Thermal expansion and high-temperature P21/c–C2/c phase transition in clinopyroxene-type LiFeGe2O6 and comparison to NaFe(Si,Ge)2O6

A synthetic clinopyroxene with composition LiFe³⁺Ge₂O₆, monoclinic s.g. P2₁/c, a = 9.8792(7), b = 8.8095(5), c = 5.3754(3) Å, β = 108.844(6)°, V = 442.75(16) ų, has been studied by in situ low- and high-temperature single-crystal X-ray diffraction. The variation of lattice parameters and the intensity of the b-type reflections (h + k = 2n + 1, only present in the P-symmetry) with increasing temperature showed a displacive phase transition from space group P2₁/c to C2/c at a transition temperature T _tr = 789 K, first order in character, with a sudden volume increase of 1.6% and a decrease of β by 1° at the transition. This spontaneous dilatation is reversible, shows a limited hysteresis of ±10°C, and corresponds to the vanishing of the b-type reflections, thus indicating a symmetry increase to space group C2/c. Below T _tr an expansion is observed for all the cell parameters, while the β angle remained almost constant; at T > T _tr the thermal volume expansion is due to dilatation of the structure in the $(\bar{1}\,0\,1) A synthetic clinopyroxene with composition LiFe³⁺Ge₂O₆, monoclinic s.g. P2₁/c, a = 9.8792(7), b = 8.8095(5), c = 5.3754(3) ?, β = 108.844(6)°, V = 442.75(16) ?³, has been studied by in situ low- and high-temperature single-crystal X-ray diffraction. The variation of lattice parameters and the intensity of the b-type reflections (h + k = 2n + 1, only present in the P-symmetry) with increasing temperature showed a displacive phase transition from space group P2₁/c to C2/c at a transition temperature T _tr = 789 K, first order in character, with a sudden volume increase of 1.6% and a decrease of β by 1° at the transition. This spontaneous dilatation is reversible, shows a limited hysteresis of ±10°C, and corresponds to the vanishing of the b-type reflections, thus indicating a symmetry increase to space group C2/c. Below T _tr an expansion is observed for all the cell parameters, while the β angle remained almost constant; at T > T _tr the thermal volume expansion is due to dilatation of the structure in the ([`1] 0 1)(\bar{1}\,0\,1) plane, mostly along [0 1 0], and pure shear in the (0 1 0) plane due to the decrease of β. From comparison with silicate analogues, the germanate clinopyroxenes are more expansible, while the P2₁/c expands more than the C2/c phase. The evolution of Q ² (calculated as the normalized intensity of b-type reflections) with T in the framework of the Landau theory has been done using a standard expression for a first order phase transition. We observe a jump of Q ₀² = 0.538(2) at T _tr, with T _c of 481(7) K, b/a = −2,290 K, and c/a = 3,192 K, and thus far from being tri-critical point. A closely related composition (LiFe³⁺Si₂O₆) shows an equivalent phase transition at 228 K, which is very close to the tri-critical point and 561 K cooler. This result indicates that a change in the composition of tetrahedral sites can have dramatic effects on the P2₁/c ↔ C2/c displacive phase transition in clinopyroxenes. The major changes observed in the evolution of the crystal structure with T are observed in the M2 polyhedron, with a volume decrease by ca. 13.3%, compared to ca. 1.3% observed in the M1 polyhedron. The tetrahedra behave as rigid units with neither a significant change of volume at T > T _tr (<1‰), nor a change of tilting of the basal plane. No change in coordination is observed at T > T _tr in the M2 polyhedron, which remains sixfold coordinated although a strong deformation of this polyhedron is observed. This deformation is related to a strong change by 51.4° at T _tr of the kinking angle (O3–O3–O3 angle) of the B-chain of tetrahedra, which switches from O-rotated to S-rotated [from 143.3(5)° to 194.7(6)°]. The A-chain is S-rotated at T < T _tr [206.8(5)° at 703 K] and extends by 12° at the transition.     

