Genesis of diamonds in the lower mantle

The “forbidden” assemblage (ferropericlase + enstatite) as inclusions in diamonds has been taken as evidence to imply that these inclusions and their host diamonds formed initially in the lower mantle. Magnesite is probably the only stable carbonate at depths greater than ∼220 km. Like dehydration reactions, the reaction boundary for the decarbonation of magnesite has a positive dT/dP slope at lower pressures, which becomes negative at higher pressures, if no other phase intervenes. This reaction boundary probably intersects the geotherm between ∼900 and ∼1100 km, below which magnesite decomposes into an assemblage periclase + diamond + oxygen. Thus, ferropericlase is the most likely inclusion in diamond formed in the lower mantle. The high frequency of sole occurrence of ferropericlase in diamonds from Sao Luiz, Brazil seems to substantiate the present speculation. Received: 8 June 1998 / Accepted: 28 September 1998     

Diamond formation and source carbonation: mineral associations in diamonds from Namibia

Mineral inclusions in diamonds from Namibia document a range of mantle sources, including eclogitic, websteritic and peridotitic parageneses. Based on unusual textural features a group of inclusions showing websteritic, peridotitic and transitional chemical features is assigned to an 'undetermined suite' (12% of the studied diamonds). The mutual characteristic of this group is the occurrence of lamellar intergrowths of clinopyroxene and orthopyroxene. In addition, the 'undetermined suite' is associated with a number of uncommon phases: in one diamond MgCO₃ is enclosed by clinopyroxene. Other minerals that form touching inclusions with the pyroxene lamellae are (1) a SiO₂ phase observed in three diamonds, together with CaCO₃ in one of them, (2) phlogopite and a Cr-rich 'titanate' (probably lindsleyite). The inclusions document a metamorphic path of decreasing pressures and temperatures after entrapment in diamond. First, homogeneous low-Ca clinopyroxenes were entrapped at high temperatures. They subsequently exsolved orthopyroxene and probably also SiO₂ (coesite) on cooling along a P,T trajectory that did not allow garnet to be exsolved as well. Phlogopite, carbonates and LIMA phases are the result of overprint of a peridotitic source rock by a carbon-rich agent. The resulting unusual, olivine-free mineral association and the host diamonds are interpreted as products of extensive carbonation of the peridotite.     

Kankan diamonds (Guinea) II: lower mantle inclusion parageneses

Frequent inclusions of ferropericlase, some coexisting with phases of MgSiO₃, CaSiO₃ and SiO₂ composition, suggest that a large proportion of diamonds from Guinea are derived from the lower mantle. Low aluminium contents in MgSiO₃ inclusions indicate derivation from the uppermost lower mantle, where Al solubility in perovskite is low. Trace element analyses (SIMS) of CaSiO₃ inclusions reveal extreme degrees of LREE (200–2000 times chondritic) and Sr enrichment (70–1000 times chondritic) together with negative and positive Eu anomalies. This implies a highly enriched lower mantle source, possibly a product of a subducted oceanic slab. A number of phases that are only stable in the upper mantle are found to coexist with lower mantle phases and thereby indicate retrograde equilibration during slow exhumation within a rising plume or convection cell. In one case, however, an inclusion paragenesis of ferropericlase and olivine can be shown to have formed within the upper mantle, indicating that the occurrence of ferropericlase inclusions alone is an unreliable indicator of lower mantle origin. Received: 26 January 2000 / Accepted: 18 May 2000     

Monohydrocalcite in speleothems: An alternative interpretation

Genesis for a mineral assemblage from Eibengrotte, a small limestone cave near Fränkische Schweiz, Western Germany, is described. The assemblage includes monohydrocalcite, hydromagnesite, nesquehonite, dolomite, aragonite and calcite. A biochemical genesis is proposed as a growth alternative to the Fischbeck and Müller (1971) evaporation-aerosol mechanism.     

Nature of diamonds in Yakutian eclogites: views from eclogite tomography and mineral inclusions in diamonds

