brazil

Abstract. Ellinaite, a natural analog of the post-spinel phase β-CaCr2O4, was discovered at the Hatrurim Basin, Hatrurim pyrometamorphic formation (the Mottled Zone), Israel, and in an inclusion within the super-deep diamond collected at the placer of the Sorriso River, Juína kimberlite field, Brazil. Ellinaite at the Hatrurim Basin is confined to a reduced rankinite–gehlenite paralava, where it occurs as subhedral grains up to 30 µm in association with gehlenite, rankinite and pyrrhotite or forms the rims overgrowing zoned chromite–magnesiochromite. The empirical formula of the Hatrurim sample is (Ca0.960Fe0.0162+Na0.012Mg0.003)0.992(Cr1.731V0.1833+Ti0.0683+Al0.023Ti0.0034+)2.008O4. The mineral crystallizes in the orthorhombic system, space group Pnma, unit-cell parameters refined from X-ray single-crystal data: a 8.868(9), b 2.885(3), c 10.355(11) Å, V 264.9(5) Å3 and Z=4. The crystal structure of ellinaite from the Hatrurim Basin has been solved and refined to R1=0.0588 based on 388 independent observed reflections. Ellinaite in the Juína diamond occurs within the micron-sized polyphase inclusion in association with ferropericlase, magnesioferrite, orthorhombic MgCr2O4, unidentified iron carbide and graphite. Its empirical formula is Ca1.07(Cr1.71Fe0.063+V0.06Ti0.03Al0.03Mg0.02Mn0.02)Σ1.93O4. The unit-cell parameters obtained from HRTEM data are as follows: space group Pnma, a 9.017, b 2.874 Å, c 10.170 Å, V 263.55 Å3, Z=4. Ellinaite belongs to a group of natural tunnel-structured oxides of the general formula AB2O4, the so-called post-spinel minerals: marokite CaMn2O4, xieite FeCr2O4, harmunite CaFe2O4, wernerkrauseite CaFe23+Mn4+O6, chenmingite FeCr2O4, maohokite MgFe2O4 and tschaunerite Fe(FeTi)O4. The mineral from both occurrences seems to be crystallized under highly reduced conditions at high temperatures (>1000 ∘C), but under different pressure: near-surface (Hatrurim Basin) and lower mantle (Juína diamond).

High-pressure crystal structure and equation of state of ferromagnesian jeffbenite: implications for stability in the transition zone and uppermost lower mantle

Jeffbenite, ideally Mg3Al2Si3O12, has been identified as inclusions in super-deep diamonds originating from depths that exceed 300 km. Although Mg-end member jeffbenite has limited stability at upper-mantle conditions, iron-bearing jeffbenite may have broader P–T stability that extends to the transition zone or uppermost lower mantle, incorporating significant amounts of ferric iron. Using synchrotron-based, single-crystal X-ray diffraction (XRD) and synchrotron Mössbauer spectroscopy (SMS) at pressures up to 29 GPa, we report the crystal structure, compressibility, and likely spin transition of iron in ferromagnesian jeffbenite (Mg2.32Al0.03Fe2+1.28Fe3+1.77Si2.85O12). High-pressure structure refinements reveal that Fe3+ substitution for Si in the T2 site, which shares edges with the M2 octahedron, likely stabilizes jeffbenite at high pressure, because it increases the cation-to-cation distance between these sites. Although ferromagnesian jeffbenite does not undergo a structural phase transition below 30 GPa, SMS hyperfine parameters suggest the onset of an electronic spin transition of iron from high-spin (HS) to low-spin (LS) at around 22 GPa, which may increase its stability at high pressures. Pressure–volume data were fit to a third order Birch–Murnaghan equation of state, resulting in V0 = 816.54(9), KT0 = 181.54(1.39), and $${K}_{T0}^{\prime}$$ = 2.76(14). These equation of state parameters are applicable to evaluating the encapsulation pressures of super-deep diamonds. The density and bulk modulus of ferromagnesian jeffbenite are similar to or higher than pyrope–almandine, pyrope–majorite, and skiagite–majorite solid solution garnets, further suggesting that jeffbenite may be an important ferric–iron silicate in the deeper parts of the mantle transition zone and uppermost lower mantle. However, future studies on the influence of temperature and oxidation state on the stability and equations of state of iron-bearing jeffbennite are still needed to determine what role, if any, jeffbenite plays in transition-zone mineralogy.

