Mangazeite,Al<Subscript>2</Subscript>(SO<Subscript>4</Subscript>)(OH)<Subscript>4</Subscript> · 3H<Subscript>2</Subscript>O,a new mineral species

Mangazeite, a new mineral species, has been found at the Mangazeya silver deposit (300 km east of the Lena River, 65°43′40″ N and 130°20′ E) in eastern Yakutia (Sakha Republic, Siberia, Russia). The new mineral was described from fractured, sericitized, and pyritized granodiorite adjacent to a quartz-arsenopyrite vein. Associated minerals are gypsum and chlorite. The new mineral occurs as radial fibrous segregations of thin lamellar crystals. The size of the fibers does not exceed 40 μm in length and 1 μm across. The mineral is white, with a white streak and a vitreous luster. Mangazeite is transparent in isolated grains. No fluorescence is observed. The Mohs hardness is 1–2. The calculated density is 2.15 g/cm³. The new mineral is biaxial; its optical character was not determined; α = 1.525(9), β was not measured, and γ = 1.545(9). The average chemical composition is as follows (wt %): Al₂O₃ 36.28, SO₃ 28.81, H₂O⁺ 34.35, total 99.44, H₂O^? 9.27. The H₂O^? content was neither included in the total nor used in formula calculation. The empirical formula is Al_1.99(SO₄)_1.01(OH)_3.94 · 3.37H₂O. The simplified formula is Al₂(SO₄)(OH)₄ · 3H₂O. The theoretical chemical composition calculated from this formula is (wt %) Al₂O₃ 37.47, SO₃ 29.42, H₂O 33.11, total 100.00. The new mineral is triclinic; the unit cell parameters refined from X-ray powder diffraction data are a = 8.286(5), b = 9.385(5), c = 11.35(1) Å, α = 96.1(1), β = 98.9(1), γ = 96.6(1)°, and Z = 4. The strongest lines in the X-ray powder diffraction pattern (d(I, %)) are 8.14(19), 7.59(49), 7.16(46), 4.258(100), 4.060(48), and 3.912(43). Mangazeite is supergene in origin and crystallized in a favorable aluminosilicate environment in the presence of sulfate ion due to pyrite oxidation.     

In situ high-temperature X-ray diffraction and spectroscopic study of fibroferrite,FeOH(SO<Subscript>4</Subscript>)·5H<Subscript>2</Subscript>O

The thermal dehydration process of fibroferrite, FeOH(SO₄)·5H₂O, a secondary iron-bearing hydrous sulfate, was investigated by in situ high-temperature synchrotron X-ray powder diffraction (HT-XRPD), in situ high-temperature Fourier transform infrared spectroscopy (HT-FTIR) and thermal analysis (TGA-DTA) combined with evolved gas mass spectrometry. The data analysis allowed the determination of the stability fields and the reaction paths for this mineral as well as characterization of its high-temperature products. Five main endothermic peaks are observed in the DTA curve collected from room T up to 800 °C. Mass spectrometry of gases evolved during thermogravimetric analysis confirms that the first four mass loss steps are due to water emission, while the fifth is due to a dehydroxylation process; the final step is due to the decomposition of the remaining sulfate ion. The temperature behavior of the different phases occurring during the heating process was analyzed, and the induced structural changes are discussed. In particular, the crystal structure of a new phase, FeOH(SO₄)·4H₂O, appearing at about 80 °C due to release of one interstitial H₂O molecule, was solved by ab initio real-space and reciprocal-space methods. This study contributes to further understanding of the dehydration mechanism and thermal stability of secondary sulfate minerals.     

Attikaite,Ca<Subscript>3</Subscript>Cu<Subscript>2</Subscript>Al<Subscript>2</Subscript>(AsO<Subscript>4</Subscript>)<Subscript>4</Subscript>(OH)<Subscript>4</Subscript> · 2H<Subscript>2</Subscript>O,a new mineral species