We have performed dissections of two diamondiferous eclogites (UX-1 and U33/1) from the Udachnaya kimberlite, Yakutia in order to understand the nature of diamond formation and the relationship between the diamonds, their mineral inclusions, and host eclogite minerals. Diamonds were carefully recovered from each xenolith, based upon high-resolution X-ray tomography images and three-dimensional models. The nature and physical properties of minerals, in direct contact with diamonds, were investigated at the time of diamond extraction. Polished sections of the eclogites were made, containing the mould areas of the diamonds, to further investigate the chemical compositions of the host minerals and the phases that were in contact with diamonds. Major- and minor-element compositions of silicate and sulfide mineral inclusions in diamonds show variations among each other, and from those in the host eclogites. Oxygen isotope compositions of one garnet and five clinopyroxene inclusions in diamonds from another Udachnaya eclogite (U51) span the entire range recorded for eclogite xenoliths from Udachnaya. In addition, the reported compositions of almost all clinopyroxene inclusions in U51 diamonds exhibit positive Eu anomaly. This feature, together with the oxygen isotopic characteristics, is consistent with the well-established hypothesis of subduction origin for Udachnaya eclogite xenoliths. It is intuitive to expect that all eclogite xenoliths in a particular kimberlite should have common heritage, at least with respect to their included diamonds. However, the variation in the composition of multiple inclusions within diamonds, and among diamonds, from the same eclogite indicates the involvement of complex processes in diamond genesis, at least in the eclogite xenoliths from Yakutia that we have studied.     

An alternative model for silica enrichment in the Kaapvaal subcontinental lithospheric mantle

The Mg- and Si-rich nature of the sub-cratonic lithospheric mantle (SCLM) beneath the Kaapvaal Craton indicates extensive melt depletion, followed by a Si-enrichment process. Six highly silica enriched peridotites from Kimberley containing high amounts of orthopyroxene (Opx) or garnet (Grt) that are locally concentrated in clots, were investigated to constrain the timing and nature of the Si-enrichment process. A clinopyroxene-bearing lherzolite containing an Opx-clot was studied to quantify the effects of recent metasomatism on the Si-enriched samples. Minerals from the lherzolite, together with Opx from harzburgites and Opx- and Grt-clots have Hf-Nd isotope ratios at the time of kimberlite eruption, 90 Ma, comparable to group I kimberlites and are close to trace element equilibrium with kimberlitic melts. This implies the xenoliths underwent major interaction with kimberlitic melts close to the time of kimberlite eruption.Harzburgites and mineral clots record equilibration pressures and temperatures of, respectively, between 3.5-4.3 GPa and 930-1060 °C. The garnets in Opx-clots have low Lu/Hf and ε_Hf(t) −15, whereas garnets from Grt-clots have high Lu/Hf and ε_Hf(t) +10. In contrast, Grt from both Grt- and Opx-clots have low Sm/Nd and ε_Nd −10. The whole rock platinum group element (PGE) concentrations are an order of magnitude higher in the Grt-clot than the Opx-clot. Measured ¹⁸⁷Os/¹⁸⁸Os range from 0.1085 to 0.1222. The Grt-clot bearing sample yields Nd-Hf-Os isotope model ages that suggest formation in the Neoproterozoic (∼650 Ma). In contrast, an Opx-clot yields T_RD ages of 2.8 Ga, which is interpreted as the time of formation of the host harzburgite. The Opx-clots and host harzburgites have comparable Lu-Hf isotope systematics that imply Opx growth at ∼1.3 Ga and hence their formation is not related to the Grt-clots.Garnets from Opx- and Grt-clots have elevated high-field strength element (HFSE) concentrations, and lack HFSE depletion relative to other trace elements with comparable degrees of incompatibility in the mantle (La/Nb < 0.5). In addition, calculated melts in equilibrium with Grt have strongly fractionated REE (Nd/Yb > 300) and HREE depletion (Yb_N < 0.1) suggesting equilibration with a hydrous melt that is more HREE depleted than a kimberlitic melt. Previous models that related Si-enrichment to subduction are inconsistent with the lack of HFSE depletion (La/Nb < 0.5). Therefore the favoured model for Opx- and Grt-clot formation is infiltration of a hydrous melt in a within plate geodynamical environment associated with volcanism in the Mid-proterozoic and Neoproterozoic, respectively. This implies that Si-enrichment of the Kaapvaal SCLM may be a consequence of numerous localised magmatic events rather than a single craton-wide process.     

Iron partitioning in pyrolitic lower mantle

The partitioning of iron between Mg-rich perovskite (Pv) and ferropericlase (Fp) was investigated for a pyrolitic bulk composition over a wide range of simulated lower-mantle pressures and temperatures from 28 to 114 GPa and from 1,900 to 2,300 K, in a laser-heated diamond anvil cell (DAC). The recovered DAC samples are chemically homogeneous, indicating a relatively small temperature gradient during laser heating. The chemical compositions of coexisting Pv, Fp, and Ca-rich perovskite (CaPv) were determined by energy-dispersive X-ray spectroscopy (EDS) using an EDS instrument attached to a transmission electron microscope. Our results demonstrate that at pressures above 90 GPa, Pv becomes more Fe-rich with increasing pressure, which is likely due to the effects of high-spin to low-spin crossover of Fe³⁺ in Pv. We highlight that such a change in Fe–Mg partitioning between Pv and Fp should have a strong influence on the physical properties of the deep lower mantle.     