The high-pressure C2/c–P21/c phase transition along the LiAlSi2O6–LiGaSi2O6 solid solution

Two synthetic single-crystals with composition Li(Al_0.53Ga_0.47)Si₂O₆ and LiGaSi₂O₆ and space group C2/c at room conditions have been studied under pressure by means of X-ray diffraction using a diamond anvil cell. The unit-cell parameters were determined at 12 and 10 different pressures up to P = 8.849 and P = 7.320 GPa for Li(Al_0.53Ga_0.47)Si₂O₆ and LiGaSi₂O₆, respectively. The sample with mixed composition shows a C2/c to P2₁/c phase transformation between 1.814 and 2.156 GPa, first-order in character. The transition is characterised by a large and discontinuous decrease in the unit-cell volume and by the appearance of the b-type reflections (h + k = odd) typical of the primitive symmetry. The Ga end-member shows the same C2/c to P2₁/c transformation at a pressure between 0.0001 and 0.39 GPa. The low-pressure value at which the transition occurred did not allow collecting any data in the C2/c pressure stability field except that on room pressure. Our results compared with those relative to spodumene (LiAlSi₂O₆, Arlt and Angel 2000a) indicate that the substitution of Al for Ga at the M1 site of Li-clinopyroxenes strongly affects the transition pressure causing a decrease from 3.17 GPa (spodumene) to less than 0.39 GPa (LiGaSi₂O₆) and decreases the volume discontinuity at the transition. As already found for other compounds, the C2/c low-pressure phases are more rigid than the P2₁ /c high-pressure ones. Moreover, the increase of the M1 cation radius causes a decrease in the bulk modulus K _T0. The axial compressibility among the Li-bearing clinopyroxenes indicates that the c axis is the most rigid for the C2/c phases while it becomes the most compressible for the P2₁ /c phases.     

Equilibrium experiments in the system MgO–SiO2–H2O (MSH): stability fields of clinohumite-OH [Mg9Si4O16(OH)2], chondrodite-OH [Mg5Si2O8(OH)2] and phase A (Mg7Si2O8(OH)6)

The water-pressure and temperature stability fields of clinohumite-OH, chondrodite-OH and phase A were determined in reversed equilibrium experiments up to 100 kbar within the system MgO–SiO₂–H₂O. Their PT-fields differ from results from former synthesis experiments. Bracketing experiments on the reaction phase A + low P-clinoenstatite ⇆ forsterite + water resulted in a slightly steeper dP/dT-slope compared to earlier experiments for this equilibrium. Clinohumite-OH and chondrodite-OH both have large stability fields which extend over pressure ranges of more than 80 kbar. However, they are hardly relevant as hydrous minerals within the subducted oceanic lithosphere. Both are too Mg-rich for a typical mantle bulk composition. In addition, the dehydration of subducted oceanic lithosphere – due to (forsterite + water)-forming reactions – will occur before the two humite-group phases even become stable. Restricted to the cool region of cold subducting slabs, phase A, however, might be formed via the reactions phase A + low P-/high P-clinoenstatite ⇆ forsterite + water or antigorite + brucite ⇆ phase A + water, before dehydration of the oceanic lithosphere occurs. Received: 22 July 1997 / Accepted: 12 March 1998     

Synthetic ANaB(Na x Li1 − x Mg1)CMg5Si8O22(OH)2 (with x = 0.6, 0.2 and 0) P21/m amphiboles at high pressure: a synchrotron infrared study