Attikaite, a new mineral species, has been found together with arsenocrandalite, arsenogoyazite, conichalcite, olivenite, philipsbornite, azurite, malachite, carminite, beudantite, goethite, quartz, and allophane at the Christina Mine No. 132, Kamareza, Lavrion District, Attiki Prefecture (Attika), Greece. The mineral is named after the type locality. It forms spheroidal segregations (up to 0.3 mm in diameter) consisting of thin flexible crystals up to 3 × 20 × 80 μm in size. Its color is light blue to greenish blue, with a pale blue streak. The Mohs’ hardness is 2 to 2.5. The cleavage is eminent mica-like parallel to {001}. The density is 3.2(2) g/cm³ (measured in heavy liquids) and 3.356 g/cm³ (calculated). The wave numbers of the absorption bands in the infrared spectrum of attikaite are (cm^?1; sh is shoulder; w is a weak band): 3525sh, 3425, 3180, 1642, 1120w, 1070w, 1035w, 900sh, 874, 833, 820, 690w, 645w, 600sh, 555, 486, 458, and 397. Attikaite is optically biaxial, negative, α = 1.642(2), β = γ = 1.644(2) (X = c) 2V _means = 10(8)°, and 2V _calc = 0°. The new mineral is microscopically colorless and nonpleochroic. The chemical composition (electron microprobe, average over 4 point analyses, wt %) is: 0.17 MgO, 17.48 CaO, 0.12 FeO, 16.28 CuO, 10.61 Al₂O₃, 0.89 P₂O₅, 45.45 As₂O₅, 1.39 SO₃, and H₂O (by difference) 7.61, where the total is 100.00. The empirical formula calculated on the basis of (O,OH,H₂O)₂₂ is: Ca_2.94Cu _1.93 ²⁺ Al_1.97Mg_0.04Fe _0.02 ²⁺ [(As_3.74S_0.16P_0.12)_Σ4.02O_16.08](OH)_3.87 · 2.05H₂ O. The simplified formula is Ca₃Cu₂Al₂(AsO₄)₄(OH)₄ · 2H₂O. Attikaite is orthorhombic, space group Pban, Pbam or Pba2; the unit-cell dimensions are a = 10.01(1), b = 8.199(5), c = 22.78(1) Å, V = 1870(3) ų, and Z = 4. In the result of the ignition of attikaite for 30 to 35 min at 128–140°, the H₂O bands in the IR spectrum disappear, while the OH-group band is not modified; the weight loss is 4.3%, which approximately corresponds to two H₂O molecules per formula; and parameter c decreases from 22.78 to 18.77 Å. The strongest reflections in the X-ray powder diffraction pattern [d, Å (I, %)((hkl)] are: 22.8(100)(001), 11.36(60)(002), 5.01(90)(200), 3.38(5)(123, 205), 2.780(70)(026), 2.682(30)(126), 2.503(50)(400), 2.292(20)(404). The type material of attikaite is deposited in the Fersman Mineralogical Museum, Russian Academy of Sciences, Moscow. The registration number is 3435/1.     

Tinnunculite,C<Subscript>5</Subscript>H<Subscript>4</Subscript>N<Subscript>4</Subscript>O<Subscript>3</Subscript> · 2H<Subscript>2</Subscript>O: Occurrences on the Kola Peninsula and Redefinition and Validation as a Mineral Species

Based on a study of samples found in the Khibiny (Mt. Rasvumchorr: the holotype) and Lovozero (Mts Alluaiv and Vavnbed) alkaline complexes on the Kola Peninsula, Russia, tinnunculite was approved by the IMA Commission on New Minerals, Nomenclature, and Classification as a valid mineral species (IMA no. 2015-02la) and, taking into account a revisory examination of the original material from burnt dumps of coal mines in the southern Urals, it was redefined as crystalline uric acid dihydrate (UAD), C₅H₄N₄O₃ · 2H₂O. Tinnunculite is poultry manure mineralized in biogeochemical systems, which could be defined as “guano microdeposits.” The mineral occurs as prismatic or tabular crystals up to 0.01 × 0.1 × 0.2 mm in size and clusters of them, as well as crystalline or microglobular crusts. Tinnunculite is transparent or translucent, colorless, white, yellowish, reddish or pale lilac. Crystals show vitreous luster. The mineral is soft and brittle, with a distinct (010) cleavage. D_calc = 1.68 g/cm³ (holotype). Tinnunculite is optically biaxial (–), α = 1.503(3), β = 1.712(3), γ = 1.74(1), 2V_obs = 40(10)°. The IR spectrum is given. The chemical composition of the holotype sample (electron microprobe data, content of H is calculated by UAD stoichiometry) is as follows, wt %: 37.5 О, 28.4 С, 27.0 N, 3.8 H_calc, total 96.7. The empirical formula calculated on the basis of (C + N+ O) = 14 apfu is: C_4.99H₈N_4.07O_4.94. Tinnunculite is monoclinic, space group (by analogy with synthetic UAD) P2₁/c. The unit cell parameters of the holotype sample (single crystal XRD data) are a = 7.37(4), b = 6.326(16), c = 17.59(4) Å, β = 90(1)°, V = 820(5) ų, Z = 4. The strongest reflections in the XRD pattern (d, Å–I[hkl]) are 8.82–84[002], 5.97–15[011], 5.63–24[102?, 102], 4.22–22[112], 3.24–27[114?,114], 3.18–100[210], 3.12–44[211?, 211], 2.576–14[024].     

Nickelpicromerite,K<Subscript>2</Subscript>Ni(SO<Subscript>4</Subscript>)<Subscript>2</Subscript>•6H<Subscript>2</Subscript>O,a new picromerite-group mineral from Slyudorudnik,South Urals,Russia