Decompression and unmixing of crystals included in diamonds from the mantle transition zone

A suite of exceptional mineral inclusions in diamonds from the São Luiz river, Juina province, Brazil, shows a wide range of garnet/majorite mineral compositions co-existing with clinopyroxene; the overall bulk compositions are eclogitic. The inclusions have a wide variety of textural arrangements, but crystallographic data obtained by EBSD shows that each inclusion consists of a single garnet with constant crystallographic orientation whilst clinopyroxene grains have preferred orientation with relation to garnet {110} and <111>. This suggests that the inclusions were originally single phase majoritic garnets, and that they preserve various states of progressive unmixing (exsolution) into lower pressure garnet and clinopyroxene compositions during transport of the host diamonds towards the Earth’s surface. On the basis of high pressure–temperature experimental data some of the original majoritic garnets must have come from depths of 450 km or more, and therefore resided in the transition zone and asthenospheric upper mantle. Particularly extensive re-equilibration of many inclusions took place at depths of ca 180–200 km (probably close to the base of the continental lithosphere). The partially unmixed state of the inclusions provides a unique opportunity for using mineral diffusion data to roughly estimate the rate of transport through the asthenospheric upper mantle, and within error this rate is found to be broadly compatible with expected transport rates by upper mantle convection or plume flow.     

Ferropericlase—a lower mantle phase in the upper mantle

Experiments on compositions along the join MgO–NaA³⁺Si₂O₆ (A=Al, Cr, Fe³⁺) show that sodium can be incorporated into ferropericlase at upper mantle pressures in amounts commonly found in natural diamond inclusions. These results, combined with the observed mineral parageneses of several diamond inclusion suites, establish firmly that ferropericlase exists in the upper mantle in regions with low silica activity. Such regions may be carbonated dunite or stalled and degassed carbonatitic melts. Ferropericlase as an inclusion in diamond on its own is not indicative of a lower mantle origin or of a deep mantle plume. Coexisting phases have to be taken into consideration to decide on the depth of origin. The composition of olivine will indicate an origin from the upper mantle or border of the transition zone to the lower mantle and whether it coexisted with ferropericlase in the upper mantle or as ringwoodite. The narrow and flat three phase loop at the border transition zone—lower mantle together with hybrid peridotite plus eclogite/sediments provides an explanation for the varying and Fe-rich nature of the diamond inclusion suite from Sao Luiz, Brazil.     

An alternative interpretation for the formation of doubly plunging folds in sandstone terrains

Folds are marvellous features of mountain terrains, but despite extensive research, many fundamental problems have still not been solved. In terrains of sandstone, fold hinges are rarely straight lines but curved, forming a pattern characterized by doubly plunging, elliptical dome‐and‐basin structures. Such structures are an obvious manifestation of coeval or successive shortening deformation in two orthogonal principal directions in the horizontal plane. Based on an anatomic investigation of the fold pattern of sandstone beds at the rocky beaches of Saint‐Jean‐Port‐Joli (Quebec, Canada), we propose that the doubly plunging folds may result from a transition from a plane deformation to a constrictional deformation due to auxetic effects of quartz‐rich rocks. The sandstone beds possessed potentially such negative values of Poisson's ratio that, when placed under compression in one direction, they become contracted in the transverse direction, producing a series of doubly plunging folds. Further work is needed to approve or disapprove the interpretation.     

Nitrogen isotopes in peridotitic diamonds from Fuxian, China: the mantle signature

Nitrogen isotopes in peridotitic diamonds from Fuxian, China, suggest that the upper mantle δ¹⁵N-value has been globally homogeneous since at least the Proterozoic (−5 to −8‰/ATM), with similar values for subcontinental and MORB mantle.
  In addition, Fuxian diamonds retain the memory of a primary nitrogen lower in δ¹⁵N (down to −25‰). For the first time δ¹⁵N- values in diamonds match those of enstatite chondrites, supporting a formation of the Earth from such meteorites and the idea of a heterogeneous accretion of the Earth's volatiles.
  Nitrogen concentrations in diamonds are believed to depend strongly on the rate of the diamond growth and not to be an indicator of C/N ratios of the fluids from which they grew.     

