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.     

Fluid Characteristics and Evolution of the Zhawulong Granitic Pegmatite Lithium Deposit in the Ganzi‐Songpan Region,Southwestern China

The Zhawulong granitic pegmatite lithium deposit is located in the Ganzi-Songpan orogenic belt. Fluid inclusions in spodumene and coexisting quartz were studied to understand the cooling path and evolution of fluid within albite–spodumene pegmatite. There are three distinguishable types of fluid inclusions: crystal-rich, CO2–NaCl–H2O, and NaCl–H2O. At more than 500°C and 350~480 MPa, crystal-rich fluid inclusions were captured during the pegmatitic magma-hydrothermal transition stage, characterized by a dense hydrous alkali borosilicate fluid with a carbonate component. Between 412°C and 278°C, CO2–NaCl–H2Ofluid inclusions developed in spodumene (I) and quartz (II) with a low salinity (3.3–11.9 wt%NaCl equivalent) and a high volatile content, which represent the boundary between the transition stage and the hydrothermal stage. The subsequentNaCl–H2Ofluid inclusions from the hydrothermal stage, between 189°C and 302°C, have a low salinity (1.1–13.9 wt%NaCl equivalent). The various types of fluid inclusions reveal the P–T conditions of pegmatite formation, which marks the transition process from magmatic to hydrothermal. The ore-forming fluids from the Zhawulong deposit have many of the same characteristics as those from the Jiajika lithium deposit. The ore-forming fluid provided not only materials for crystallization of rare metal minerals, such as spodumene and beryl, but also the ideal conditions forthe growth of ore minerals. Therefore, this area has favorable conditions for lithium enrichment and excellent prospecting potential.     

The Formation of Chrysoberyl in Metamorphosed Pegmatites

Mineral assemblages in pegmatite samples from Kolsva, Swedenand Marikov, Czechoslovakia show that chrysoberyl is alwaysaccompanied by quartz, and is a breakdown product of primarypegmatitic beryl. Textures and the mineral-forming process forthe Kolsva pegmatite are explained by the reactions beryl +K-feldspar + H+ = chrysoberyl + quartz + SiO_{2, aq} + K⁺ + H₂Oor alternatively beryl —K—feldspar + H₂O = chrysoberyl+ quartz + melt. Mineral assemblages from mica-rich parts ofthe pegmatite include sillimanite—K—feldspar, muscovite—K—feldspar—sillimanite,and annite—magnetite—spinel—sillimanite—garnet.Details about the composition and the textural relationshipsof these minerals are given; they indicate a post-pegmatiticmetamorphic event at P—T conditions near to the anatecticregime. The samples from Marikov show textures, which are explainedby the reactions beryl + albite + H⁺ = chrysoberyl + quartz+ Na⁺ + H₂O or alternatively beryl + albite + H₂O = chrysoberyl+ quartz + melt. Breakdown of muscovite produces sillimaniteaccording to the reactions beryl + albite + muscovite + H⁺ =chrysoberyl + quartz + sillimanite + Na⁺ + K⁺ + H₂O or alternativelyberyl + albite + muscovite + H₂O = chrysoberyl + quartz + sillimanite+ melt. Similar reaction textures and mineral assemblages were foundin other chrysoberyl-bearing pegmatites (Maroankora, Madagascar;Helsinki, Finland; Haddam, Greenfield, Greenwood, U.S.A.). Hydrothermal experiments located the reaction beryl + alkalifeldspar + H₂O = chrysoberyl + phenakite + melt at P—Tconditions between the K—feldspar—quartz—H₂Osolidus and the K—feldspar—albite—quartz-H₂Osolidus. It is concluded that the formation of Al-rich minerals likechrysoberyl and sillimanite in pegmatites is due to a post-pegmatiticevent at high P—T conditions. The question as to whichof the alternative set of reactions is more likely, the ionicequilibria or the anatectic chrysoberyl formation, must be leftopen. The previous hypothesis of a desilification of a pegmatitewhich intruded into SiO₂-poor country rocks, or of the assimilationof Al₂O₃-rich country rocks, cannot explain the mineral assemblagesof the two pegmatites.     

