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A general characteristic of the structural features of rock-forming silicates is given. The important results of studying high-pressure (HP) minerals, obtained in 2018–2022, are reviewed. The emphasis is on the characteristic of the polymorphs of olivine (asimowite, poirierite) and wollastonite (breyite and davemaoite). Poirierite (ε-Mg2SiO4) contains a new type of (Si,O) chains with a period of one tetrahedron. Correspondingly, the structural formula of this natural phase is Mg2[SiO3]O, and its intergrowths with wadsleyite/ringwoodite in impact chondrites confirm the idea that the transformation of olivine into ringwoodite occurs through formation of poirierite. The stability of the wollastonite polymorphs (1T, 2М, pseudowollastonite, and synthetic analog of breyite) in a wide range of upper mantle depths is noted. The structure and composition of new HP minerals from impact regions, meteorites, and diamond inclusions carry information about the complex petrology of deep geospheres, which cannot be manifested in products of laboratory experiments. [ABSTRACT FROM AUTHOR]

Phase relations in one of the key petrological systems, CaSiO3, have been comprehensively investigated for the first time in the pressure range 0–100 GPa and temperatures 0–2500 K within the density functional theory using the method of lattice dynamics in the quasi-harmonic approximation. The results showed that at atmospheric pressure and 0 K CaSiO3 is stable in the wollastonite structure, which above 1250 K transforms to the high-temperature pseudowollastonite modification. Above a pressure of 4 GPa, CaSiO3 is stable in the breyite structure. The phase equilibrium curve has a negative slope of dP/dT = –0.6 MPa/K. At 8 GPa, CaSiO3 decomposes into an assemblage of Ca2SiO4-larnite and titanite-structured CaSi2O5. The phase equilibrium curve has a positive slope of dP/dT = 1.35 MPa/K. At a pressure of 13 GPa, Ca2SiO4-larnite reacts with CaSi2O5, forming a phase with a perovskite-like structure – CaSiO3-perovskite. The pressure of this phase transition is practically independent of temperature. In the low-temperature region, Ca-perovskite is stable in the tetragonal modification CaSiO3-I4/mcm. Above 340 K at 13 GPa, Ca-perovskite is stable in the cubic modification CaSiO3- The phase transition temperature increases to 755 K with pressure increase to 100 GPa. The thermodynamic parameters were also calculated for the first time for wollastonite, pseudowollastonite, and titanite-structured CaSi2O5. [ABSTRACT FROM AUTHOR]

The margarosanite group (now officially confirmed by IMA-CNMNC) consists of triclinic Ca-(Ba, Pb) cyclosilicates with three-membered [Si3O9]6– rings (3R), with the general formula AB2Si3O9, where A = Pb, Ba and Ca and B = Ca. A closest-packed arrangement of O atoms parallel to (101) hosts Si and B cations in interstitial sites in alternating layers. The 3R layer has three independent Si sites in each ring. Divalent cations occupy three independent sites: Ca in B occupies two nonequivalent sites, Ca1 (8-fold coordinated), and Ca2 (6-fold coordinated). A (=Ca3) is occupied by Pb2+ (or Ba2+) in 6+4 coordination, or 6+1 when occupied by Ca; this third site occurs within the 3R-layer in a peripheral position. Three minerals belong to this group: margarosanite (ideally PbCa2Si3O9), walstromite (BaCa2Si3O9) and breyite (CaCa2Si3O9). So far, no solid solutions involving the Ca1 and Ca2 sites have been described. Therefore, root names depend on the composition of the Ca3 site only. Isomorphic replacement at the Ca3 sites has been noted. We here report data on a skarn sample from the Jakobsberg Mn–Fe oxide deposit, in Värmland, Sweden, representing intermediate compositions on the walstromite–margarosanite binary, in the range ca. 50–70% mol.% BaCa2Si3O9. The Pb-rich walstromite is associated closely with celsian, phlogopite, andradite, vesuvianite, diopside and nasonite. A crystal-structure refinement (R1 = 4.8%) confirmed the structure type, and showed that the Ca3 (Ba, Pb) site is split into two positions separated by 0.39 Å, with the Ba atoms found slightly more peripheral to the 3R-layers. [ABSTRACT FROM AUTHOR]

Earth'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: P 1) 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. [ABSTRACT FROM AUTHOR]

The equations of state of different phases in the CaSiO3 system (wollastonite, pseudowollastonite, breyite (walstromite), larnite (Ca2SiO4), titanite-structured CaSi2O5 and CaSiO3-perovskite) are constructed using a thermodynamic model based on the Helmholtz free energy. We used known experimental measurements of heat capacity, enthalpy, and thermal expansion at zero pressure and high temperatures, and volume measurements at different pressures and temperatures for calculation of parameters of equations of state of studied Ca-silicates. The used thermodynamic model has allowed us to calculate a full set of thermodynamic properties (entropy, heat capacity, bulk moduli, thermal expansion, Gibbs energy, etc.) of Ca-silicates in a wide range of pressures and temperatures. The phase diagram of the CaSiO3 system is constructed at pressures up to 20 GPa and temperatures up to 2000 K and clarifies the phase boundaries of Ca-silicates under upper mantle conditions. The calculated wollastonite–breyite equilibrium line corresponds to equation P(GPa) = −4.7 × T(K) + 3.14. The calculated density and adiabatic bulk modulus of CaSiO3-perovskite is compared with the PREM model. The calcium content in the perovskite composition will increase the density of mineral and it good agree with the density according to the PREM model at the lower mantle region.