Rare and unusual mineral inclusions in diamonds from Mwadui, Tanzania

Syngenetic diamond inclusions from the Mwadui kimberlite reveal that an unusually fertile section of lithospheric mantle beneath the Central African Craton was sampled. This is shown by a very high ratio of lherzolitic to harzburgitic garnet inclusions (1:2) and low Mg/Fe-ratios in olivine and orthopyroxene. Geothermometry applied to the peridotitic inclusions indicates disequilibrium between non-touching inclusion pairs to be common. Disequilibrium between garnet-olivine and garnet-orthopyroxene pairs suggests successive iron enrichment during diamond formation, e.g. leading to the presence of harzburgitic garnet and lherzolitic olivine in the same diamond. Apart from the dominant peridotitic inclusion suite (88%), rare eclogitic inclusions occur (2%) and a number of uncertain paragenesis. Two diamonds, one with eclogitic garnets with moderate pyroxene solid solution and the other with a single ferro-periclase inclusion, suggest the contribution of a small sub-lithospheric component. The finding of the association Fe-FeO-Fe₃O₄ in one single diamond indicates diamond formation over a large range of f _O2 conditions, possibly along redox fronts. Steep compositional gradients may also be reflected by the joint occurrence of harzburgitic garnet and a SiO₂-phase in the same diamond. Alternatively the formation of the SiO₂-phase may be due to extreme carbonation of the peridotitic source. Further unusual findings include the exsolution of a silicate phase from magnetite inclusions, (i.e. primary solution of γ-olivine) and an ilmenite inclusion with an eskolaite (Cr₂O₃) component of 14.5 mol%, the latter together with harzburgitic paragenesis silicate inclusions. Received: 23 August 1997 / Accepted: 7 January 1998     

Cymrite as mineral clathrate: An overlooked redox insensitive transporter of nitrogen in the mantle

We study the phase relations and mineral chemistry in the systems muscovite–NH₃–N₂-H₂O and eclogite + muscovite–NH₃–N₂-H₂O at 6.3–7.8 GPa, 1000–1200 °C, and oxygen fugacity (fO₂) from ∼IW (Fe–FeO) to ∼ NNO (Ni–NiO) equilibria. The quenched H₂O-bearing fluids differ in nitrogen speciation from NH₃-rich to N₂–rich, and the respective N₂/(NH₃+N₂) ratio varies from <0.1 to ∼ 1. N-bearing K-cymrite is obtained in association with a kyanite-garnet-jadeite ± muscovite ± corundum assemblage in the muscovite–NH₃–N₂-H₂O system and coexists with pyrope-almandine garnet and omphacite in the eclogite + muscovite–NH₃–N₂-H₂O system. The presence of an N-bearing fluid in the studied systems stabilizes the K-cymrite structure. Muscovite does not convert to K-cymrite in the absence of NH₃–N₂-bearing fluid up to 7.8 GPa and 1070–1120 °C. According to FTIR and Raman spectroscopy, K-cymrite in equilibrium with an N-rich fluid can capture a huge amount of nitrogen in cages of its framework, mainly as N₂ molecules at fO₂ ∼NNO and predominantly as NH₃ molecules at fO₂ ∼IW. The storage capacity of K-cymrite with respect to nitrogen increases from 2.9 to 6.3 wt% with increase of fO₂. FTIR spectroscopy of muscovite equilibrated with K-cymrite shows that the clathrate mechanism of nitrogen entrapment by aluminosilicates (as neutral N₂ and NH₃ molecules) is much more efficient than the K⁺ → (NH₄)⁺ substitution. The structure of N-bearing K-cymrite (K,(NH₄⁺))[AlSi₃O₈]·(N₂,NH₃,H₂O) determined using X-ray single-crystal diffraction is very similar to that of H₂O-bearing K- and Ba-cymrites. It includes aluminosilicate layers consisting of double six-membered tetrahedral rings and cation sites statistically occupied with K⁺, Ba²⁺ and (NH₄)⁺ on the six-fold symmetry axis in interlayer space. The N₂ and NH₃ molecules are located near the cage centers and, unlike H₂O molecules, are included in the coordination environment of the cations. Our study confirms that NH₃- and N₂-rich K-cymrite may be stable in metapelites and can act as a redox insensitive carrier of nitrogen to >250 km mantle depths in downgoing slabs. The stability field of N-rich K-cymrite in the presence of an N₂–H₂O–NH₃-bearing fluid is inferred to be P ≥ 4 GPa in metasediments rich in K-feldspar and P ≥ 6 GPa in those containing phengite. As the slab material sinks deeper than 250–300 km where N-bearing K-cymrite may lose stability, the releasing nitrogen may migrate to metal-saturated mantle and become stored there in γ−Fe, Fe₃C, metal melt, or even iron nitride phases.     

