Search Results (8)

Superdeep diamonds and their syngenetic inclusions are crucial for understanding Earth’s deep carbon cycle and slab–mantle redox dynamics. The origins of these diamonds, especially their links to iron (Fe) carbides and ferropericlase with varying Mg# [=Mg/(Mg+Fe)_at], however, remain elusive. In this study, we performed high pressure–temperature (P-T) experiments (10–16 GPa and 1200–1700 K) across cold-to-warm subduction zones using a multi-anvil press. The results reveal a stepwise Fe-mediated carbonate reduction process for the formation of superdeep diamonds: MgCO₃ → Fe-carbides (Fe₃C/Fe₇C₃) → graphite/diamond. This mechanism explains two phenomena regarding superdeep diamonds: (1) anomalous ¹³C depletion results from kinetic isotope fractionation during ¹²C enrichment into the intermediate Fe-carbides; (2) nitrogen scarcity is due to Fe-carbides acting as nitrogen sinks. Ferropericlase [(Mg,Fe)O] formed during the reactions in our experiments shows Mg# variations (0.2–0.9), similar to those found in natural samples. High Mg# (>0.7) variants from lower temperature experiments indicate diamond crystallization from carbonatitic melts in the shallow lower mantle, while the broad Mg# range (0.2–0.9) from experiments at higher temperatures suggests multi-depth formation processes as found in Brazilian diamonds. These findings suggest that slab–mantle interactions produce superdeep diamonds with distinctive Fe-carbides and ferropericlase assemblages as inclusions, coupled with their ¹³C- and nitrogen-depleted signatures, which underscore thermochemical carbon cycling as a key factor in deep carbon storage and mantle mineralogy. Full article

New data, including Raman spectroscopy, characterize unusual mineral assemblages from rocks of the Naylga and Khamaryn–Khyral–Khiid combustion metamorphic complexes in Mongolia. Several samples of melilite–nepheline paralava and other thermally altered (metamorphosed) sedimentary rocks contain troilite (FeS), metallic iron Fe⁰, kamacite α-(Fe,Ni) or Ni-bearing Fe⁰, taenite γ-(Fe,Ni) or Ni-rich Fe⁰, barringerite or allabogdanite Fe₂P, schreibersite Fe₃P, steadite Fe₄P = eutectic α-Fe + Fe₃P, wüstite FeO, and cohenite Fe₃C. The paralava matrix includes a fragment composed of magnesiowüstite–ferropericlase (FeO–MgO solid solution), as well as of spinel (Mg,Fe)Al₂O₄ and forsterite. The highest-temperature mineral assemblage belongs to a xenolithic remnant, possibly Fe-rich sinter, which is molten ash left after underground combustion of coal seams. The crystallization temperatures of the observed iron phases were estimated using phase diagrams for the respective systems: Fe–S for iron sulfides and Fe–P ± C for iron phosphides. Iron monosulfides (high-temperature pyrrhotite) with inclusions of Fe⁰ underwent solid-state conversion into troilite at 140 °C. Iron phosphides in inclusions from the early growth zone of anorthite–bytownite in melilite–nepheline paralava crystallized from <1370 to 1165 °C (Fe₂P), 1165–1048 °C (Fe₃P), and <1048 °C (Fe₄P). Phase relations in zoned spherules consisting of troilite +Fe⁰ (or kamacite + taenite) +Fe₃P ± (Fe₃C, Fe₄P) reveal the potential presence of a homogeneous Fe–S–P–C melt at T~1350 °C, which separated into two immiscible melts in the 1350–1250 °C range; namely, a dense Fe–P–C melt in the core and a less dense Fe–S melt in the rim. The melts evolved in accordance with cooling paths in the Fe–S and Fe–P–C phase diagrams. Cohenite and schreibersite in the spherules crystallized between 988 °C and 959 °C. The crystallization temperatures of minerals were used to reconstruct redox patterns with respect to the CCO, IW, IM, and MW buffer equilibria during melting of marly limestone and subsequent crystallization and cooling of melilite–nepheline paralava melts. The origin of the studied CM rocks was explained in a model implying thermal alteration of low-permeable overburden domains in reducing conditions during wild subsurface coal fires, while heating was transferred conductively from adjacent parts of ignited coal seams. The fluid (gas) regime in the zones of combustion was controlled by the CCO buffer at excess atomic carbon. Paralava melts exposed to high-temperature extremely reducing conditions contained droplets of immiscible Fe–S–P–C, Fe–S, Fe–P, and Fe–P–C melts, which then crystallized into reduced mineral assemblages. Full article

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. Full article

It is widely accepted that the lower mantle consists of mainly three major minerals—ferropericlase, bridgmanite and calcium silicate perovskite. Ferropericlase ((Mg,Fe)O) is the second most abundant of the three, comprising approximately 16–20 wt% of the lower mantle. The stability of ferropericlase at conditions of the lowermost mantle has been highly investigated, with controversial results. Amongst other reasons, the experimental conditions during laser heating (such as duration and achieved temperature) have been suggested as a possible explanation for the discrepancy. In this study, we investigate the effect of pulsed laser heating on the stability of ferropericlase, with a geochemically relevant composition of Mg_0.76Fe_0.24O (Fp24) at pressure conditions corresponding to the upper part of the lower mantle and at a wide temperature range. We report on the decomposition of Fp24 with the formation of a high-pressure (Mg,Fe)₃O₄ phase with CaTi₂O₄-type structure, as well as the dissociation of Fp24 into Fe-rich and Mg-rich phases induced by pulsed laser heating. Our results provide further arguments that the chemical composition of the lower mantle is more complex than initially thought, and that the compositional inhomogeneity is not only a characteristic of the lowermost part, but includes depths as shallow as below the transition zone. Full article