A new picromerite-group mineral, nickelpicromerite, K₂Ni(SO₄)₂?·?6H₂O (IMA 2012–053), was found at the Vein #169 of the Ufaley quartz deposit, near the town of Slyudorudnik, Kyshtym District, Chelyabinsk area, South Urals, Russia. It is a supergene mineral that occurs, with gypsum and goethite, in the fractures of slightly weathered actinolite-talc schist containing partially vermiculitized biotite and partially altered sulfides: pyrrhotite, pentlandite, millerite, pyrite and marcasite. Nickelpicromerite forms equant to short prismatic or tabular crystals up to 0.07 mm in size and anhedral grains up to 0.5 mm across, their clusters or crusts up to 1 mm. Nickelpicromerite is light greenish blue. Lustre is vitreous. Mohs hardness is 2–2½. Cleavage is distinct, parallel to {10–2}. D _meas is 2.20(2), D _calc is 2.22 g cm^?3. Nickelpicromerite is optically biaxial (+), α?=?1.486(2), β?=?1.489(2), γ?=?1.494(2), 2V_meas =75(10)°, 2V_calc =76°. The chemical composition (wt.%, electron-microprobe data) is: K₂O 20.93, MgO 0.38, FeO 0.07, NiO 16.76, SO₃ 37.20, H₂O (calc.) 24.66, total 100.00. The empirical formula, calculated based on 14 O, is: K_1.93Mg_0.04Ni_0.98S_2.02O_8.05(H₂O)_5.95. Nickelpicromerite is monoclinic, P2₁/c, a?=?6.1310(7), b?=?12.1863(14), c?=?9.0076(10) Å, β?=?105.045(2)°, V?=?649.9(1) ų, Z?=?2. Eight strongest reflections of the powder XRD pattern are [d,Å-I(hkl)]: 5.386–34(110); 4.312–46(002); 4.240–33(120); 4.085–100(012, 10–2); 3.685–85(031), 3.041–45(040, 112), 2.808–31(013, 20–2, 122), 2.368–34(13–3, 21–3, 033). Nickelpicromerite (single-crystal X-ray data, R?=?0.028) is isostructural to other picromerite-group minerals and synthetic Tutton’s salts. Its crystal structure consists of [Ni(H₂O)₆]²⁺ octahedra linked to (SO₄)^2? tetrahedra via hydrogen bonds. K⁺ cations are coordinated by eight anions. Nickelpicromerite is the product of alteration of primary sulfide minerals and the reaction of the acid Ni-sulfate solutions with biotite.     

Effect of KCl on melting in the Mg<Subscript>2</Subscript>SiO<Subscript>4</Subscript>–MgSiO<Subscript>3</Subscript>–H<Subscript>2</Subscript>O system at 5 GPa

To examine the effect of KCl-bearing fluids on the melting behavior of the Earth’s mantle, we conducted experiments in the Mg₂SiO₄–MgSiO₃–H₂O and Mg₂SiO₄–MgSiO₃–KCl–H₂O systems at 5 GPa. In the Mg₂SiO₄–MgSiO₃–H₂O system, the temperature of the fluid-saturated solidus is bracketed between 1,200–1,250°C, and both forsterite and enstatite coexist with the liquid under supersolidus conditions. In the Mg₂SiO₄–MgSiO₃–KCl–H₂O systems with molar Cl/(Cl + H₂O) ratios of 0.2, 0.4, and 0.6, the temperatures of the fluid-saturated solidus are bracketed between 1,400–1,450°C, 1,550–1,600°C, and 1,600–1,650°C, respectively, and only forsterite coexists with liquid under supersolidus conditions. This increase in the temperature of the solidus demonstrates the significant effect of KCl on reducing the activity of H₂O in the fluid in the Mg₂SiO₄–MgSiO₃–H₂O system. The change in the melting residues indicates that the incongruent melting of enstatite (enstatite = forsterite + silica-rich melt) could extend to pressures above 5 GPa in KCl-bearing systems, in contrast to the behavior in the KCl-free system.     

Hydrosilicate liquids in the system rare-metal granite–Na<Subscript>2</Subscript>O–SiO<Subscript>2</Subscript>–H<Subscript>2</Subscript>O as accumulators of ore components at high pressure and temperature

Experimental investigations in the system rare-metal granite–Na₂O–SiO₂–H₂O with the addition of aqueous solutions containing Rb, Cs, Sn, W, Mo, and Zn at 600°C and 1.5 kbar showed that the typical elements of rare-metal granites (Li, Rb, Cs, Be, Nb, and Ta) are preferentially concentrated in hydrosilicate liquids coexisting with aqueous fluid. The same behavior is characteristic of Zn and Sn, the minerals of which are usually formed under hydrothermal conditions. In contrast, Mo and W are weakly extracted by hydrosilicate liquids and almost equally distributed between them and aqueous fluids. Liquids similar to those described in this paper are formed during the final stages of magmatic crystallization in granite and granitepegmatite systems. The formation of hydrosilicate liquids in late magmatic and postmagmatic processes will be an important factor controlling the redistribution of metal components between residual magmatic melts, minerals, and aqueous fluids and, consequently, the mobility of these components in fluid-saturated magmatic systems enriched in rare metals.     

Fluid–mineral reactions and melting of orthopyroxene–cordierite–biotite gneiss in the presence of H<Subscript>2</Subscript>O-CO<Subscript>2</Subscript>-NaCl and H<Subscript>2</Subscript>O-CO<Subscript>2</Subscript>-KCl fluids under parameters of granulite-facies metamorphism

