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.     

Experiments on the kinetics of partial melting of a leucogranite at 200 MPa H<Subscript>2</Subscript>O and 690–800°C: compositional variability of melts during the onset of H<Subscript>2</Subscript>O-saturated crustal anatexis

We have experimentally investigated the kinetics of melting of an aplitic leucogranite (quartz+sodic plagioclase of ≈Ab₉₀+K-feldspar+traces of biotite) at 690, 740, and 800°C, all at 200 MPa H₂O. Leucogranite cylinders, 3.5 mm in diameter and 7 mm in length, were run in the presence of excess H₂O using cold-seal pressure vessels for 11–2,925 h. At 690 and 740°C and any experimental time, and 800°C and short run times, silicate glass (melt at run conditions) occurs as interconnected films along most of the mineral boundaries and in fractures, with the predominant volume occurring along quartz/feldspars boundaries and quartz/plagioclase/K-feldspar triple junctions. Glass film thickness is roughly constant throughout a given experimental charge and increases with experimental temperature and run duration. The results indicate that H₂O-saturated partial melting of a quartzo-feldspathic protolith will produce an interconnected melt phase even at very low degrees (<5 vol%) of partial melting. Crystal grain boundaries are therefore completely occluded with melt films even at the lowest degrees of partial melting, resulting in a change in the mechanism of mass transport through the rock from advection of aqueous vapor to diffusion through silicate melt. At 690 and 740°C the compositions of glasses are homogeneous and (at both temperatures) close to, but not on, the H₂O-saturated 200 MPa haplogranite eutectic; glass compositions do not change with run duration. At 800°C glasses are heterogeneous and plot away from the minimum, although their molar ratios ASI (=mol Al₂O₃/CaO+Na₂O+K₂O) and Al/Na are constant throughout the entire charge at any experimental time. Glass compositions within individual 800°C experiments form linear trends in (wt%) normative quartz–albite–orthoclase space. The linear trends are oriented perpendicular to the 200 MPa H₂O haplogranite cotectic line, reflecting nearly constant albite/orthoclase ratio versus variable quartz/feldspar ratio, and have endpoints between the 800°C isotherms on the quartz and feldspar liquidus surfaces. With increasing experimental duration the trends migrate from the potassic side of the minimum toward the bulk rock composition located on the sodic side, due to more rapid (and complete) dissolution of K-feldspar relative to plagioclase. The results indicate that partial melting at or slightly above the solidus (690–740°C) is interface reaction-controlled, and produces disequilibrium melts of near-minimum composition that persist metastably for up to at least 3 months. Relict feldspars show no change in composition or texture, and equilibration between melt and feldspars might take from a few to tens of millions of years. Partial melting at temperatures well above the solidus (800°C) produces heterogeneous, disequilibrium liquids whose compositions are determined by the diffusive transport properties of the melt and local equilibrium with neighboring mineral phases. Feldspars recrystallize and change composition rapidly. Partial melting and equilibration between liquids and feldspars might take from a few to tens of years (H₂O-saturated conditions) at these temperatures well above the solidus.     

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.     

Liquid immiscibility in the system NaF–H<Subscript>2</Subscript>O and microlite solubility at 800°C

The NaF effect on microlite solubility at 800°C and 170, 200, and 230 MPa is studied experimentally. The immiscibility boundaries and compositions of fluid phases L₁ and L₂ are defined in the system NaF–H₂O at 800°C. It is established that microlite solubility increase in the L₁ phase, as compared with a homogeneous solution, is explained by the appearance in the L₁ phase of “free” HF in an amount of 0.025 ± 0.003 mol kg^–1 H₂O. The model of “acidification” L₁ and “alkalizing” L₂ is supposed.     

Experimental Study of the SiO<Subscript>2</Subscript>–H<Subscript>2</Subscript>O–KF–KCl–NaF System at 700–800°C and 1–2 kbar Based on Synthetic Fluid Inclusions in Quartz

The phase state of the fluid in the H₂O–KF ± KCl ± NaF system is studied in the presence of quartz for an experimental assay of the mutual influence of various salts of the fluid-forming mixture on heterogeneous fluid equilibria. The fluid inclusions were synthesized in quartz by the fracture healing method from solutions with KF + KCl and KF + NaF mixtures at 1 or 2 kbar and 700, 750, or 800°C. The results of the fluid inclusion study indicate a heterogeneous state of the fluid and variation in the fluid composition during experiments as a result of its interaction with quartz. The increase in temperature and pressure, as well as variation in the proportions of the salt contents in the fluid-forming mixture, changed the course of chemical reactions. After all the experiments, a glassy phase was observed in some types of inclusions. It is known that aqueous KF or KCl solutions, the solubility of which increases during heating, are characterized by phase equilibria of systems of the first type (Valyashko, 1990), when liquid and vapor are equilibrated for a heterogeneous state of the fluid. In this case, some inclusions should homogenize to vapor. However, no similar inclusions were observed in contrast to denser fluid phases (liquids), which are typical of the upper heterogeneous area of systems of the second (P–Q) type. Some inclusions host solid phases, the solubility of which decreases as the temperature increases. The results of experiments in the presence of KF + NaF solutions showed that the amount of inclusions of heterogeneous entrapment increases at higher temperatures simultaneously with a decrease in the H₂O content of the glassy phase.     