The high-pressure behavior of three synthetic amphiboles crystallized with space group P2₁/m at room conditions in the system Li₂O–Na₂O–MgO–SiO₂–H₂O has been studied by in situ synchrotron infrared absorption spectroscopy. The amphiboles have compositions ^ANa ^B(Na _x Li_1 − x Mg₁) ^CMg₅ Si₈ O₂₂(OH)₂ with x = 0.6, 0.2 and 0.0, respectively. The high-P experiments up to 32 GPa were carried out on the U2A beamline at Brookhaven National Laboratory (NY, USA) using a diamond anvil cell under non-hydrostatic or quasi-hydrostatic conditions. The two most intense absorption bands in the OH-stretching infrared spectra can be assigned to two non-equivalent O–H dipoles in the P2₁/m structure, bonded to the same local environment ^M1M3Mg₃–OH–^ANa, and pointing toward two differently kinked tetrahedral rings. In all samples these bands progressively merge to give a unique symmetrical absorption with increasing pressure, suggesting a change in symmetry from P2₁/m to C2/m. The pressure at which the transition occurs appears to be linearly correlated to the aggregate B-site dimension. The infrared spectra collected for amphibole ^B(Na_0.2Li_0.8Mg₁) in the frequency range 50 to 1,400 cm⁻¹ also show a series of changes with increasing pressure. The data reported here support the inference of Iezzi et al. (Am Miner 91:479–482, 2006a) regarding a new high-pressure amphibole polymorph.     

Thermodynamic behaviour of the high-temperature P\bar 1{\text{-}}I\bar 1 phase transition along the CaAl2Si2O8–SrAl2Si2O8 join

In situ high-temperature synchrotron radiation powder diffraction patterns were taken from room temperature to T = 740°C from synthetic feldspars along the join CaAl₂Si₂O₈–SrAl₂Si₂O₈ (An–SrF). Three samples of composition An₉₅SrF₅, An₉₀SrF₁₀ and An₈₅SrF₁₅ were investigated, and the evolution of cell parameters with T was determined by Rietveld analysis of powder X-ray diffraction patterns. The high-temperature $P\bar 1{\text{-}}I\bar 1$ phase transition, previously observed with T _c = 241°C in anorthite, was found in An₉₅SrF₅, An₉₀SrF₁₀ and An₈₅SrF₁₅ feldspars at T _c = 233(5)°, 195(2)° and 174(2)°C respectively. The transition was revealed by the disappearance of critical reflections and variations in the rate of change of cell parameters with temperature. A significant, although small (between 0.0025 and 0.0012 at room temperature), spontaneous strain could be measured, allowing the thermodynamic behaviour of the transition to be modelled. A second-order trend for An₉₀SrF₁₀ and An₈₅SrF₁₅ [β = 0.504(7) and 0.505(7) respectively] or nearly second-order for An₉₅SrF₅[β = 0.458(4)] was observed in contrast with tricritical behaviour of end member anorthite. An extrapolation of the T _c versus composition to room temperature indicates that the critical composition for the $P\bar 1$ phase is An₆₀SrF₄₀.     

Phase relations and formation of sodium-rich majoritic garnet in the system Mg3Al2Si3O12–Na2MgSi5O12 at 7.0 and 8.5 GPa

The pseudo-binary system Mg₃Al₂Si₃O₁₂–Na₂MgSi₅O₁₂ modelling the sodium-bearing garnet solid solutions has been studied at 7 and 8.5 GPa and 1,500–1,950°C. The Na-bearing garnet is a liquidus phase of the system up to 60 mol% Na₂MgSi₅O₁₂ (NaGrt). At higher content of NaGrt in the system, enstatite (up to ∼80 mol%) and then coesite are observed as liquidus phases. Our experiments provided evidence for a stable sodium incorporation in garnet (0.3–0.6 wt% Na₂O) and its control by temperature and pressure. The highest sodium contents were obtained in experiments at P = 8.5 GPa. Near the liquidus (T = 1,840°C), the equilibrium concentration of Na₂O in garnet is 0.7–0.8 wt% (∼6 mol% Na₂MgSi₅O₁₂). With the temperature decrease, Na concentration in Grt increases, and the maximal Na₂MgSi₅O₁₂ content of ∼12 mol% (1.52 wt% Na₂O) is gained at the solidus of the system (T = 1,760°С). The data obtained show that most of natural diamonds, with inclusions of Na-bearing garnets usually containing <0.4 wt% Na₂O, could be formed from sodium-rich melts at pressures lower than 7 GPa. Majoritic garnets with higher sodium concentrations (>1 wt% Na₂O) may crystallize at a pressure range of 7.0–8.5 GPa. However the upper pressure limit for the formation of naturally occurring Na-bearing garnets is restricted by the eclogite/garnetite bulk composition.     