Reactions and partial melting of peraluminous rocks in the presence of H₂O-CO₂–salt fluids under parameters of granulite-facies metamorphism were modeled in experiments on interaction between orthopyroxene–cordierite–biotite–plagioclase–quartz metapelite with H₂O, H₂O-CO₂, H₂O-CO₂-NaCl, and H₂O-CO₂-KCl fluids at 600 MPa and 850°C. Rock melting in the presence of H₂O and equimolar H₂O-CO₂ fluids generates peraluminous (A/CNK¹ > 1.1) melts whose composition corresponds to magnesian calcic or calc–alkaline S-type granitoids. The melts are associated with peritectic phases: magnesian spinel and orthopyroxene containing up to 9 wt % Al₂O₃. In the presence of H₂O-CO₂-NaCl fluid, cordierite and orthopyroxene are replaced by the association of K-Na biotite, Na-bearing gedrite, spinel, and albite. The Na₂O concentrations in the biotite and gedrite are functions of the NaCl concentrations in the starting fluid. Fluids of the composition H₂O-CO₂-KCl induce cordierite replacement by biotite with corundum and spinel and by these phases in association with potassium feldspar at X _KCl = 0.02 in the fluid. When replaced by these phases, cordierite is excluded from the melting reactions, and the overall melting of the metapelite is controlled by peritectic reactions of biotite and orthopyroxene with plagioclase and quartz. These reactions produce such minerals atypical of metapelites as Ca-Na amphibole and clinopyroxene. The compositions of melts derived in the presence of salt-bearing fluids are shifted toward the region with A/CNK < 1.1, as is typical of so-called peraluminous granites of type I. An increase in the concentrations of salts in the fluids leads to depletion of the melts in Al₂O₃ and CaO and enrichment in alkalis. These relations suggest that the protoliths of I-type peraluminous granites might have been metapelites that were melted when interacting with H₂O-CO₂-salt fluids. The compositions of the melts can evolve from those with A/CNK > 1.1 (typical of S-type granites) toward those with A/CNK = 1.0–1.1 in response to an increase in the concentrations of alkali salts in the fluids within a few mole percent. Our experiments demonstrate that the origin of new mineral assemblages in metapelite in equilibrium with H₂O-CO₂-salt fluids is controlled by the activities of alkaline components, while the H₂O and CO₂ activities play subordinate roles. This conclusion is consistent with the results obtained by simulating metapelite mineral assemblages by Gibbs free energy minimization (using the PERPE_X software), as shown in log(\({a_{{H_2}O}}\))–log(\({a_{N{a_2}O}}\)) and log(\({a_{{H_2}O}}\))–log(\({a_{{K_2}O}}\)) diagrams.     

The high-pressure stability of chlorite and other hydrates in subduction mélanges: experiments in the system Cr<Subscript>2</Subscript>O<Subscript>3</Subscript>–MgO–Al<Subscript>2</Subscript>O<Subscript>3</Subscript>–SiO<Subscript>2</Subscript>–H<Subscript>2</Subscript>O

The solubility of chromium in chlorite as a function of pressure, temperature, and bulk composition was investigated in the system Cr₂O₃–MgO–Al₂O₃–SiO₂–H₂O, and its effect on phase relations evaluated. Three different compositions with X _Cr = Cr/(Cr + Al) = 0.075, 0.25, and 0.5 respectively, were investigated at 1.5–6.5 GPa, 650–900 °C. Cr-chlorite only occurs in the bulk composition with X _Cr = 0.075; otherwise, spinel and garnet are the major aluminous phases. In the experiments, Cr-chlorite coexists with enstatite up to 3.5 GPa, 800–850 °C, and with forsterite, pyrope, and spinel at higher pressure. At P > 5 GPa other hydrates occur: a Cr-bearing phase-HAPY (Mg_2.2Al_1.5Cr_0.1Si_1.1O₆(OH)₂) is stable in assemblage with pyrope, forsterite, and spinel; Mg-sursassite coexists at 6.0 GPa, 650 °C with forsterite and spinel and a new Cr-bearing phase, named 11.5 Å phase (Mg:Al:Si = 6.3:1.2:2.4) after the first diffraction peak observed in high-resolution X-ray diffraction pattern. Cr affects the stability of chlorite by shifting its breakdown reactions toward higher temperature, but Cr solubility at high pressure is reduced compared with the solubility observed in low-pressure occurrences in hydrothermal environments. Chromium partitions generally according to \(X_{\text{Cr}}^{\text{spinel}}\) ? \(X_{\text{Cr}}^{\text{opx}}\) > \(X_{\text{Cr}}^{\text{chlorite}}\) ≥ \(X_{\text{Cr}}^{\text{HAPY}}\) > \(X_{\text{Cr}}^{\text{garnet}}\). At 5 GPa, 750 °C (bulk with X _Cr = 0.075) equilibrium values are \(X_{\text{Cr}}^{\text{spinel}}\) = 0.27, \(X_{\text{Cr}}^{\text{chlorite}}\) = 0.08, \(X_{\text{Cr}}^{\text{garnet}}\) = 0.05; at 5.4 GPa, 720 °C \(X_{\text{Cr}}^{\text{spinel}}\) = 0.33, \(X_{\text{Cr}}^{\text{HAPY}}\) = 0.06, and \(X_{\text{Cr}}^{\text{garnet}}\) = 0.04; and at 3.5 GPa, 850 °C \(X_{\text{Cr}}^{\text{opx}}\) = 0.12 and \(X_{\text{Cr}}^{\text{chlorite}}\) = 0.07. Results on Cr–Al partitioning between spinel and garnet suggest that at low temperature the spinel- to garnet-peridotite transition has a negative slope of 0.5 GPa/100 °C. The formation of phase-HAPY, in assemblage with garnet and spinel, at pressures above chlorite breakdown, provides a viable mechanism to promote H₂O transport in metasomatized ultramafic mélanges of subduction channels.     

