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.

Electrical discharge triggers quasicrystal formation in an eolian dune.

We report the discovery of a dodecagonal quasicrystal Mn72.3Si15.6Cr9.7Al1.8Ni0.6-composed of a periodic stacking of atomic planes with quasiperiodic translational order and 12-fold symmetry along the two directions perpendicular to the planes-accidentally formed by an electrical discharge event in an eolian dune in the Sand Hills near Hyannis, Nebraska, United States. The quasicrystal, coexisting with a cubic crystalline phase with composition Mn68.9Si19.9Ni7.6Cr2.2Al1.4, was found in a fulgurite consisting predominantly of fused and melted sand along with traces of melted conductor metal from a nearby downed power line. The fulgurite may have been created by a lightning strike that combined sand with material from downed power line or from electrical discharges from the downed power line alone. Extreme temperatures of at least 1,710 °C were reached, as indicated by the presence of SiO2 glass in the sample. The dodecagonal quasicrystal is an example of a quasicrystal of any kind formed by electrical discharge, suggesting other places to search for quasicrystals on Earth or in space and for synthesizing them in the laboratory.

Accidental synthesis of a previously unknown quasicrystal in the first atomic bomb test.

The first test explosion of a nuclear bomb, the Trinity test of 16 July 1945, resulted in the fusion of surrounding sand, the test tower, and copper transmission lines into a glassy material known as "trinitite." Here, we report the discovery, in a sample of red trinitite, of a hitherto unknown composition of icosahedral quasicrystal, Si61Cu30Ca7Fe2 It represents the oldest extant anthropogenic quasicrystal currently known, with the distinctive property that its precise time of creation is indelibly etched in history. Like the naturally formed quasicrystals found in the Khatyrka meteorite and experimental shock syntheses of quasicrystals, the anthropogenic quasicrystals in red trinitite demonstrate that transient extreme pressure-temperature conditions are suitable for the synthesis of quasicrystals and for the discovery of new quasicrystal-forming systems.

Kanatzidisite: A Natural Compound with Distinctive van der Waals Heterolayered Architecture.

New minerals have long been a source of inspiration for the design and discovery. Many quantum materials, including superconductors, quantum spin liquids, and topological materials, have been unveiled through mineral samples with unusual structure types. In this report, we present kanatzidisite, a new naturally occurring material with formula [BiSbS3]2[Te2] and monoclinic symmetry (space group of P21/m) with lattice parameters a = 4.0021(5) Å, b = 3.9963(5) Å, c = 21.1009(10) Å, and ß = 95.392(3)°. The mineral exhibits a unique structure consisting of alternating BiSbS3 double van der Waals layers and distorted [Te] square nets essentially forming an array of parallel zigzag Te chains. Our theoretical calculations suggest that the band structure of kanatzidisite may exhibit topological features characteristic of a Dirac semimetal.

Evidence for complex iron oxides in the deep mantle from FeNi(Cu) inclusions in superdeep diamond.

The recent discovery in high-pressure experiments of compounds stable to 24-26 GPa with Fe4O5, Fe5O6, Fe7O9, and Fe9O11 stoichiometry has raised questions about their existence within the Earth's mantle. Incorporating both ferric and ferrous iron in their structures, these oxides if present within the Earth could also provide insight into diamond-forming processes at depth in the planet. Here we report the discovery of metallic particles, dominantly of FeNi (Fe0.71Ni0.24Cu0.05), in close spatial relation with nearly pure magnetite grains from a so-called superdeep diamond from the Earth's mantle. The microstructural relation of magnetite within a ferropericlase (Mg0.60Fe0.40)O matrix suggests exsolution of the former. Taking into account the bulk chemistry reconstructed from the FeNi(Cu) alloy, we propose that it formed by decomposition of a complex metal M oxide (M4O5) with a stoichiometry of (Fe3+2.15Fe2+1.59Ni2+0.17Cu+0.04)Σ=3.95O5 We further suggest a possible link between this phase and variably oxidized ferropericlase that is commonly trapped in superdeep diamond. The observation of FeNi(Cu) metal in relation to magnetite exsolved from ferropericlase is interpreted as arising from a multistage process that starts from diamond encapsulation of ferropericlase followed by decompression and cooling under oxidized conditions, leading to the formation of complex oxides such as Fe4O5 that subsequently decompose at shallower P-T conditions.

Producing highly complicated materials. Nature does it better.