The measurement of sulfate mineral solubilities in the Na-K-Ca-Cl-SO4-H2O system at temperatures of 100, 150 and 200°C

At T > 100°C development of thermodynamic models suffers from missing experimental data, particularly for solubilities of sulfate minerals in mixed solutions. Solubilities in Na⁺-K⁺-Ca²⁺-Cl⁻-SO₄²⁻/H₂O subsystems were investigated at 150, 200°C and at selected compositions at 100°C. The apparatus used to examine solid-liquid phase equilibria under hydrothermal conditions has been described.In the system NaCl-CaSO₄-H₂O the missing anhydrite (CaSO₄) solubilities at high NaCl concentrations up to halite saturation have been determined. In the system Na₂SO₄-CaSO₄-H₂O the observed glauberite (Na₂SO₄ · CaSO₄) solubility is higher than that predicted by the high temperature model of Greenberg and Møller (1989), especially at 200°C. At high salt concentrations, solubilities of both anhydrite and glauberite increase with increasing temperature. Stability fields of the minerals syngenite (K₂SO₄ · CaSO₄ · H₂O) and goergeyite (K₂SO₄ · 5 CaSO₄ · H₂O) were determined, and a new phase was found at 200°C in the K₂SO₄-CaSO₄-H₂O system. Chemical and single crystal structure analysis give the formula K₂SO₄ · CaSO₄. The structure is isostructural with palmierite (K₂SO₄ · PbSO₄). The glaserite (“3 K₂SO₄ · Na₂SO₄”) appears as solid solution in the system Na₂SO₄-K₂SO₄-H₂O. Its solubility and stoichiometry was determined as a function of solution composition.     

Composition,Structure, and Conditions of Formation of Fluorine-Bearing Sodalite: Experimental Evidence

Fluoro-sodalite was synthesized for the first time at temperatures of 400–800°C and H₂O pressures of 1–2 kbar in the Si–Al–Na–H–O–F system. X-ray diffraction and infrared spectroscopic investigations showed that fluorine is incorporated in the sodalite structure as anionic octahedral groups, [AlF₆]^3–, the number of which can vary from 0 to 1. Correspondingly, the end-members of the F-sodalite series are Na₇(H₂O)₈[Si₅Al₇O₂₄] and Na₈(AlF₆)(H₂O)₄[Si₇Al₅O₂₄]. Depending on the composition of the system, F-sodalite associates at 500–650°C with nepheline, albite, cryolite, and villiaumite, which are joined by analcime below 500°C and aluminosilicate melt above 650°C. Fluorine-bearing sulfate–chlorine-sodalite was found for the first time in a pegmatite sample from the Lovozero massif. The highest fraction of the fluorine end-member in natural sodalite is 0.2. The incorporation of F into the sodalite structure requires much more energy compared with Cl^– and SO ₄ ^2- , because it is accompanied by a structural rearrangement and a transition from tetrahedral Al to octahedral Al.     

The effect of medium chemistry on the solubility and morphology of brushite crystals

An experimental study of the particulars of the solubility and crystallization of brushite Ca(HPO₄) · 2H₂O from aqueous solution in conditions of a variable pH (6.0–3.0) and the contents of impurity ions (K⁺, Na⁺, NH ₄ ⁺ , Mg²⁺, SO ₄ ^2? , CO ₃ ^2? ) has been conducted. It is established that brushite solubility markedly rises with a decrease in pH from 6 to 3 and slightly rises with an increase in Mg²⁺ and SO ₄ ^2? concentrations. The enrichment in K⁺, Na⁺, and NH ₄ ⁺ does not affect brushite solubility. The changeable chemistry of the medium results in variation of the synthetic crystal habit, from rhombic tabular to thickened prismatic crystals.     

Phase Chemistry Study of the Zabuye Salt Lake Brine: Isothermal Evaporation at 15°C and 25°C

Zabuye Salt Lake in Tibet, China is a carbonate-type salt lake, which has some unique characteristics that make it different from other types of salt lakes. The lake is at the latter period in its evolution and contains liquid and solid resources. Its brine is rich in Li, B, K and other useful minor elements that are of great economic value. We studied the concentration behavior of these elements and the crystallization paths of salts during isothermal evaporation of brine at 15°C and 25°C. The crystallization sequence of the primary salts from the brine at 25°C is halite (NaCl) → aphthitalite (3K2SO4·Na2SO4) → zabuyelite (Li2CO3)→ trona (Na2CO3·NaHCO3·2H2O) → thermonatrite (Na2CO3·H2O) → sylvite (KCl), while the sequence is halite (NaCl) → sylvite (KCl) → trona (Na2CO3·NaHCO3·2H2O) → zabuyelite (Li2CO3) → thermonatrite (Na2CO3·H2O) → aphthitalite (3K2SO4·Na2SO4) at 15°C. They are in accordance with the metastable phase diagram of the Na+, K+-Cl?, CO32?, SO42?-H2O quinary system at 25°C, except for Na2CO3·7H2O which is replaced by trona and thermonatrite. In the 25°C experiment, zabuyelite (Li2CO3) was precipitated in the early stage because Li2CO3 is supersaturated in the brine at 25°C, in contrast with that at 15°C, it precipitated in the later stage. Potash was precipitated in the middle and late stages in both experiments, while boron was concentrated in the early and middle stages and precipitated in the late stage.     