Behaviour at high pressure of Rb<Subscript>7</Subscript>NaGa<Subscript>8</Subscript>Si<Subscript>12</Subscript>O<Subscript>40</Subscript>·3H<Subscript>2</Subscript>O (a zeolite with EDI topology): a combined experimental–computational study

The high-pressure behaviour and the P-induced structural evolution of a synthetic zeolite Rb₇NaGa₈Si₁₂O₄₀·3H₂O (with edingtonite-type structure) were investigated both by in situ synchrotron powder diffraction (with a diamond anvil cell and the methanol:ethanol:water = 16:3:1 mixture as pressure-transmitting fluid) up to 3.27 GPa and by ab initio first-principles computational modelling. No evidence of phase transition or penetration of P-fluid molecules was observed within the P-range investigated. The isothermal equation of state was determined; V ₀ and K _T0 refined with a second-order Birch–Murnaghan equation of state are V ₀ = 1311.3(2) ų and K _T0 = 29.8(7) GPa. The main deformation mechanism (at the atomic scale) in response to the applied pressure is represented by the cooperative rotation of the secondary building units (SBU) about their chain axis (i.e. [001]). The direct consequence of SBU anti-rotation on the zeolitic channels parallel to [001] is the increase in pore ellipticity with pressure, in response to the extension of the major axis and to the contraction of the minor axis of the elliptical channel parallel to [001]. The effect of the applied pressure on the bonding configuration of the extra-framework content is only secondary. A comparison between the P-induced main deformation mechanisms observed in Rb₇NaGa₈Si₁₂O₄₀·3H₂O and those previously found in natural fibrous zeolites is made.     

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.     

Measurements and calculations of solid-liquid equilibria in the ternary systems NaBr–Na<Subscript>2</Subscript>SO<Subscript>4</Subscript>–H<Subscript>2</Subscript>O and KBr–K<Subscript>2</Subscript>SO<Subscript>4</Subscript>–H<Subscript>2</Subscript>O at 348 K

According to the compositions of the underground brine resources in the west of Sichuan Basin, solubilities of the ternary systems NaBr–Na₂SO₄–H₂O and KBr–K₂SO₄–H₂O were investigated by isothermal method at 348 K. The equilibrium solid phases, solubilities of salts, and densities of the solutions were determined. On the basis of the experimental data, the phase diagrams and the density-composition diagrams were plotted. In the two ternary systems, the phase diagrams consist of two univariant curves, one invariant point and two crystallization fields. Neither solid solution nor double salts were found. The equilibrium solid phases in the ternary system NaBr–Na₂SO₄–H₂O are NaBr and Na₂SO₄, and those in the ternary system KBr–K₂SO₄–H₂O are KBr and K₂SO₄. Using the solubilities data of the two ternary subsystems at 348 K, mixing ion-interaction parameters of Pitzer’s equation θxxx, Ψxxx and Ψxxx were fitted by multiple linear regression method. Based on the chemical model of Pitzer’s electrolyte solution theory, the solubilities of phase equilibria in the two ternary systems NaBr–Na₂SO₄–H₂O and KBr–K₂SO₄–H₂O were calculated with corresponding parameters. The calculation diagrams were plotted. The results showed that the calculated values have a good agreement with experimental data.     

Deliquescence of NaCl–NaNO<Subscript>3</Subscript>, KNO<Subscript>3</Subscript>–NaNO<Subscript>3</Subscript>, and NaCl–KNO<Subscript>3</Subscript>salt mixtures from 90 to 120°C

We conducted reversed deliquescence experiments in saturated NaCl–NaNO₃–H₂O, KNO₃–NaNO₃–H₂O, and NaCl–KNO₃–H₂O systems from 90 to 120°C as a function of relative humidity and solution composition. NaCl, NaNO₃, and KNO₃ represent members of dust salt assemblages that are likely to deliquesce and form concentrated brines on high-level radioactive waste package surfaces in a repository environment at Yucca Mountain, NV. Discrepancy between model prediction and experiment can be as high as 8% for relative humidity and 50% for dissolved ion concentration. The discrepancy is attributed primarily to the use of 25°C models for Cl–NO₃ and K–NO₃ ion interactions in the current Yucca Mountain Project high-temperature Pitzer model to describe the nonideal behavior of these highly concentrated solutions.     

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.     