The high-temperature P2/c<Subscript>1</Subscript>–C2/c phase transition in Fe-free Ca-rich P2<Subscript>1</Subscript>/c clinopyroxenes

An in situ, high-temperature, powder diffraction investigation was performed for iron-free clinopyroxenes with compositions Ca_0.40Mg_1.60Si₂O₆, Ca_0.52Mg_1.46Al_0.05Si_1.98O₆, Ca_0.59Mg_1.41Si₂O₆ and Ca_0.70Mg_1.30Si₂O₆, up to 850 °C using synchrotron radiation (ESRF, Grenoble). In samples with compositions Ca_0.52Mg_1.46Al_0.05Si_1.98O₆ and Ca_0.59Mg_1.41Si₂O₆, evidence of for the P2₁/c-C2/c displacive phase transition was seen in changes in lattice parameters at T 550 and 300 °C respectively. Landau modelling of the phase transition behaviour for the sample with composition Ca_0.52Mg_1.46Al_0.05Si_1.98O₆ shows a tricritical behaviour [T _c =547(16)]. Comparison with the transition behaviour in other samples with lower Ca contents along the join diopside–enstatite indicates that a decrease in T _{c ,} and a switch from first-order to tricritical behavior occurs with increasing Ca content. The change in the transition behaviour was related to an interaction with the antiphase domains at the nanoscale.     

Devitrite (Na2Ca3Si6O16)—structural, spectroscopic and computational investigations on a crystalline impurity phase in industrial soda-lime glasses

Single crystals of devitrite (Na₂Ca₃Si₆O₁₆) were synthesized as pale-yellow transparent needle shaped crystals using a Na₂MoO₄-flux. Experiments aiming to prepare the K-equivalent of devitrite from the corresponding K₂MoO₄-flux were unsuccessful. The crystal structure of devitrite was determined from single-crystal X-ray diffraction data (Mo-K_α radiation, 2θ_max.?=?25.34°, R_int?=?2.66%) and refined in space group P $ \bar{1} $ (no. 2) to R(|F|)?=?3.08% using 2,513 observed reflections with I?>?2σ(I). Unit-cell parameters are: a?=?7.2291(8), b?=?10.1728(12), c?=?10.6727(12) Å, α?=?95.669(9), β?=?109.792(10), γ?=?99.156(9)°, V?=?719.19(14) ų, Z?=?2. The structure belongs to the group of multiple chain silicates consisting of dreier quadruple chains, i.e. the crystallochemical formula can be written as $ {\hbox{N}}{{\hbox{a}}_2}{\hbox{C}}{{\hbox{a}}_3}\left\{ {{\mathbf{uB}}{,4}_\infty^1} \right\}\left[ {^3{\hbox{S}}{{\hbox{i}}_6}} \right.\left. {{{\hbox{O}}_{16}}} \right\} $ . Linkage between the bands running along [100] is provided by double chains of edge sharing CaO₆-octahedra as well as additional more irregularly coordinated Na- and Ca-cations located in the tunnel-like cavities of the mixed tetrahedral-octahedral framework. Structural investigations were completed by Raman and infrared spectroscopical studies. The allocation of the bands to certain vibrational species was aided by density functional theory (DFT) calculations.     

Lavoisierite, Mn2+ 8[Al10(Mn3+Mg)][Si11P]O44(OH)12, a new mineral from Piedmont, Italy: the link between “ardennite” and sursassite