湖南尖峰岭稀有金属花岗岩地球化学特征及成矿作用

湖南尖峰岭矿床是一个典型的花岗岩型Li、Nb和Ta稀有金属矿床,为研究花岗岩成矿作用以及指导湘南地区稀有金属找矿工作,采用XRF、ICP-MS和ISE法分析了与成矿有关的黑云母花岗岩、钠长石花岗岩及云英岩的中主量、微量元素和挥发分。结果表明:钠长石花岗岩和云英岩中的SiO_2(70.6%~84.85%)和挥发分F(2.43%~3.74%)质量分数高,富Al_2O_3(9.36%~22.99%),且A/CNK1.0,为过铝质岩石,全碱(w(Na_2O+K_2O)=1.51%~7.52%)和w(CaO)(0.1%~3.44%)变化大,w(Fe_2O_3)、w(MgO)、w(TiO_2)、w(MnO)、w(P_2O_5)较低;稀土元素组成具显著的Eu负异常和"M"型四分组效应,强烈富集Rb、Th、U、Nb、Ta元素,亏损Ba、Sr、Ti元素。花岗岩地球化学特征显示在演化过程中经历了高程度分异演化作用和岩浆不混溶作用,其挥发分F对稀有元素有明显的富集作用,并制约着熔体/流体体系的地球化学行为及其成矿效应。钠长石花岗岩和云英岩的稀有金属富集成矿受到岩浆不混溶作用、水岩反应、风化淋滤作用的共同控制。     

Crystallization behavior of NaNO3–Na2SO4 salt mixtures in sandstone and comparison to single salt behavior

We report on the crystallization behavior and the salt weathering potential in natural rock and porous stone of single salts (NaNO₃, Na₂SO₄) and salt mixtures in the ternary NaNO₃–Na₂SO₄–H₂O system. Geochemical modeling of the phase diagram of the ternary NaNO₃–Na₂SO₄–H₂O system was used to determine the equilibrium pathways during wetting (or deliquescence) of incongruently soluble minerals and evaporation of mixed electrolyte solutions. Experiments were carried out in order to study the phase changes during dissolution either induced by deliquescence or by the addition of liquid water. In situ Raman spectroscopy was used to study the phase transformations during wetting of pure Na₂SO₄ (thenardite) and of Na₃NO₃SO₄·H₂O (darapskite). In both experiments crystallization of Na₂SO₄·10H₂O (mirabilite) from highly supersaturated solutions is demonstrated confirming the high salt weathering potential of thenardite and darapskite wetting. In order to study the damage potential of darapskite experimentally, wetting–drying experiments with porous sandstone with the two single salts (Na₂SO₄, NaNO₃) and two NaNO₃–Na₂SO₄ salt mixtures were carried out. Different destructive and non-destructive techniques were tested for damage monitoring. NaNO₃ was found to be the least damaging salt and Na₂SO₄ is the most damaging one. The classification of the two salt mixtures was less obvious.     

Crystallization behavior of Na2SO4–MgSO4 salt mixtures in sandstone and comparison to single salt behavior

We report on the crystallization behavior and the salt weathering potential of Na₂SO₄, MgSO₄ and an equimolar mixture of these salts in natural rock and porous stone. Geochemical modeling of the phase diagram of the ternary Na₂SO₄–MgSO₄–H₂O system was used to determine the equilibrium pathways during wetting (or deliquescence) of incongruently soluble minerals and evaporation of mixed electrolyte solutions. Model calculations include stable and metastable solubilities of the various hydrated states of the single salts and the double salts Na₂Mg(SO₄)₂·4H₂O (bloedite), Na₂Mg(SO₄)₂·5H₂O (konyaite), Na₁₂Mg₇(SO₄)₁₃·15H₂O (loeweite) and Na₆Mg(SO₄)₄ (vanthoffite). In situ Raman spectroscopy was used to study the phase transformations during wetting of pure MgSO₄·H₂O (kieserite) and of the incongruently soluble salts bloedite and konyaite. Dissolution of kieserite leads to high supersaturation resulting in crystallization of higher hydrated phases, i.e. MgSO₄·7H₂O (epsomite) and MgSO₄·6H₂O (hexahydrite). This confirms the high damage potential of magnesium sulfate in salt damage of building materials. The dissolution of the incongruently soluble double salts leads to supersaturation with respect to Na₂SO₄·10H₂O (mirabilite). However, the supersaturation was insufficient for mirabilite nucleation. The damage potential of the two single salts and an equimolar salt mixture was tested in wetting–drying experiments with porous sandstone. While the high damage potential of the single salts is confirmed, it appears that the supersaturation achieved during wetting of the double salts at room temperature is not sufficient to generate high crystallization pressures. In contrast, very high damage potentials of the double salts were found in experiments at low temperature under high salt load.1     