Crystal structure and refined formula of garyansellite Mg<Subscript>2</Subscript>Fe<Superscript>3+</Superscript>(PO<Subscript>4</Subscript>)<Subscript>2</Subscript>(OH) · 2H<Subscript>2</Subscript>O

Single-crystal study of the structure (R = 0.0268) was performed for garyansellite from Rapid Creek, Yukon, Canada. The mineral is orthorhombic, Pbna, a = 9.44738(18), b = 9.85976(19), c = 8.14154(18) Å, V = 758.38(3) ų, Z = 4. An idealized formula of garyansellite is Mg₂Fe³⁺(PO₄)₂(OH) · 2H₂O. Structurally the mineral is close to other members of the phosphoferrite–reddingite group. The structure contains layers of chains of M(2)O₄(OH)(H₂O) octahedra which share edges to form dimers and connected by common edges with isolated from each other M(1)O₄(H₂O)₂ octahedra. The neighboring chains are connected to the layer through the common vertices of M(2) octahedra and octaahedral layers are linked through PO₄ tetrahedra.     

Thermal expansion of hydrated six-coordinate silicon in thaumasite,Ca<Subscript>3</Subscript>Si(OH)<Subscript>6</Subscript>(CO<Subscript>3</Subscript>)(SO<Subscript>4</Subscript>)·12H<Subscript>2</Subscript>O

Thaumasite, Ca₃Si(OH)₆(CO₃)(SO₄)12H₂O, occurs as a low-temperature secondary alteration phase in mafic igneous and metamorphic rocks, and is recognized as a product and indicator of sulfate attack in Portland cement. It is also the only mineral known to contain silicon in six-coordination with hydroxyl (OH)^? that is stable at ambient P–T conditions. Thermal expansion of the various components of this unusual structure has been determined from single-crystal X-ray structure refinements of natural thaumasite at 130 and 298 K. No phase transitions were observed over this temperature range. Cell parameters at room temperature are: a= 11.0538(6) Å, c=10.4111(8) Å and V=1101.67(10) ų, and were measured at intervals of about 50 K between 130 and 298 K, resulting in mean axial and volumetric coefficients of thermal expansion (×10^?5K^?1); α _a =1.7(1), α _c =2.1(2), and α _V =5.6(2). Although the unit cell and ^VIIICaO₈ polyhedra show significant positive thermal expansion over this temperature range, the silicate octahedron, sulfate tetrahedron, and carbonate group show zero or negative thermal expansion, with α _V (^VISiO₆) = ?0.6 ± 1.1, α _V (^IVSO₄)=?5.8 ± 1.4, and α _R (C–O)= 0.0 ± 1.8 (×10^?5 K^?1). Most of the thermal expansion is accommodated by lengthening of the R(O...O) hydrogen bond distances by on average 5σ, although the hydrogen bonds involving hydroxyl sites on ^VISi expand twice as much as those on molecular water, causing the [Ca₃Si(OH)₆(H₂O)₁₂]⁴⁺ columns to expand in diameter more than they move apart over this temperature range. The average Si–OH bond length of the six-coordinated Si atom 〈R(^VISi–OH)〉 in thaumasite is 1.783(1) Å, being about 0.02 Å (?20σ) shorter than ^VISi–OH in the dense hydrous magnesium silicate, phase D, MgSi₂H₂O₆.     

Avdoninite: New data,crystal structure and refined formula K<Subscript>2</Subscript>Cu<Subscript>5</Subscript>Cl<Subscript>8</Subscript>(OH)<Subscript>4</Subscript> · 2H<Subscript>2</Subscript>O

The paper reports new findings of avdoninite from deposits of active fumaroles in the Second Scoria Cone at the Northern Breach of the Great Fissure Tolbachik Eruption, Tolbachik Volcano, Kamchatka Peninsula, Russia. The crystal structure of the mineral has been determined for the first time, which has allowed reliable determination of its space group and unit cell dimensions, refinement of its formula K₂Cu₅-Cl₈(OH)₄ · 2H₂O, and correct indexing of its X-ray powder diffraction pattern. Avdoninite is monoclinic, space group P2₁/c, a = 11.592(2), b = 6.5509(11), c = 11.745(2) Å, β = 91.104(6)°, V = 891.8(3) ų, Z = 2. The crystal structure of this mineral has been determined on a single crystal R ₁ [F > 4σ (F)] = 0.063. It is based on sheets of copper–oxo-chloride complexes [Cu₅Cl₈(OH)₄]^2– parallel to (100). The K⁺ cation and H₂O molecules are interlayers.     

Mineral-fluid equilibria in the system CaO–MgO–SiO<Subscript>2</Subscript>–H<Subscript>2</Subscript>O–CO<Subscript>2</Subscript>–NaCl and the record of reactive fluid flow in contact metamorphic aureoles