Through the years, mineralogical studies have produced a tremendous amount of data on the atomic arrangement and mineral properties. Quite often, structural analysis has led to elucidate the role played by minor components, giving interesting insights into the physico-chemical conditions of mineral crystallization and allowing the description of unpredictable structures that represented a body of knowledge critical for assessing their technological potentialities. Using such a rich database, containing many basic acquisitions, further steps became appropriate and possible, into the directions of more advanced knowledge frontiers. Some of these frontiers assume the name of modularity, complexity, aperiodicity, and matter organization at not conventional levels, and will be discussed in this review.

Shock synthesis of quasicrystals with implications for their origin in asteroid collisions.

We designed a plate impact shock recovery experiment to simulate the starting materials and shock conditions associated with the only known natural quasicrystals, in the Khatyrka meteorite. At the boundaries among CuAl5, (Mg0.75Fe(2+) 0.25)2SiO4 olivine, and the stainless steel chamber walls, the recovered specimen contains numerous micron-scale grains of a quasicrystalline phase displaying face-centered icosahedral symmetry and low phason strain. The compositional range of the icosahedral phase is Al68-73Fe11-16Cu10-12Cr1-4Ni1-2 and extends toward higher Al/(Cu+Fe) and Fe/Cu ratios than those reported for natural icosahedrite or for any previously known synthetic quasicrystal in the Al-Cu-Fe system. The shock-induced synthesis demonstrated in this experiment reinforces the evidence that natural quasicrystals formed during a shock event but leaves open the question of whether this synthesis pathway is attributable to the expanded thermodynamic stability range of the quasicrystalline phase at high pressure, to a favorable kinetic pathway that exists under shock conditions, or to both thermodynamic and kinetic factors.

Evidence for the extraterrestrial origin of a natural quasicrystal.

We present evidence that a rock sample found in the Koryak Mountains in Russia and containing icosahedrite, an icosahedral quasicrystalline phase with composition Al(63)Cu(24)Fe(13), is part of a meteorite, likely formed in the early solar system about 4.5 Gya. The quasicrystal grains are intergrown with diopside, forsterite, stishovite, and additional metallic phases [khatyrkite (CuAl(2)), cupalite (CuAl), and ß-phase (AlCuFe)]. This assemblage, in turn, is enclosed in a white rind consisting of diopside, hedenbergite, spinel (MgAl(2)O(4)), nepheline, and forsterite. Particularly notable is a grain of stishovite (from the interior), a tetragonal polymorph of silica that only occurs at ultrahigh pressures (≥ 10 Gpa), that contains an inclusion of quasicrystal. An extraterrestrial origin is inferred from secondary ion mass spectrometry (18)O/(16)O and (17)O/(16)O measurements of the pyroxene and olivine intergrown with the metal that show them to have isotopic compositions unlike any terrestrial minerals and instead overlap those of anhydrous phases in carbonaceous chondrite meteorites. The spinel from the white rind has an isotopic composition suggesting that it was part of a calcium-aluminum-rich inclusion similar to those found in CV3 chondrites. The mechanism that produced this exotic assemblage is not yet understood. The assemblage (metallic copper-aluminum alloy) is extremely reduced, and the close association of aluminum (high temperature refractory lithophile) with copper (low temperature chalcophile) is unexpected. Nevertheless, our evidence indicates that quasicrystals can form naturally under astrophysical conditions and remain stable over cosmic timescales, giving unique insights on their existence in nature and stability.

Routes to reduction of phosphate by high-energy events.

Phosphate minerals such as those in the apatite group tend to be the dominant forms of phosphorus in minerals on the Earth's surface. Phosphate can be reduced to phosphides during high-energy events, such as lightning and impacts. Here we show that, in addition to formation of metal phosphides, a new compound was formed by lightning in a fulgurite from New Port Richey, Florida, USA. A calcium phosphite material, ideally CaHPO3, was found in spherules mainly consisting of iron silicides that formed by lightning-induced fusion of sand around a tree root. This phosphite material bears a phosphorus oxidation state intermediate of that of phosphides and phosphates in a geologic sample and implicates phosphites as being potentially relevant to other high-energy events where phosphorus may partially change its redox state, and material similar to this phosphite may also be the source of phosphite that makes up part of the phosphorus biogeochemical cycle.

New Minerals from Inclusions in Corundum Xenocrysts from Mt. Carmel, Israel: Magnéliite, Ziroite, Sassite, Mizraite-(Ce) and Yeite.