The new mineral species lavoisierite, ideally Mn²⁺ ₈[Al₁₀(Mn³⁺Mg)][Si₁₁P]O₄₄(OH)₁₂, has been discovered in piemontite-bearing micaschists belonging to the Piedmontese Nappe from Punta Gensane, Viù Valley, Western Alps, Italy. It occurs as yellow-orange acicular to prismatic-tabular crystals up to a few millimeters in length, with white streak and vitreous luster, elongated along [010] and flattened on {001}. Lavoisierite is associated with quartz, “mica,” sursassite, piemontite, spessartine, braunite, and “tourmaline.” Calculated density is 3.576 g cm^?3. In plane-polarized light, it is transparent, pleochroic, with pale yellow parallel to [010] and yellow-orange normal to this direction; extinction is parallel and elongation is positive. Birefringence is moderate; the calculated average refraction index n is 1.750. Lavoisierite is orthorhombic, space group Pnmm, with a 8.6891(10), b 5.7755(3), c 36.9504(20) Å, V 1854.3(2) Å³, Z = 2. Calculated main diffraction lines of the X-ray powder diffraction pattern are [d in Å, (I), (hkl); relative intensities are visually estimated]: 4.62 (m) (112), 2.931 (vs) (1110), 2.765 (s) (1111), 2.598 (s) (310), 2.448 (ms) (028). Chemical analyses by electron microprobe give (in wt%) P₂O₅ 2.08, V₂O₅ 0.37, SiO₂ 34.81, TiO₂ 0.13, Al₂O₃ 22.92, Cr₂O₃ 0.32, Fe₂O₃ 0.86, Mn₂O₃ 6.92, MnO 19.09, MgO 5.73, CaO 1.94, Na₂O 0.01, H₂O 5.44, sum 100.62 wt%. H₂O content was calculated from structure refinement. The empirical formula, based on 56 anions, is (Mn _5.340 ²⁺ Mg_1.810Ca_0.686Na_0.006)_Σ=7.852(Al_8.921Mn _1.739 ³⁺ Mg_1.010Fe _0.214 ³⁺ Cr_0.084Ti_0.032)_Σ=12.000(Si_11.496P_0.582V_0.081)_Σ=12.159O_43.995(OH)_12.005. The crystal structure of lavoisierite was solved by direct methods and refined on the basis of 1743 observed reflections to R ₁ = 4.6 %. The structure is characterized by columns of edge-sharing octahedra running along [010] and linked to each other by means of [SiO₄], [Si₂O₇], and [Si₃O₁₀] groups. Lavoisierite, named after the French chemist and biologist Antoine-Laurent de Lavoisier (1743–1794), displays an unprecedented kind of structure, related to those of “ardennite” and sursassite.     

The Mg3Al2Si3O12-Na2MgSi5O12 system at pressures of 7.0 and 8.5 GPa and a temperature of 1300–1800°C: Phase relationships and crystallization of Na-bearing majoritic garnet

The results of an experimental study of the pyrope (Mg₃Al₂Si₃O₁₂)-jadeite (NaAlSi₂O₆) system at P = 7.0 and 8.5 GPa and T = 1300?C1800°C are summarized in this paper. The main phases that were obtained in the experiments are garnet, pyroxene, kyanite (in some cases corundum), and quenched melt. Garnets are characterized by a stable Na₂O admixture (up to 0.6 wt % at 7.0 GPa and up to 0.8 wt % at 8.5 GPa) and the high silicon content (Si = 3.016?C3.166). The maximal sodium concentrations in garnet were found at the solidus of the system, which results from an increase of the coefficient of sodium partitioning between garnet and melt during a temperature decrease.     

HTP21/c–C2/c phase transition and kinetics of Fe2+–Mg order–disorder of an Fe-poor pigeonite: implications for the cooling history of ureilites