Phase equilibria in the system CaO–MgO–SiO₂–CO₂–H₂O–NaCl are calculated to illustrate phase relations in metacarbonates over a wide-range of P–T–X[H₂O–CO₂–NaCl] conditions. Calculations are performed using the equation of state of Duan et al. (Geochim Cosmochim Acta 59:2869–2882, 1995) for H₂O–CO₂–NaCl fluids and the internally consistent data set of Gottschalk (Eur J Mineral 9:175–223, 1997) for thermodynamic properties of solids. Results are presented in isothermal-isobarical plots showing stable mineral assemblages as a function of fluid composition. It is shown that in contact-metamorphic P–T regimes the presence of very small concentrations of NaCl in the fluid causes almost all decarbonation reactions to proceed within the two fluid solvus of the H₂O–CO₂–NaCl system. Substantial flow of magma-derived fluids into marbles has been documented for many contact aureoles by shifts in stable isotope geochemistry of the host rocks and by the progress of volatile-producing mineral reactions controlled by fluid compositions. Time-integrated fluid fluxes have been estimated by combining fluid advection/dispersion models with the spatial arrangement of mineral reactions and isotopic resetting. All existing models assume that minerals react in the presence of a single phase H₂O–CO₂ fluid and do not allow for the effect that fluid immiscibility has on the flow patterns. It is shown that fluids emanating from calc-alkaline melts that crystallize at shallow depths are brines. Their salinity may vary depending mainly on pressure and fraction of crystallized melt. Infiltration-driven decarbonation reactions in the host rocks inevitably proceed at the boundaries of the two fluid solvus where the produced CO₂ is immiscible and may separate from the brine as a low salinity, low density H₂O–CO₂ fluid. Most parameters of fluid–rock interaction in contact aureoles that are derived from progress of mineral reactions and stable isotope resetting are probably incorrect because fluid phase separation is disregarded.     

Structural changes and valence states in the MgCr<Subscript>2</Subscript>O<Subscript>4</Subscript>–FeCr<Subscript>2</Subscript>O<Subscript>4</Subscript> solid solution series

The influence on the structure of Fe²⁺ Mg substitution was studied in synthetic single crystals belonging to the MgCr₂O₄–FeCr₂O₄ series produced by flux growth at 900–1200 °C in controlled atmosphere. Samples were analyzed by single-crystal X-ray diffraction, electron microprobe analyses, optical absorption-, infrared- and Mössbauer spectroscopy. The Mössbauer data show that iron occurs almost exclusively as ^IVFe²⁺. Only minor Fe³⁺ (<0.005 apfu) was observed in samples with very low total Fe. Optical absorption spectra show that chromium with few exceptions is present as a trivalent cation at the octahedral site. Additional absorption bands attributable to Cr²⁺ and Cr³⁺ at the tetrahedral site are evident in spectra of end-member magnesiochromite and solid-solution crystals with low ferrous contents. Structural parameters a₀, u and T–O increase with chromite content, while the M–O bond distance remains nearly constant, with an average value equal to 1.995(1) Å corresponding to the Cr³⁺ octahedral bond distance. The ideal trend between cell parameter, T–O bond length and Fe²⁺ content (apfu) is described by the following linear relations: a₀=8.3325(5) + 0.0443(8)Fe²⁺ (Å) and T–O=1.9645(6) + 0.033(1)Fe²⁺ (Å) Consequently, Fe²⁺ and Mg tetrahedral bond lengths are equal to 1.998(1) Å and 1.965(1) Å, respectively.     

Paragonite stability at 700°C in the presence of H<Subscript>2</Subscript>O–NaCl fluids: constraints on H<Subscript>2</Subscript>O activity and implications for high pressure metamorphism

We carried out reversed piston-cylinder experiments on the equilibrium paragonite = jadeite + kyanite + H₂O at 700°C, 1.5–2.5 GPa, in the presence of H₂O-NaCl fluids. Synthetic paragonite and jadeite and natural kyanite were used as starting materials. The experiments were performed on four different nominal starting compositions: X(H₂O)=1.0, 0.90, 0.75 and 0.62. Reaction direction and extent were determined from the weight change in H₂O in the capsule, as well as by optical and scanning electron microscopy (SEM). At X(H₂O)=1.0, the equilibrium lies between 2.25 and 2.30 GPa, in good agreement with the 2.30–2.45 GPa reversal of Holland (Contrib Miner Petrol 68:293–301, 1979). Lowering X(H₂O) decreases the pressure of paragonite breakdown to 2.10–2.20 GPa at X(H₂O)=0.90 and 1.85–1.90 GPa at X(H₂O)=0.75. The experiments at X(H₂O) = 0.62 yielded the assemblage albite + corundum at 1.60 GPa, and jadeite + kyanite at 1.70 GPa. This constrains the position of the isothermal paragonite–jadeite–kyanite–albite–corundum–H₂O invariant point in the system Na₂O–Al₂O₃–SiO₂–H₂O to be at 1.6–1.7 GPa and X(H₂O)~0.65±0.05. The data indicate that H₂O activity, a(H₂O), is 0.75–0.86, 0.55–0.58, and <0.42 at X(H₂O)=0.90, 0.75, and 0.62, respectively. These values approach X(H₂O)², and agree well with the a(H₂O) model of Aranovich and Newton (Contrib Miner Petrol 125:200–212, 1996). Our results demonstrate that the presence or absence of paragonite can be used to place limits on a(H₂O) in high-pressure metamorphic environments. For example, nearly pure jadeite and kyanite from a metapelite from the Sesia Lanzo Zone formed during the Eo-Alpine metamorphic event at 1.7–2.0 GPa, 550–650°C. The absence of paragonite requires a fluid with low a(H₂O) of 0.3–0.6, which could be due to the presence of saline brines.     