The secondary origin of diamonds: multi-modal radiation tomography of diamondiferous mantle eclogites

Three-dimensional neutron and X-ray tomography reveals the textural and spatial relationship of diamonds and associated minerals in situ, in a unique suite of 17 diamondiferous eclogites. We emphasize the reporting of X-ray imaging on mantle xenoliths, which in combination with neutron imaging enables the clear identification of diamonds and interstitial metasomatic secondary minerals. In particular, neutrons are highly sensitive to hydrogen (H), allowing for the identification of OH- and H₂O-bearing metasomatic minerals. The identification of metasomatic minerals allows for the delineation of distinct metasomatic pathways through the eclogite xenoliths. Diamonds are readily identified as the darkest greyscales due to their low attenuation, and are typically surrounded by secondary minerals, never in contact with primary minerals, and always confined within metasomatic pathways. The ubiquitous occurrence of diamonds in association with pathways suggests a potential genetic link. Both octahedral and dodecahedral diamonds are observed within individual xenoliths, suggesting multiple heterogeneous growth and dissolution processes at small scales. The distinct age dichotomy between eclogite xenoliths and metasomatic mineral assemblages implies that the observed textural relationship of diamonds and late-stage metasomatic pathways for this suite of 17 eclogites casts doubt on the theory that eclogitic diamonds formed billions of years ago. Diamonds are interpreted to have formed from multiple growth episodes, with the last of these episodes represented by the metasomatic assemblages observed in this study. This further indicates that eclogitic diamond inclusions may span large time scales from ancient ages (>2 Ga) all the way to the last growth event, perhaps even close to the time of kimberlite emplacement (~360 Ma), which has significant implications for age-dating of diamonds and the study of diamonds as a whole.     

The behaviour of platelets in natural diamonds and the development of a new mantle thermometer

Platelets are one of the most common defects occurring in natural diamonds but their behaviour has not previously been well understood. Recent technical advances, and a much improved understanding of the correct interpretation of the main infrared (IR) feature associated with platelets (Speich et al. 2017), facilitated a systematic study of platelets in 40 natural diamonds. Three different types of platelet behaviour were identified here. Regular diamonds show linear correlations between both B-centre concentrations and platelet density and also between platelet size and platelet density. Irregular diamonds display reduced platelet density due to platelet breakdown, anomalously large or small platelets and a larger platelet size distribution. These features are indicative of high mantle storage temperatures. Finally, a previously unreported category of subregular diamonds is defined. These diamonds experienced low mantle residence temperatures and show smaller than expected platelets. Combining the systematic variation in platelet density with temperatures of mantle storage, determined by nitrogen aggregation, we can demonstrate that platelet degradation proceeds at a predictable rate. Thus, in platelet-bearing diamonds where N aggregation is complete, an estimate of annealing temperature can now be made for the first time.     

Mineral inclusions in fibrous diamonds: constraints on cratonic mantle refertilization and diamond formation

We analyzed mineral microinclusions in fibrous diamonds from the Wawa metaconglomerate (Superior craton) and Diavik kimberlites (Slave craton) and compared them with published compositions of large mineral inclusions in non-fibrous diamonds from these localities. The comparison, together with similar datasets available for Ekati and Koffiefontein kimberlites, suggest a general pattern of metasomatic alteration imposed on the ambient mantle by formation of fibrous diamond. Calcium and Fe enrichment of peridotitic garnet and pyroxenes and Fe enrichment of olivine associated with fibrous diamond-forming fluids contributes to refertilization of the cratonic mantle. Saline—carbonatitic—silicic fluid trapped by fibrous diamonds may represent one of the elusive agents of mantle refertilization. Calcium enrichment of peridotitic garnet and pyroxenes is expected in local mantle segments during fibrous diamond production, as Ca in the carbonatitic fluids is deposited into the surrounding mantle when oxidized carbon is reduced to diamond. Harzburgitic garnet evolves towards Ca-rich compositions even when it interacts with Ca-poor saline fluids. An unusual trend of Mg enrichment to Fo_95–98 is observed in some olivine inclusions in Wawa fibrous diamonds. The trend may result from the carbonatitic composition of the fluid that promotes crystallization of magnesian olivine and preferentially oxidizes the fayalite component. We propose a generic model of fibrous and non-fibrous diamond formation from carbonatitic fluids that explains enrichment of the mantle in mafic magmaphile and incompatible elements and accounts for locally metasomatized compositions of diamond inclusions.