Geochemical features of ore fluid for gold deposits related to alkaline rocks in China

Fluid inclusion studies of 5 gold deposits connected with alkaline rocks show that quartz separated from auriferous quartz veins contains abundant three-phase CO2-NaCl-H2O inclusions and two-phase CO2-dominated ones,measuring 5-20um in diameter,Homogenization temperatures of the fluid inclusions are mostly within the range of 150-300℃,and the salinities,mainly 0.2wt%-12 wt%(NaCl),Gold mineralizations occurred at depths of 1.4-2.8km,The most striking character of fluid composition is that among the cations,Na^ in dominant,followed by K^ ,Ca^2 ,among the anions,Cl^- is slightly higher than SO4^2-,In the evaporate,H2O is dominant,followed by CO2,The pH values are mainly within the range of 6.5-8.5,indicating that the ore-forming solutions are alkaline in nature.The hydrogen and oxygen isotopic ratios indicate that the ore fluid is composed mainly of magmatic water.With the dropping of temperature in the ore fluid,the contents of CO2 decreased while the salinity increased.The relations between Au and other components of the ore fluid are discussed in the paper,and it is concluded that in these deposits,Chlorides,H2S,SiO2,CO2,etc.in the fluid all are involved in the migration and concentration of Au.     

Experimental metasomatism of monazite and xenotime: mineral stability, REE mobility and fluid composition

In this study a Th-bearing monazite from a Brazil beach sand, a low Th monazite from a Malawi carbonatite, and a xenotime from a pegmatite in northern Pakistan were experimentally metasomatised in a series of common metamorphic and igneous fluids at 600°C/500 MPa and 900°C/1000 MPa. Fluids included H₂O, NaCl, and KCl brines, CaF₂?+?H₂O, 1m and 2m HCl, 1m and 2m H₂SO₄, 1m NaOH, and Na₂Si₂O₅?+?H₂O. The monazite show a variety of responses to the fluids ranging from no reaction (KCl?+?H₂O) to small compositional changes and partial replacement of the monazite grain rim by Th-enriched monazite in the NaOH and (Na₂Si₂O₅?+?H₂O) experiments respectively. The other acid and brine fluids induced varying degrees of partial dissolution in the monazite and xenotime, but no compositional alteration. Partial replacement of monazite grain rims by Th-enriched monazite occurred only in the alkaline fluids as the result of a coupled dissolution-reprecipitation process.     

西藏驱龙斑岩铜钼矿地球化学异常特征

驱龙铜矿发育多元素的岩石地球化学异常.成矿元素Cu、Mo、(Ag)异常强、规模大,异常与矿化区一致;伴生元素Au、Bi、Pb、As、Sb、Hg异常在Cu、Mo异常边部并套合产出的B Co、Ni Mn Zn的异常主要分布铜钼矿化带外侧.Na₂O在矿化区显示负异常,K₂O为正异常.从异常元素组合、水平分带性和贫Na₂O、富K₂O的成矿环境表明,矿床属典型的斑岩型铜矿地球化学特征,并受到了强烈的剥蚀.     