Our nanomineralogical investigation of melt inclusions in corundum xenocrysts from the Mt. Carmel area, Israel has revealed seven IMA-approved new minerals since 2021. We report here four new oxide minerals and one new alloy mineral. Magnéliite (Ti3+2Ti4+2O7; IMA 2021-111) occurs as subhedral crystals, ~4 µm in size, with alabandite, zirconolite, Ti,Al,Zr-oxide, and hibonite in corundum Grain 767-1. Magnéliite has an empirical formula (Ti3+1.66Al0.13Ti4+0.15Mg0.10Ca0.01Sc0.01)Σ2.06 (Ti4+1.93Zr0.08)Σ2.01O7 and the triclinic P1¯ Ti4O7-type structure with the cell parameters: a = 5.60(1) Å, b = 7.13(1) Å, c = 12.47(1) Å, α = 95.1(1)°, ß = 95.2(1)°, γ = 108.7(1)°, V = 466(2) Å3, Z = 4. Ziroite (ZrO2; IMA 2022-013) occurs as irregular crystals, ~1-4 µm in size, with baddeleyite, hibonite, and Ti,Al,Zr-oxide in corundum Grain 479-1a. Ziroite has an empirical formula (Zr0.72Ti4+0.26Mg0.02Al0.02Hf0.01)Σ1.03O2 and the tetragonal P42/nmc zirconia(HT)-type structure with the cell parameters: a = 3.60(1) Å, c = 5.18(1) Å, V = 67.1(3) Å3, Z = 2. Sassite (Ti3+2Ti4+O5; IMA 2022-014) occurs as subhedral-euhedral crystals, ~4-16 µm in size, with Ti,Al,Zr-oxide, mullite, osbornite, baddeleyite, alabandite, and glass in corundum Grain 1125C1. Sassite has an empirical formula (Ti3+1.35Al0.49Ti4+0.08Mg0.07)Σ1.99(Ti4+0.93Zr0.06Si0.01)Σ1.00O5 and the orthorhombic Cmcm pseudobrookite-type structure with the cell parameters: a = 3.80(1) Å, b = 9.85(1) Å, c = 9.99(1) Å, V = 374(1) Å3, Z = 4. Mizraite-(Ce) (Ce(Al11Mg)O19; IMA 2022-027) occurs as euhedral crystals, <1-14 µm in size, with Ce-silicate, Ti-sulfide, Ti,Al,Zr-oxide, ziroite, and thorianite in corundum Grain 198-8. Mizraite-(Ce) has an empirical formula (Ce0.76Ca0.10La0.07Nd0.01)Σ0.94(Al10.43Mg0.84Ti3+0.60Si0.09Zr0.04)Σ12.00O19 and the hexagonal P63/mmc magnetoplumbite-type structure with the cell parameters: a = 5.61(1) Å, c = 22.29(1) Å, V = 608(2) Å3, Z = 2. Yeite (TiSi; IMA 2022-079) occurs as irregular-subhedral crystals, 1.2-3.5 µm in size, along with wenjiite (Ti5Si3) and zhiqinite (TiSi2) in Ti-Si alloy inclusions in corundum Grain 198c. Yeite has an empirical formula (Ti0.995Mn0.003V0.001Cr0.001)(Si0.996P0.004) and the orthorhombic Pnma FeB-type structure with the cell parameters: a = 6.55(1) Å, b = 3.64(1) Å, c = 4.99(1) Å, V = 119.0(4) Å3, Z = 4. The five minerals are high-temperature oxide or alloy phases, formed in melt pockets in corundum xenocrysts derived from the upper mantle beneath Mt. Carmel.

Cubic Fe-bearing majorite synthesized at 18-25 GPa and 1000 °C: implications for element transport, subducted slab rheology and diamond formation.

The chemistry and mineralogy of slabs subducted into lower mantle control slab rheology and impact the deep volatile cycle. It is known that the metamorphism of little-altered oceanic crust results in eclogite rocks with subequal proportions of garnet and clinopyroxene. With increasing pressure, these minerals react to stabilize pyrope-rich tetragonal majoritic garnet. However, some eclogites contain higher proportions of omphacitic clinopyroxene, caused by Na- and Si-rich metasomatism on the ocean floor or during subduction. The mineralogy of such eclogites is expected to evolve differently. Here, we discuss the results of the crystallization products of omphacitic glass at ~ 18 and ~ 25 GPa and 1000 °C to simulate P-T regimes of cold subduction. The full characterization of the recovered samples indicates evidence of crystallization of Na-, Si-rich cubic instead of tetragonal majorite. This cubic majorite can incorporate large amounts of ferric iron, promoting redox reactions with surrounding volatile-bearing fluids and, ultimately, diamond formation. In addition, the occurrence of cubic majorite in the slab would affect the local density, favoring the continued buoyancy of the slab as previously proposed by seismic observations. Attention must be paid to omphacitic inclusions in sublithospheric diamonds as these might have experienced back-transformation from the HP isochemical cubic phase.