Avdoninite,K<Subscript>2</Subscript>Cu<Subscript>5</Subscript>Cl<Subscript>8</Subscript>(OH)<Subscript>4</Subscript> · H<Subscript>2</Subscript>O,a new mineral species from volcanic exhalations and the technogenic zone at volcanic-hosted massive sulfide deposits

Avdoninite, a new mineral species, has been found together with euchlorite, paratacamite, atacamite, belloite, and langbeinite hosted in exhalation sediments of the Yadovitaya fumarole in the Second Cinder Cone at the Northern Breach of the Great Fissure Tolbachik Eruption, Tolbachik volcano, Kamchatka Peninsula, Russia. Avdoninite occurs as imperfect, short prismatic and thick tabular crystals up to 0.2 mm long, with (001) and (100) forms, crystal aggregates, and pseudomorphs (together with atacamite) after melanothallite observed. The new mineral is brittle, with the Mohs hardness 3 (for aggregates). Density is 3.03 g/cm³ (meas.) and 3.066 g/cm³ (calc.). Avdoninite is biaxial and optically neutral, with α = 1.669, β = 1.688, γ = 1.707, 2V = ?90°. Dispersion is not observed. Optical orientation: Y = c, X = b? Pleochroism is absent. The infrared spectrum suggests the presence of water molecules in avdoninite. Electron microprobe chemical analysis has given (wt %) K₂O 11.94 (±0.4), CuO 51.43 (±0.7), Cl 37.07 (±0.6), H₂O (determined by the Penfield method) 6.9, ?O=Cl₂ ?8.37, total 98.97. The empirical formula is K_1.96Cu_5.00Cl_8.09(OH)_3.87. · 1.03H₂O. Avdoninite is monoclinic, space group P2/m, P2, or Pm; a = 24.34(2) Å, b = 5.878(4) Å, c = 11.626(5) Å, β = 93.3(1)°, V = 1660.6(20) ų, Z = 4. The compatibility index is good: 1 ? K _p/K _c = 0.056 for D _calc and 0.044 for D _meas. The strongest lines in the X-ray powder diffraction pattern (d, Å (I, %) (hkl)) are 11.63(100)(001), 5.88(20)(010), 5.80(27)(002), 5.73(17)(\(\overline 1 \)02), 2.518(19)(21\(\overline 4 \)), 2.321(17)(005). Avdoninite is identical to a technogenic analogue previously described from the Blyava volcanic-hosted massive sulfide deposit, Orenburg oblast, Russia. The new mineral is named after Vladimir Nikolaevich Avdonin (born 1925), a senior researcher of the Ural Geological Museum of the Ural State Mining University. The type material of avdoninite from Kamchatka is deposited in the Mineralogical Museum of the Department of Mineralogy, St. Petersburg State University, St. Petersburg, Russia. The registration number is 19175.     

Contrasting interactions of sodium and potassium with H<Subscript>2</Subscript>O in haplogranitic liquids and glasses at 200 MPa from hydration–diffusion experiments

This study examines hydration–diffusion in the metaluminous haplogranite system at 200 MPa H₂O and 800–300°C. At 800°C hydration is accompanied by melting and uphill diffusion of sodium from anhydrous glass toward the region of hydration and melting, whereas potassium diffuses away from the hydration front and into anhydrous glass. Silicon and aluminum are simply diluted upon hydration. There is no change in molecular Al/(Na + K) throughout the entire hydration-diffusion aureole and, therefore, (1) there is no loss of alkalis to the vapor, and (2) K migrates to replace Na in order to maintain local charge balance required by ^IVAl. Alkali diffusion occurs over a viscosity contrast from 10^4.1 Pa s in hydrous liquid to 10^11.8–10^13.5 Pa s in anhydrous glass. From these results, we interpret that: (1) Na is structurally or energetically favored over K as a charge-balancing cation for ^IVAl in hydrous granitic liquids, whereas the opposite behavior has been observed for anhydrous melts, and (2) the diffusion of alkalis through silicate melts is largely independent of viscosity. Results from 600°C are similar to those at 800°C, but hydration at 300°C involves a loss of Na and concomitant increase in molar Al/(Na + K) in the hydration zone due to hydrogen-alkali exchange between fluid and glass. Hydration behavior at 400°C is transitional between those at 300°C and 600°C, suggesting that the change in hydration mechanism occurs near the glass transition.     

X-ray single-crystal and Raman study of (Na<Subscript>0.86</Subscript>Mg<Subscript>0.14</Subscript>)(Mg<Subscript>0.57</Subscript>Ti<Subscript>0.43</Subscript>)Si<Subscript>2</Subscript>O<Subscript>6</Subscript>, a new pyroxene synthesized at 7 GPa and 1700 °C

A new pyroxene with formula (Na_0.86Mg_0.14)(Mg_0.57Ti_0.43)Si₂O₆, synthesized in a high-pressure toroidal ‘anvil-with-hole’ apparatus at P = 7 GPa and T = 1700 °C, was characterized by X-ray single-crystal diffraction and Raman spectroscopy. The compound was found to be monoclinic (R1 = 2.56 %), space group C2/c, with lattice parameters a = 9.687(2), b = 8.814(1), c = 5.290(1) Å, β = 107.853(2)°, V = 430.08(1) ų. The coexistence of Mg and Ti⁴⁺ at the M1 site does not induce strong modifications either to the M1 site or to the adjacent M2 site. The Raman spectrum of synthetic Na–Ti-pyroxene was obtained for the first time and compared with that of Mg₂Si₂O₆ (with very low concentrations of Na and Ti). The structural characterization of the Na–Ti–Mg-pyroxene is important, because the study of its thermodynamic constants provides new constraints on thermobarometry of the upper mantle assemblages.     

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.