Trace elements play a significant role in interpretation of different processes in the deep Earth. However, the systematics of interphase rare-earth element (REE) partitioning under the conditions of the uppermost lower mantle are poorly understood. We performed high-pressure experiments to study the phase relations in key solid-phase reactions CaMgSi₂O₆ = CaSiO₃-perovskite + MgSiO₃-bridgmanite and (Mg,Fe)₂SiO₄-ringwoodite = (Mg,Fe)SiO₃-bridgmanite + (Mg,Fe)O with addition of 1 wt % of REE oxides. Atomistic modeling was used to obtain more accurate quantitative estimates of the interphase REE partitioning and displayed the ideal model for the high-pressure minerals. HREE (Er, Tm, Yb, and Lu) are mostly accumulated in bridgmanite, while LREE are predominantly redistributed into CaSiO₃. On the basis of the results of experiments and atomistic modeling, REE in bridgmanite are clearly divided into two groups (from La to Gd and from Gd to Lu). Interphase REE partition coefficients in solid-state reactions were calculated at 21.5 and 24 GPa for the first time. The new data are applicable for interpretation of the trace-element composition of the lower mantle inclusions in natural diamonds from kimberlite; the experimentally determined effect of pressure on the interphase (bridgmanite/CaSiO₃-perovskite) REE partition coefficients can be a potential qualitative geobarometer for mineral inclusions in super-deep diamonds. Full article

Ultralow-velocity zones (ULVZs) at the core–mantle boundary (CMB) represent some of the most preternatural features in Earth’s mantle. These zones most likely contain partial melt, extremely high iron content ferropericlase, or combinations of both. We analyzed a new collection of 58,155 carefully processed and quality-controlled broadband recordings of the seismic phase SPdKS in the epicentral distance range from 106° to 115°. These data sample 56.9% of the CMB by surface area. From these recordings we searched for the most anomalous seismic waveforms that are indicative of ULVZ presence. We used a Bayesian approach to identify the regions of the CMB that have the highest probability of containing ULVZs, thereby identifying sixteen regions of interest. Of these regions, we corroborate well-known ULVZ existence beneath the South China Sea, southwest Pacific, the Samoa hotspot, the southwestern US/northern Mexico, and Iceland. We find good evidence for new ULVZs beneath North Africa, East Asia, and north of Papua New Guinea. We provide further evidence for ULVZs in regions where some evidence has been hinted at before beneath the Philippine Sea, the Pacific Northwest, and the Amazon Basin. Additional evidence is shown for potential ULVZs at the base of the Caroline, San Felix and Galapagos hotspots. Full article

It is always a goal of scientists to develop new techniques to identify the composition of mantle materials and understand geodynamic processes accurately. Ferropericlase (Mg,Fe)O is a prominent mineral in the lower mantel. It is a common practice in the research community to prepare ferropericlase using a solid-phase synthesis method or high-pressure experiment synthesis method. This conventional method contains a number of ambiguities a great deal of time is needed. In this paper, we have addressed the drawbacks of the conventional technique using a liquid-phase synthesis method to prepare ferropericlase. During the experiment, oxalic acid was added to a mixed solution of ferrous sulfate and magnesium chloride and mixed according to the molar ratio. The formed magnesium iron oxalate precipitate was sintered and reduced into the final sample. Furthermore, the final sample was analyzed using XRD and SEM. Compared to the solid-phase method, this coprecipitation method could produce ferropericlase with a shorter sintering time, lower sintering temperature, and a reduction in the amount of gas consumed. XRD and SEM results show that the liquid-phase method produced samples with better composition homogeneity. Full article

Seismic anisotropy is observed above the core-mantle boundary in regions of slab subduction and near the margins of Large Low Shear Velocity Provinces (LLSVPs). Ferropericlase is believed to be the second most abundant phase in the lower mantle. As it is rheologically weak, it may be a dominant source for anisotropy in the lowermost mantle. Understanding deformation mechanisms in ferropericlase over a range of pressure and temperature conditions is crucial to interpret seismic anisotropy. The effect of temperature on deformation mechanisms of ferropericlase has been established, but the effects of pressure are still controversial. With the aim to clarify and quantify the effect of pressure on deformation mechanisms, we perform room temperature compression experiments on polycrystalline periclase to 50 GPa. Lattice strains and texture development are modeled using the Elasto-ViscoPlastic Self Consistent method (EVPSC). Based on modeling results, we find that $\left\{110\right\}⟨1\overline{1}0⟩$ slip is increasingly activated with higher pressure and is fully activated at ~50 GPa. Pressure and temperature have a competing effect on activities of dominant slip systems. An increasing $\left\{100\right\}⟨011⟩$ : $\left\{110\right\}⟨1\overline{1}0⟩$ ratio of slip activity is expected as material moves from cold subduction regions towards hot upwelling region adjacent to LLSVPs. This could explain observed seismic anisotropy in the circum-Pacific region that appears to weaken near margins of LLVSPs. Full article