In search of natural quasicrystals.

The concept of quasicrystals was first introduced twenty-eight years ago and, since then, over a hundred types have been discovered in the laboratory under precisely controlled physical conditions designed to avoid crystallization. Yet the original theory suggested that quasicrystals can potentially be as robust and stable as crystals, perhaps even forming naturally. These considerations motivated a decade-long search for a natural quasicrystal culminating in the discovery of icosahedrite (Al(63)Cu(24)Fe(13)), an icosahedral quasicrystal found in a rock sample composed mainly of khatyrkite (crystalline (Cu,Zn)Al(2)) labeled as coming from the Koryak Mountains of far eastern Russia. In this paper, we review the search and discovery, the analysis showing the sample to be of extraterrestrial origin and the initial results of an extraordinary geological expedition to the Koryak Mountains to seek further evidence.

Redetermination of Mg(2)B(25) based on single-crystal X-ray data.

The crystal structure of Mg(2)B(25), dimagnesium penta-eicosa-boride, was reexamined from single-crystal X-ray diffraction data. The structural model previously reported on the basis of powder X-ray diffraction data [Giunchi et al. (2006 ▶). Solid State Sci.8, 1202-1208] has been confirmed, although a much higher precision refinement was achieved, leading to much smaller standard uncertainties on bond lengths and refined occupancy factors. Moreover, all atoms were refined with anisotropic displacement parameters. Mg(2)B(25) crystallizes in the ß-boron structure type and is isostructural with other rhombohedral compounds of the boron-rich metal boride family. Magnesium atoms are found in inter-stitial sites on special positions (two with site symmetry .m, one with .2 and one with 3m), all with partial occupancies.

Structural and vibrational properties of arsenic sulfides: alacranite (As8S9).

Alacranite, As(8)S(9), has been studied by a combined approach based on micro-Raman measurements and ab initio molecular dynamics simulations, with the Car-Parrinello method. The structure of this arsenic sulfide mineral consists of an ordered packing of As(4)S(4) and As(4)S(5) cagelike molecules, with a topology closely resembling that found in the ß-As(4)S(4). The presence in the crystal structure of molecular clusters with permanent dipole moment induces stronger intermolecular interactions than those observed in other arsenic sulfides, making the adoption of ab initio computational methods particularly important for a complete characterization of the structural and spectroscopic properties.

Insight into the structure of decagonite - the extraterrestrial decagonal quasicrystal.

A set of X-ray data collected on a fragment of decagonite, Al71Ni24Fe5, the only known natural decagonal quasicrystal found in a meteorite formed at the beginning of the Solar System, allowed us to determine the first structural model for a natural quasicrystal. It is a two-layer structure with decagonal columnar clusters arranged according to the pentagonal Penrose tiling. The structural model showed peculiarities and slight differences with respect to those obtained for other synthetic decagonal quasicrystals. Interestingly, decagonite is found to exhibit low linear phason strain and a high degree of perfection despite the fact it was formed under conditions very far from those used in the laboratory.

Evidence for the charge disproportionation of iron in extraterrestrial bridgmanite.

Bridgmanite, MgSiO3 with perovskite structure, is considered the most abundant mineral on Earth. On the lower mantle, it contains Fe and Al that strongly influence its behavior. Experimentalists have debated whether iron may exist in a mixed valence state, coexistence of Fe2+ and Fe3+ in bridgmanite, through charge disproportionation. Here, we report the discovery of Fe-rich aluminous bridgmanite coexisting with metallic iron in a shock vein of the Suizhou meteorite. This is the first direct evidence in nature of the Fe disproportionation reaction, which so far has only been observed in some high-pressure experiments. Furthermore, our discovery supports the idea that the disproportionation reaction would have played a key role in redox processes and the evolution of Earth.

First synthesis of a unique icosahedral phase from the Khatyrka meteorite by shock-recovery experiment.