Walstromite, BaCa2Si3O9, known only from metamorphic rocks of North America, was found in small veins of unusual rankinite paralava within gehlenite hornfelses of the Hatrurim Complex, Israel. It was detected at two localities—Gurim Anticline and Zuk Tamrur, Hatrurim Basin, Negev Desert. The structure of Israeli walstromite [with P 1 ¯ space group and cell parameters a = 6.74874(10) Å, b = 9.62922(11) Å, c = 6.69994(12) Å, α = 69.6585(13)°, β = 102.3446(14)°, γ = 96.8782(11)°, Z = 2, V = 398.314(11) Å3] is analogous to the structure of walstromite from type locality—Rush Creek, eastern Fresno County, California, USA. The Raman spectra of all tree minerals exhibit bands related to stretching symmetric vibrations of Si-O-Si at 650–660 cm−1 and Si-O at 960–990 cm−1 in three-membered rings (Si3O9)6−. This new genetic pyrometamorphic type of walstromite forms out of the differentiated melt portions enriched in Ba, V, S, P, U, K, Na, Ti and F, a residuum after crystallization of rock-forming minerals of the paralava (rankinite, gehlenite-åkermanite-alumoåkermanite, schorlomite-andradite series and wollastonite). Walstromite associates with other Ba-minerals, also products of the residual melt crystallization as zadovite, BaCa6[(SiO4)(PO4)](PO4)2F and gurimite, Ba3(VO4)2. The genesis of unusual barium mineralization in rankinite paralava is discussed. Walstromite is isostructural with minerals—margarosanite, BaCa2Si3O9 and breyite, CaCa2(Si3O9), discovered in 2018.

The equations of state of different phases in the CaSiO3 system (wollastonite, pseudowollastonite, breyite (walstromite), larnite (Ca2SiO4), titanite-structured CaSi2O5 and CaSiO3-perovskite) are constructed using a thermodynamic model based on the Helmholtz free energy. We used known experimental measurements of heat capacity, enthalpy, and thermal expansion at zero pressure and high temperatures, and volume measurements at different pressures and temperatures for calculation of parameters of equations of state of studied Ca-silicates. The used thermodynamic model has allowed us to calculate a full set of thermodynamic properties (entropy, heat capacity, bulk moduli, thermal expansion, Gibbs energy, etc.) of Ca-silicates in a wide range of pressures and temperatures. The phase diagram of the CaSiO3 system is constructed at pressures up to 20 GPa and temperatures up to 2000 K and clarifies the phase boundaries of Ca-silicates under upper mantle conditions. The calculated wollastonite–breyite equilibrium line corresponds to equation P(GPa) = −4.7 × T(K) + 3.14. The calculated density and adiabatic bulk modulus of CaSiO3-perovskite is compared with the PREM model. The calcium content in the perovskite composition will increase the density of mineral and it good agree with the density according to the PREM model at the lower mantle region. [ABSTRACT FROM AUTHOR]

Walstromite, BaCa2Si3O9, known only from metamorphic rocks of North America, was found in small veins of unusual rankinite paralava within gehlenite hornfelses of the Hatrurim Complex, Israel. It was detected at two localities—Gurim Anticline and Zuk Tamrur, Hatrurim Basin, Negev Desert. The structure of Israeli walstromite [with P 1 ¯ space group and cell parameters a = 6.74874(10) Å, b = 9.62922(11) Å, c = 6.69994(12) Å, α = 69.6585(13)°, β = 102.3446(14)°, γ = 96.8782(11)°, Z = 2, V = 398.314(11) Å3] is analogous to the structure of walstromite from type locality—Rush Creek, eastern Fresno County, California, USA. The Raman spectra of all tree minerals exhibit bands related to stretching symmetric vibrations of Si-O-Si at 650–660 cm−1 and Si-O at 960–990 cm−1 in three-membered rings (Si3O9)6−. This new genetic pyrometamorphic type of walstromite forms out of the differentiated melt portions enriched in Ba, V, S, P, U, K, Na, Ti and F, a residuum after crystallization of rock-forming minerals of the paralava (rankinite, gehlenite-åkermanite-alumoåkermanite, schorlomite-andradite series and wollastonite). Walstromite associates with other Ba-minerals, also products of the residual melt crystallization as zadovite, BaCa6[(SiO4)(PO4)](PO4)2F and gurimite, Ba3(VO4)2. The genesis of unusual barium mineralization in rankinite paralava is discussed. Walstromite is isostructural with minerals—margarosanite, BaCa2Si3O9 and breyite, CaCa2(Si3O9), discovered in 2018. [ABSTRACT FROM AUTHOR]