Geology,Fluid Inclusion Characteristics and H–O–C Isotopes of Large Lijiagou Pegmatite Spodumene Deposit in Songpan–Garze Fold Belt,Eastern Tibet: Implications for ore Genesis

The large, newly discovered Lijiagou pegmatite spodumene deposit, is located southeast of the Ke'eryin pegmatite ore field, in the central Songpan–Garze Fold Belt (SGFB), Eastern Tibet. The Lijiagou albite spodumene pegmatites are unzoned, granite‐pegmatites of the subtype LCT (Lithium, Cesium, and Tantalum) and consist of medium‐ to coarse‐grained spodumene, lepidolite, microcline, albite, quartz, muscovite, and accessory amounts of beryl, cassiterite, columbite–tantalite and zircon. Secondary fluid inclusions in quartz and spodumene include two‐phase aqueous inclusions (V + L), mono‐phase vapor inclusions (V); three‐phase CO₂‐rich CO₂–H₂O inclusions (CO₂ + V + L) and less abundant liquid inclusions (L). The homogenization temperature of the fluid inclusions are low (257.3 to 204.3°C in early stage, 250.3 to 199.6°C in middle stage, 218.7 to 200.6°C in late stage). Fluid inclusions were formed during the long cooling period from the temperature of the pegmatite emplacement. Liquid–vapor–gas boiling was extensive during the middle and late stages. The salinity of the corresponding stages are 15.4 to 13.0 wt.% NaCl equiv., 12.5 to 9.1 wt.% NaCl equiv. and 9.8 to 7.8 wt.% NaCl equiv., respectively. δ¹⁸O values of fluid are 7.2 to 5.2‰, 5.6 to 3.9‰ and 2.7 to −0.2‰ from early to late stages; and δD range from −75.1 to −76.8‰, −59.0 to −73.5‰ and −61.6 to −85.5‰ respectively. The δ¹³C of CO₂ values are −5.6 to −6.6‰, −8.5 to −19.9‰, −11.8 to −18.7‰ from early to late stages, suggesting that CO₂ in the fluids were probably sourced from a magmatic system, possibly with some mixing of CO₂ dissolved in groundwater. δD and δ¹⁸O values of fluid indicate that the fluids were originally magmatic water and mixed with some meteoric water in late stage. The magma evolution sequence in the Ke'eryin orefield, from the central two‐mica granite through the Lijiagou deposit out to the distal pegmatites, with the ages gradually decreasing, indicates that the Ke'eryin complex rocks are the product of multistage magmatic activity. The large Lijiagou spodumene deposit is a typical magmatic, fractional crystallization related pegmatite deposit.     

Grands gisements d'albite dans le massif métamorphique de Menderes (Turquie occidentale)

Albite deposits of western Turkey occur within gneiss in the basal part of the Menderes Metamorphic Massif. The most important deposits are located along the Karadere mineralization zone, within an anticlinorium of 15-km length with a direction of N10–30E. Detailed study of the four deposits forming the northern part of this zone has allowed us to discover large reserves of 100.65 million tons, of which 78% is composed of high-grade ore with a content of 10.27% Na₂O. The remainder is formed by low-grade ore with 8.37% Na₂O and 1.11% K₂O and mixed ore with 4.61% Na₂O and 4.05% K₂O, with reserves of 14.4 and 8.2 million tons, respectively. To cite this article: U. Çak?r, C. R. Geoscience 337 (2005).     

The use of major elemental ratios in detailed geochemical prospecting utilizing primary halos

The behaviour of the ratios K₂O/Na₂O, SiO₂/CO₂, and $\text{SiO}{}_2\text{H}{}_2\text{O}\text{+ CO}{}_2\text{+ S}$ in the alteration envelopes of a variety of epigenetic deposits is documented. It is concluded that the ratio K₂O/Na₂O is the most suitable for estimating proximity to ore during exploration drilling programs. The other two ratios are useful in indicating proximity to ore only under certain geological conditions. Before the use of ratios is contemplated in detailed exploration programs within a given mineral belt orientation studies should be carried out to determine the trend of the ratios with proximity to mineralization.     

Thermochemistry of jarosite-alunite and natrojarosite-natroalunite solid solutions