A natural Ca-poor pigeonite (Wo₆En₇₆Fs₁₈) from the ureilite meteorite sample PCA82506-3, free of exsolved augite, was studied by in situ high-temperature single-crystal X-ray diffraction. The sample, monoclinic P2₁/c, was annealed up to 1,093°C to induce a phase transition from P2₁/c to C2/c symmetry. The variation with increasing temperature of the lattice parameters and of the intensity of the b-type reflections (h + k = 2n + 1, present only in the P2₁/c phase) showed a displacive phase transition P2₁/c to C2/c at a transition temperature T _Tr = 944°C, first order in character. The Fe–Mg exchange kinetics was studied by ex situ single-crystal X-ray diffraction in a range of temperatures between the closure temperature of the Fe–Mg exchange reaction and the transition temperature. Isothermal disordering annealing experiments, using the IW buffer, were performed on three crystals at 790, 840 and 865°C. Linear regression of ln k _D versus 1/T yielded the following equation: ln k_\textD = - 3717( ±416)/T(K) + 1.290( ±0.378);    (R² = 0.988) \ln \,k_{\text{D}} = - 3717( \pm 416)/T(K) + 1.290( \pm 0.378);\quad (R^{2} = 0.988) . The closure temperature (T _c) calculated using this equation was ∼740(±30)°C. Analysis of the kinetic data carried out taking into account the e.s.d.'s of the atomic fractions used to define the Fe–Mg degree of order, performed according to Mueller’s model, allowed us to retrieve the disordering rate constants C ₀ K _dis⁺ for all three temperatures yielding the following Arrhenius relation: ln( C₀ K_\textdis ⁺ ) = ln K₀ - Q/(RT) = 20.99( ±3.74) - 26406( ±4165)/T(K);    (R² = 0.988) \ln \left( {C_{0} K_{\text{dis}}^{ + } } \right) = \ln \,K_{0} - Q/(RT) = 20.99( \pm 3.74) - 26406( \pm 4165)/T(K);\quad (R^{2} = 0.988) . An activation energy of 52.5(±4) kcal/mol for the Fe–Mg exchange process was obtained. The above relation was used to calculate the following Arrhenius relation modified as a function of X _Fe (in the range of X _Fe = 0.20–0.50): ln( C₀ K_\textdis ⁺ ) = (21.185 - 1.47X_\textFe ) - \frac(27267 - 4170X_\textFe )T(K) \ln \left( {C_{0} K_{\text{dis}}^{ + } } \right) = (21.185 - 1.47X_{\text{Fe}} ) - {\frac{{(27267 - 4170X_{\text{Fe}} )}}{T(K)}} . The cooling time constant, η = 6 × 10⁻¹ K⁻¹ year⁻¹ calculated on the PCA82506-3 sample, provided a cooling rate of the order of 1°C/min consistent with the extremely fast late cooling history of the ureilite parent body after impact excavation.     

The solubility of BaCO3(cr) (witherite) in CO2-H2O solutions between 0 and 90°C,evaluation of the association constants of BaHCO3+(aq) and BaCO30(aq) between 5 and 80°C,and a preliminary evaluation of the thermodynamic properties of Ba2+(aq)

One hundred and fifty new measurements of the solubility of witherite were used to evaluate the equilibrium constant of the reaction BaCO₃(cr) = Ba²⁺(aq) + CO₃²⁻(aq) between 0 and 90°C and 1 atm total pressure. The temperature dependence of the equilibrium constant is given by logK = 607.642 + 0.121098T − 20011.25/T − 236.4948 logT where T is in degrees Kelvin. The logK of BaCO₃(cr), the Gibbs energy, the enthalpy and entropy of the reaction at 298.15 K are −8.562, 48.87 kJ · mol⁻¹, 2.94 kJ · mol⁻¹ and −154.0 J · mol⁻¹ · K⁻¹, respectively. The equilibrium constants are consistent with an aqueous model that includes the ion pairs BaHCO₃⁺(aq) and BaCO₃⁰(aq) Three different methods were used to evaluate the association constant of BaHCO₃⁺(aq), and all yielded similar results. The temperature dependence of the association constant for the reaction Ba²⁺(aq) + HCO₃⁻(aq) = BaHCO₃⁺(aq) is given by logK_BaHCO3⁺ = −3.0938 + 0.013669T.The log of the association constant, the Gibbs energy, the enthalpy and entropy of the reaction at 298.15°K are 0.982, −5.606 kJ · mol⁻¹, 23.26 kJ · mol⁻¹ and 96.8 J · mol⁻¹ · K⁻¹, respectively. The temperature dependence of the equilibrium constant for the reaction Ba²⁺(aq) + CO²⁻₃(aq) = BaCO₀³(aq) is given by logK_BaCO3⁰ = 0.113 + 0.008721T.The log of the association constant, the Gibbs energy, the enthalpy and entropy of the reaction at 298.15° K are 2.71, −15.49 kJ · mol⁻¹, 14.84 kJ · mol⁻¹ and 101.7 J· mol⁻¹ · K⁻¹.The above model leads to reliable calculations of the aqueous speciation and solubility of witherite in the system BaCO₃-CO₂-H₂O from 0 to more than 90°C. Literature data on witherite solubility were re-evaluated and compared with the results of this study.Problems in the thennodynamic selections of Ba compounds are considered. Newer data require the revision of Δ_fH° and Δ_fG° of Ba²⁺(aq) to −532.5 and −555.36 kJ · mol⁻¹, respectively, for agreement with solubility data.     