Ferromagnesian jeffbenite synthesized at 15 GPa and 1200 °C

Abstract Single crystals of Al-free, ferromagnesian jeffbenite up to 200 µm in size have been synthesized at 15 GPa and 1200 °C in a 1200 tonne multi-anvil press from a starting composition in the forsteritefayalite-magnetite-water system. This phase has the approximate formula Mg2.62Fe0.872+Fe1.633+Si2.88O12 and is observed to coexist with a Ca-free clinopyroxene plus what appears to be quenched melt. The crystal structure has been refined from single-crystal X-ray diffraction data and is similar to that determined for natural Al-bearing jeffbenite, Mg3Al2Si3O12, reported from inclusions in superdeep diamonds. The structure is a tetragonal orthosilicate in space group I42d with a = 6.6449(4) Å, c = 18.4823(14) Å, and is structurally more closely related to zircon than to garnet. The T2 site is larger than T1, shares an edge with the M2 octahedron, and incorporates significant Fe3+. Because of the tetrahedral incorporation of trivalent cations, jeffbenite appears to be compositionally distinct from garnet. Previous speculations that the phase may only occur as a retrograde decompression product from bridgmanite are not supported by its direct synthesis under transition zone conditions. The phase has a calculated density of 3.93 g/cm3, which is indistinguishable from a garnet of comparable composition, and is a possible component in the mantle transition zone under oxidizing conditions or with Al-rich compositions.

Diamonds from the Mir Pipe (Yakutia): Spectroscopic Features and Annealing Studies

For this study, 21 samples of colorless octahedral diamonds (weighing 5.4–55.0 mg) from the Mir pipe (Yakutia) were investigated with photoluminescence (PL), infrared (IR), and electron paramagnetic resonance (EPR) spectroscopies. Based on the IR data, three groups of diamonds belonging to types IIa, IaAB, and IaB were selected and their spectroscopic features were analyzed in detail. The three categories of stones exhibited different characteristic PL systems. The type IaB diamonds demonstrated dominating nitrogen–nickel complexes S2, S3, and 523 nm, while they were less intensive or even absent in the type IaAB crystals. The type IIa diamonds showed a double peak at 417.4 + 418.7 nm (the 418 center in this study), which is assumed to be a nickel–boron defect. In the crystals analyzed, no matter which type, 490.7, 563.5, 613, and 676.3 nm systems of various intensity could be detected; moreover, N3, H3, and H4 centers were very common. The step-by-step annealing experiments were performed in the temperature range of 600–1700 °C. The treatment at 600 °C resulted in the 563.5 nm system’s disappearance; the interstitial carbon vacancy annihilation could be considered as a reason. The 676.5 nm and 613 nm defects annealed out at 1500 °C and 1700 °C, respectively. Furthermore, as a result of annealing at 1500 °C, the 558.5 and 576 nm centers characteristic of superdeep diamonds from São Luis (Brazil) appeared. These transformations could be explained by nitrogen diffusion or interaction with the dislocations and/or vacancies produced.

Origin, properties, and structure of breyite: The second most abundant mineral inclusion in super-deep diamonds