Tatarinovite Са<Subscript>3</Subscript>Al(SO<Subscript>4</Subscript>)[В(ОH)<Subscript>4</Subscript>](ОH)<Subscript>6</Subscript> · 12H<Subscript>2</Subscript>O,a new ettringite-group mineral from the Bazhenovskoe deposit,Middle Urals,Russia, and its crystal structure

A new mineral, tatarinovite, ideally Са₃Аl(SO₄)[В(ОН)₄](ОН)₆ · 12Н₂O, has been found in cavities of rhodingites at the Bazhenovskoe chrysotile asbestos deposit, Middle Urals, Russia. It occurs (1) colorless, with vitreous luster, bipyramidal crystals up to 1 mm across in cavities within massive diopside, in association with xonotlite, clinochlore, pectolite and calcite, and (2) as white granular aggregates up to 5 mm in size on grossular with pectolite, diopside, calcite, and xonotlite. The Mohs hardness is 3; perfect cleavage on (100) is observed. D _meas = 1.79(1), D _calc = 1.777 g/cm³. Tatarinovite is optically uniaxial (+), ω = 1.475(2), ε = 1.496(2). The IR spectrum contains characteristic bands of SO₄ ^2?, CO₃ ^2?, B(OH)₄ ^?, B(OH)₃, Al(OH)₆ ^3-, Si(OH)₆ ^2-, OH^–, and H₂O. The chemical composition of tatarinovite (wt %; ICP-AES; H₂O was determined by the Alimarin method; CO₂ was determined by selective sorption on askarite) is as follows: 27.40 CaO, 4.06 B₂O₃, 6.34 A1₂O₃, 0.03 Fe₂O₃, 2.43 SiO₂, 8.48 SO₃, 4.2 CO₂, 46.1 H₂O, total is 99.04. The empirical formula (calculated on the basis of 3Ca apfu) is H_31.41Ca_3.00(Al_0.76Si_0.25)_Σ1.01 · (B_0.72S_0.65C_0.59)Σ_1.96O_24.55. Tatarinovite is hexagonal, space gr. P6₃, a = 11.1110(4) Å, c = 10.6294(6) Å, V = 1136.44(9) A³, Z = 2. Its crystal chemical formula is Са₃(Аl_0.70Si_0.30) · {[SO₄]_0.34[В(ОН)₄]_0.33[СO₃]0.₂₄}{[SO₄]_0.30[В(ОН)₄]_0.34[СО₃]_0.30[В(ОН)₃]_0.06}(ОН_5·73О_0.27) · 12Н₂O. The strongest reflections of the powder X-ray diffraction pattern [d, Å (I, %) (hkl)] are 9.63 (100) (100), 5.556 (30) (110), 4.654 (14) (102), 3.841 (21) (112), 3.441 (12) (211), 2.746 (10) (302), 2.538 (12) (213). Tatarinovite was named in memory of the Russian geologist and petrologist Pavel Mikhailovich Tatarinov (1895–1976), a well-known specialist in chrysotile asbestos deposits. Type specimens have been deposited at the Fersman Mineralogical Museum of the Russian Academy of Sciences, Moscow.     

Behaviour of Fe<Subscript>4</Subscript>O<Subscript>5</Subscript>–Mg<Subscript>2</Subscript>Fe<Subscript>2</Subscript>O<Subscript>5</Subscript> solid solutions and their relation to coexisting Mg–Fe silicates and oxide phases

Experiments at high pressures and temperatures were carried out (1) to investigate the crystal-chemical behaviour of Fe₄O₅–Mg₂Fe₂O₅ solid solutions and (2) to explore the phase relations involving (Mg,Fe)₂Fe₂O₅ (denoted as O₅-phase) and Mg–Fe silicates. Multi-anvil experiments were performed at 11–20 GPa and 1100–1600 °C using different starting compositions including two that were Si-bearing. In Si-free experiments the O₅-phase coexists with Fe₂O₃, hp-(Mg,Fe)Fe₂O₄, (Mg,Fe)₃Fe₄O₉ or an unquenchable phase of different stoichiometry. Si-bearing experiments yielded phase assemblages consisting of the O₅-phase together with olivine, wadsleyite or ringwoodite, majoritic garnet or Fe³⁺-bearing phase B. However, (Mg,Fe)₂Fe₂O₅ does not incorporate Si. Electron microprobe analyses revealed that phase B incorporates significant amounts of Fe²⁺ and Fe³⁺ (at least ~?1.0 cations Fe per formula unit). Fe-L_2,3-edge energy-loss near-edge structure spectra confirm the presence of ferric iron [Fe³⁺/Fe_tot?=?~?0.41(4)] and indicate substitution according to the following charge-balanced exchange: [4]Si⁴⁺?+?[6]Mg²⁺?=?2Fe³⁺. The ability to accommodate Fe²⁺ and Fe³⁺ makes this potential “water-storing” mineral interesting since such substitutions should enlarge its stability field. The thermodynamic properties of Mg₂Fe₂O₅ have been refined, yielding H°_1bar,298?=???1981.5 kJ mol^??1. Solid solution is complete across the Fe₄O₅–Mg₂Fe₂O₅ binary. Molar volume decreases essentially linearly with increasing Mg content, consistent with ideal mixing behaviour. The partitioning of Mg and Fe²⁺ with silicates indicates that (Mg,Fe)₂Fe₂O₅ has a strong preference for Fe²⁺. Modelling of partitioning with olivine is consistent with the O₅-phase exhibiting ideal mixing behaviour. Mg–Fe²⁺ partitioning between (Mg,Fe)₂Fe₂O₅ and ringwoodite or wadsleyite is influenced by the presence of Fe³⁺ and OH incorporation in the silicate phases.     