Burovaite-Ca, (Na,K)4Ca2(Ti,Nb)8[Si4O12]4(OH,O)8·12H2O, a new labuntsovite-group mineral species and its place in low-temperature mineral formation in pegmatites of the Khibiny pluton, Kola Peninsula, Russia

This paper presents data on burovaite-Ca, the first Ti-dominant member of the labuntsovite group with a calcium D-octahedron. The idealized formula of burovaite-Ca is (K,Na)₄Ca₂(Ti,Nb)₈[Si₄O₁₂]₄(OH,O)₈ · 12H₂O. The mineral has been found in the hydrothermal zone of aegirine-microcline pegmatite located in khibinite at Mt. Khibinpakhkchorr, the Khibiny pluton, Kola Peninsula, Russia. Radiaxial intergrowths of burovaite-Ca and labuntsovite-Mn associated with lemmleynite-Ba, analcime, and apophyllite have been identified in caverns within microcline. The mean composition of the mineral is as follows, wt %: 3.72 Na₂O, 2.76 K₂O, 4.22 CaO, 0.47 SrO, 0.23 BaO, 0.01 MnO, 0.30 Fe₂O₃, 0.14 Al₂O₃, 42.02 SiO₂, 17.30 TiO₂, 15.21 Nb₂O₅, 12.60 H₂O (measured); the total is 98.98. Its empirical formula has been calculated on the basis of [(Si,Al)₁₆O₄₈]: {(Na_3.10K_1.07Ca_0.37Sr_0.04Ba_0.04)_4.62}(Ca_1.28Zn_0.01)_1.29(Ti_4.97Nb_2.56Fe_0.08Ta_0.02)_7.63(Si_15.93Al_0.07)₁₆O₄₈(OH_6.70O_0.93)_7.63 · 12H₂O. The strongest lines in the X-ray powder diffraction pattern of burovaite-Ca (I-d ?] are as follows: 70–7.08, 40–6.39, 40–4.97, 30–3.92, 40–3.57, 100–3.25, 70–3.11, 50–2.61, 70–2.49, 40–2.15, 50–2.05, 70–1.712, 70–1.577, and 70–1.444. The structure of burovaite-Ca was solved by A.A. Zolotarev, Jr. The mineral is monoclinic, space group C2/m. The unit-cell dimensions are a = 14.529(3), b = 14.203(3), c = 7.899(1), β = 117.37(1)°, V = 1447.57 ?₃. Burovaite-Ca is an isostructural Ti-dominant analogue of karupm?llerite-Ca and gjerdingenite-Ca. Two stages of mineral formation—pegmatite proper and hydrothermal—have been recognized in the host pegmatite. The hydrothermal stage included K-Ba-Na, Na-K-Ca, and Na-Sr substages. Burovaite-Ca is related to the intermediate Na-K-Ca substage. At the first substage, labuntsovite-Mn and lemmleynite-Ba were formed, and tsepinite-Na, paratsepinite-Nd, and tsepinite-Sr were formed at the final substage. Thus, the sequence of crystallization of labuntsovite-group minerals is characterized by the replacement of the potassium regime by the sodium regime of alkaline solutions in the evolved host pegmatite.