Icosahedral quasicrystals (i-phases) in the Al-Cu-Fe system are of great interest because of their perfect quasicrystalline structure and natural occurrences in the Khatyrka meteorite. The natural quasicrystal of composition Al62Cu31Fe7, referred to as i-phase II, is unique because it deviates significantly from the stability field of i-phase and has not been synthesized in a laboratory setting to date. Synthetic i-phases formed in shock-recovery experiments present a novel strategy for exploring the stability of new quasicrystal compositions and prove the impact origin of natural quasicrystals. In this study, an Al-Cu-W graded density impactor (GDI, originally manufactured as a ramp-generating impactor but here used as a target) disk was shocked to sample a full range of Al/Cu starting ratios in an Fe-bearing 304 stainless-steel target chamber. In a strongly deformed region of the recovered sample, reactions between the GDI and the steel produced an assemblage of co-existing Al61.5Cu30.3Fe6.8Cr1.4 i-phase II + stolperite (ß, AlCu) + khatyrkite (θ, Al2Cu), an exact match to the natural i-phase II assemblage in the meteorite. In a second experiment, the continuous interface between the GDI and steel formed another more Fe-rich quinary i-phase (Al68.6Fe14.5Cu11.2Cr4Ni1.8), together with stolperite and hollisterite (λ, Al13Fe4), which is the expected assemblage at phase equilibrium. This study is the first laboratory reproduction of i-phase II with its natural assemblage. It suggests that the field of thermodynamically stable icosahedrite (Al63Cu24Fe13) could separate into two disconnected fields under shock pressure above 20 GPa, leading to the co-existence of Fe-rich and Fe-poor i-phases like the case in Khatyrka. In light of this, shock-recovery experiments do indeed offer an efficient method of constraining the impact conditions recorded by quasicrystal-bearing meteorite, and exploring formation conditions and mechanisms leading to quasicrystals.

Extraordinary structural complexity of ilmajokite: a multilevel hierarchical framework structure of natural origin.

The crystal structure of ilmajokite, a rare Na-K-Ba-Ce-titanosilicate from the Khibiny mountains, Kola peninsula, Russia, has been solved using single-crystal X-ray diffraction data. The crystal structure is based on a 3D titanosilicate framework consisting of trigonal prismatic titanosilicate (TPTS) clusters centered by Ce3+ in [9]-coordination. Four adjacent TPTS clusters are linked into four-membered rings within the (010) plane and connected via ribbons parallel to 101. The ribbons are organized into layers parallel to (010) and modulated along the a axis with a modulation wavelength of csinß = 32.91 Šand an amplitude of ∼b/2 = 13.89 Å. The layers are linked by additional silicate tetrahedra. Na+, K+, Ba2+ and H2O groups occur in the framework cavities and have different occupancies and coordination environments. The crystal structure of ilmajokite can be separated into eight hierarchical levels: atoms, coordination polyhedra, TPTS clusters, rings, ribbons, layers, the framework and the whole structure. The information-based analysis allows estimation of the complexity of the structure as 8.468 bits per atom and 11990.129 bits per cell. According to this analysis, ilmajokite is the third-most complex mineral known to date after ewingite and morrisonite, and is the most complex mineral framework structure, comparable in complexity to paulingite-(Ca) (11 590.532 bits per cell).

Daliranite, PbHgAs2S5: determination of the incommensurately modulated structure and revision of the chemical formula.

The incommensurately modulated crystal structure of the mineral daliranite has been determined using 3D electron diffraction data obtained on nanocrystalline domains. Daliranite is orthorhombic with a = 21, b = 4.3, c = 9.5 Šand shows modulation satellites along c. The solution of the average structure in the Pnma space group together with energy-dispersive X-ray spectroscopy data obtained on the same domains indicate a chemical formula of PbHgAs2S5, which has one S fewer than previously reported. The crystal structure of daliranite is built from columns of face-sharing PbS8 bicapped trigonal prisms laterally connected by [2+4]Hg polyhedra and (As3+2S5)4- groups. The excellent quality of the electron diffraction data allows a structural model to be built for the modulated structure in superspace, which shows that the modulation is due to an alternated occupancy of a split As site.

Routhierite, Tl(Cu,Ag)(Hg,Zn)(2)(As,Sb)(2)s(6).

The crystal structure of the mineral routhierite, Tl(Cu,Ag)(Hg,Zn)(2)(As,Sb)(2)S(6), was solved and refined for the first time by means of single-crystal X-ray diffraction. The crystal structure consists of (Cu,Ag)S(4) and (Hg,Zn)S(4) tetrahedra, which share corners to form a framework with channels parallel to [001]. These channels contain TlS(6) and (As,Sb)S(3) polyhedra that share corners and edges with the tetrahedra. The crystal-chemical relationships with other Tl-Hg sulfosalts are outlined. The structure determination reported in this study definitively confirms that routhierite and stalderite possess the same crystal structure.