AbstractEarth's lower mantle most likely mainly consists of ferropericlase, bridgmanite, and a CaSiO3- phase in the perovskite structure. If separately trapped in diamonds, these phases can be transported to Earth's surface without reacting with the surrounding mantle. Although all inclusions will remain chemically pristine, only ferropericlase will stay in its original crystal structure, whereas in almost all cases bridgmanite and CaSiO3-perovskite will transform to their lower-pressure polymorphs. In the case of perovskite structured CaSiO3, the new structure that is formed is closely related to that of walstromite. This mineral is now approved by the IMA commission on new minerals and named breyite. The crystal structure is triclinic (space group: P1) with lattice parameters a0 = 6.6970(4) Å, b0 = 9.2986(7) Å, c0 = 6.6501(4) Å, α = 83.458(6)°, β = 76.226(6)°, γ = 69.581(7)°, and V = 376.72(4) Å. The major element composition found for the studied breyite is Ca3.01(2)Si2.98(2)O9. Breyite is the second most abundant mineral inclusion after ferropericlase in diamonds of super-deep origin. The occurrence of breyite has been widely presumed to be a strong indication of lower mantle (=670 km depth) or at least lower transition zone (=520 km depth) origin of both the host diamond and the inclusion suite.In this work, we demonstrate through different formation scenarios that the finding of breyite alone in a diamond is not a reliable indicator of the formation depth in the transition zone or in the lower mantle and that accompanying paragenetic phases such as ferropericlase together with MgSiO3 are needed.

Thermal equation of state of phase egg (AlSiO3OH): implications for hydrous phases in the deep earth

Phase egg (AlSiO3OH), an important hydrous phase in the Al2O3–SiO2–H2O ternary system, was found in the superdeep diamond from the mantle transition zone. Here, we have investigated the compressibility and the crystal structural evolution of phase egg using the synchrotron-based single-crystal X-ray diffraction and infrared spectroscopy combined with diamond anvil cells up to 32 GPa and 900 K. Present results show that the hydrogen atom flips its position and forms a new hydrogen bond configuration at ~ 14 GPa and room temperature, leading to a first-order phase transition of phase egg, but this behavior is smeared out because of thermal disordering of hydrogen atom at high temperatures. These findings provide important implications for revealing the complex state of hydrogen in the deep earth. Along the cold and warm subducting slab geotherms, the density and bulk velocity of phase egg are greater than those of preliminary reference Earth model in the mantle transition zone, presenting negative buoyancy force for deep-water transportation. Based on the obtained thermal elastic parameters, we further demonstrate that topaz-OH transforms to phase egg with a ~ 11.7% increase in bulk velocity and a ~ 4.2% increase in density, and phase egg decomposes into δ-AlOOH and stishovite with a ~ 6.2% increase in bulk velocity and a ~ 4.0% increase in density under subduction zone conditions.

The lithospheric-to-lower-mantle carbon cycle recorded in superdeep diamonds.

The transport of carbon into Earth's mantle is a critical pathway in Earth's carbon cycle, affecting both the climate and the redox conditions of the surface and mantle. The largest unconstrained variables in this cycle are the depths to which carbon in sediments and altered oceanic crust can be subducted and the relative contributions of these reservoirs to the sequestration of carbon in the deep mantle1. Mineral inclusions in sublithospheric, or 'superdeep', diamonds (derived fromdepths greater than250 kilometres) can be used to constrain these variables. Here we present oxygen isotope measurements of mineral inclusions within diamonds from Kankan, Guineathat are derived from depths extending from the lithosphere to the lower mantle (greater than 660 kilometres). These data, combined with the carbon and nitrogen isotope contents of the diamonds, indicate that carbonated igneous oceanic crust, not sediment, is the primary carbon-bearing reservoir in slabs subducted to deep-lithospheric and transition-zone depths (less than 660 kilometres). Within this depth regime, sublithospheric inclusions are distinctly enriched in 18O relative to eclogitic lithospheric inclusions derived from crustal protoliths. The increased 18O content of these sublithospheric inclusions results from their crystallization from melts of carbonate-rich subducted oceanic crust. In contrast, lower-mantle mineral inclusions and their host diamonds (deeper than 660 kilometres) have a narrow range of isotopic values that are typical of mantle that has experienced little or no crustal interaction. Because carbon is hosted in metals, rather than in diamond, in the reduced, volatile-poor lower mantle2, carbon must be mobilized and concentrated to form lower-mantle diamonds. Our data support a model in which the hydration of the uppermost lower mantle by subducted oceanic lithosphere destabilizes carbon-bearing metals to form diamond, without disturbing the ambient-mantle stable-isotope signatures. This transition from carbonate slab melting in the transition zone to slab dehydration in the lower mantle supports a lower-mantle barrier for carbon subduction.