Middendorfite,K<Subscript>3</Subscript>Na<Subscript>2</Subscript>Mn<Subscript>5</Subscript>Si<Subscript>12</Subscript>(O,OH)<Subscript>36</Subscript> · 2H<Subscript>2</Subscript>O,a new mineral species from the Khibiny pluton,Kola Peninsula

Middendorfite, a new mineral species, has been found in a hydrothermal assemblage in Hilairite hyperperalkaline pegmatite at the Kirovsky Mine, Mount Kukisvumchorr apatite deposit, Khibiny alkaline pluton, Kola Peninsula, Russia. Microcline, sodalite, cancrisilite, aegirine, calcite, natrolite, fluorite, narsarsukite, labuntsovite-Mn, mangan-neptunite, and donnayite are associated minerals. Middendorfite occurs as rhombshaped lamellar and tabular crystals up to 0.1 × 0.2 × 0.4 mm in size, which are combined in worm-and fanlike segregations up to 1 mm in size. The color is dark to bright orange, with a yellowish streak and vitreous luster. The mineral is transparent. The cleavage (001) is perfect, micalike; the fracture is scaly; flakes are flexible but not elastic. The Mohs hardness is 3 to 3.5. Density is 2.60 g/cm³ (meas.) and 2.65 g/cm³ (calc.). Middendorfite is biaxial (?), α = 1.534, β = 1.562, and γ = 1.563; 2V (meas.) = 10°. The mineral is pleochroic strongly from yellowish to colorless on X through brown on Y and to deep brown on Z. Optical orientation: X = c. The chemical composition (electron microprobe, H₂O determined with Penfield method) is as follows (wt %): 4.55 Na₂O, 10.16 K₂O, 0.11 CaO, 0.18 MgO, 24.88 MnO, 0.68 FeO, 0.15 ZnO, 0.20 Al₂O₃, 50.87 SiO₂, 0.17 TiO₂, 0.23 F, 7.73 H₂O; ?O=F₂?0.10, total is 99.81. The empirical formula calculated on the basis of (Si,Al)₁₂(O,OH,F)₃₆ is K_3.04(Na_2.07Ca_0.03)_Σ2.10(Mn_4.95Fe_0.13Mg_0.06Ti_0.03Zn_0.03)_Σ5.20(Si_11.94Al_0.06)_Σ12O_27.57(OH)_8.26F_0.17 · 1.92H₂O. The simplified formula is K₃Na₂Mn₅Si₁₂(O,OH)₃₆ · 2H₂O. Middenforite is monoclinic, space group: P2₁/m or P2₁. The unit cell dimensions are a = 12.55, b = 5.721, c = 26.86 Å; β = 114.04°, V = 1761 ų, Z = 2. The strongest lines in the X-ray powder pattern [d, Å, (I)(hkl)] are: 12.28(100)(002), 4.31(81)(11\(\overline 4 \)), 3.555(62)(301, 212), 3.063(52)(008, 31\(\overline 6 \)), 2.840(90)(312, 021, 30\(\overline 9 \)), 2.634(88)(21\(\overline 9 \), 1.0.\(\overline 1 \)0, 12\(\overline 4 \)), 2.366(76)(22\(\overline 6 \), 3.1.\(\overline 1 \)0, 32\(\overline 3 \)), 2.109(54)(42–33, 42–44, 51\(\overline 9 \), 414), 1.669(64)(2.2.\(\overline 1 \)3, 3.2.\(\overline 1 \)3, 62\(\overline 3 \), 6.1.\(\overline 1 \)3), 1.614(56)(5.0.\(\overline 1 \)6, 137, 333, 71\(\overline 1 \)). The infrared spectrum is given. Middendorfite is a phyllosilicate related to bannisterite, parsenttensite, and the minerals of the ganophyllite and stilpnomelane groups. The new mineral is named in memory of A.F. von Middendorff (1815–1894), an outstanding scientist, who carried out the first mineralogical investigations in the Khibiny pluton. The type material of middenforite has been deposited at the Fersman Mineralogical Museum, Russian Academy of Sciences, Moscow.     

High-pressure X-ray diffraction and Raman spectroscopy of CaFe<Subscript>2</Subscript>O<Subscript>4</Subscript>-type β-CaCr<Subscript>2</Subscript>O<Subscript>4</Subscript>

In situ high-pressure synchrotron X-ray diffraction and Raman spectroscopic studies of orthorhombic CaFe₂O₄-type β-CaCr₂O₄ chromite were carried out up to 16.2 and 32.0 GPa at room temperature using multi-anvil apparatus and diamond anvil cell, respectively. No phase transition was observed in this study. Fitting a third-order Birch–Murnaghan equation of state to the P–V data yields a zero-pressure volume of V ₀ = 286.8(1) ų, an isothermal bulk modulus of K ₀ = 183(5) GPa and the first pressure derivative of isothermal bulk modulus K ₀′ = 4.1(8). Analyses of axial compressibilities show anisotropic elasticity for β-CaCr₂O₄ since the a-axis is more compressible than the b- and c-axis. Based on the obtained and previous results, the compressibility of several CaFe₂O₄-type phases was compared. The high-pressure Raman spectra of β-CaCr₂O₄ were analyzed to determine the pressure dependences and mode Grüneisen parameters of Raman-active bands. The thermal Grüneisen parameter of β-CaCr₂O₄ is determined to be 0.93(2), which is smaller than those of CaFe₂O₄-type CaAl₂O₄ and MgAl₂O₄.