The thermochemistry of jarosite-alunite and natrojarosite-natroalunite solid solutions was investigated. Members of these series were either coprecipitated or synthesized hydrothermally and were characterized by XRD, FTIR, electron microprobe analysis, ICP-MS, and thermal analysis. Partial alkali substitution and vacancies on the Fe/Al sites were observed in all cases, and the solids studied can be described by the general formula K_1-x-yNa_y(H₃O)_xFe_zAl_w(SO₄)₂(OH)_6-3(3-z-w)(H₂O)_3(3-z-w). A strong preferential incorporation of Fe over Al in the jarosite/alunite structure was observed. Heats of formation from the elements, ΔH°_f, were determined by high-temperature oxide melt solution calorimetry. The solid solutions deviate slightly from thermodynamic ideality by exhibiting positive enthalpies of mixing in the range 0 to +11 kJ/mol. The heats of formation of the end members of both solid solutions were derived. The values ΔH°_f = −3773.6 ± 9.4 kJ/mol, ΔH°_f = −4912.2 ± 24.2 kJ/mol, ΔH°_f = −3734.6 ± 9.7 kJ/mol and ΔH°_f = −4979.7 ± 7.5kJ/mol were found for K_0.85(H₃O)_0.15Fe_2.5(SO₄)₂(OH)_4.5(H₂O)_1.5, K_0.85(H₃O)_0.15Al_2.5(SO₄)₂(OH)_4.5(H₂O)_1.5, Na_0.7(H₃O)_0.3Fe_2.7(SO₄)₂(OH)_5.1(H₂O)_0.9, and Na_0.7(H₃O)_0.3Al_2.7(SO₄)₂(OH)_5.1(H₂O)_0.9 respectively. To our knowledge, this is the first experimentally-based report of ΔH°_f for such nonstoichiometric alunite and natroalunite samples. These thermodynamic data should prove helpful to study, under given conditions, the partitioning of Fe and Al between the solids and aqueous solution.     

An example of occurence and breakdown of paragonite

Paragonite occurs in pelitic schists and amphibole schists of the Ötztal Alps (Tyrol); its occurence in amphibole schists is controlled by the Na₂O/K₂O, in pelitic schists by the local fabric. Some analysis of the bulk chemistry of the paragonite bearing rocks and one microprobe analysis of paragonite are given. Paragonite is stable together with muscovite, together with quartz it is unstable. Its breakdown can be described by the reaction: paragonite+quartz kyanite+albite+H₂O. The age of this breakdown is discussed by comparison of experimental, field and radiometric data, it is thought to be of Variscian age.     

Vesiculation of hydrous andesitic melt and transport of alkalies by separated vapor phase

Experiments have been carried out on the separation of H₂O-rich vapor phase from a hydrous andesite melt at pressures between 5 and 15 kbar at 1,150 ° C. The pressure at which the vapor phase separates from the melt by isothermal decompression depends on the H₂O content in the melt; for example, 14 kbar for 12wt.% and 8 kbar for 9wt.% H₂O. These values are lower than the solubility of H₂O in andesite melt previously estimated. Extensive decompression to near atmospheric pressure resulted in the formation of pumiceous glass.Vapor phase separated from the melt moves upward and transports significant amounts of alkalies (Na₂O and K₂O), resulting in the depletion of alkalies near the bottom and concentration of alkalies near the top of the container. The maximum concentration observed is 5.0 wt.% for Na₂O and 1.7% for K₂O, compared to the initial contents 3.3 and 1.3 wt.% respectively. The approximate viscosity of hydrous andesitic melt with 7.5–12 wt.% H₂O was roughly estimated to be less than 10 poise. The results of the present experiments imply that when H₂O-rich vapor separates from magma in a magma chamber (or in a conduit) and moves upward, the top of the chamber would be enriched in alkalies while the bottom would be depleted.     

Crystal structure model for metavoltine from Sierra Gorda

Summary The crystal structure of metavoltine from Sierra Gorda, Chile, has been solved from photographic X-ray data by the heavy atom method. The space group used wasP3 witha=9.575(5) andc=18.17(1)Å; cell content: K₂Na₆ (Fe ²⁺, Cu, Zn)Fe ₆ ³⁺ (SO₄)₁₂O₂·18H₂O. From the relatively small number and the somewhat poor quality of the X-ray data, the least squares refinement did not give very satisfactory results-especially so for the light atoms. Therefore, steric considerations and information from the Fourier maps were also used when choosing the final atomic coordinates. The salient features of the structure are clusters of Fe ₃ ³⁺ O(H₂O)₃(SO₄)₆ with Fe³⁺ in octahedral coordination, and Fe²⁺(H₂O)₆ octahedra. The Na⁺ ions show octahedral coordination, the K⁺ ions irregular nine coordination.

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Ein Kristallstrukturmodell für den Metavoltin von Sierra Gorda

Zusammenfassung Die Kristallstruktur des Metavoltins von Sierra Gorda (Chile) wurde aus photographischen Röntgendaten mit der Schweratommethode gelöst. Als Raumgruppe wurdeP3 mita ₀9,575(5) undc ₀=18,17(1) Å verwendet; Zellinhalt K₂Na₆ (Fe ²⁺, Cu, Zn) Fe ₆ ³⁺ (SO₄)₁₂O₂·18H₂O.Wegen der relativ kleinen Zahl und der nicht sehr guten Qualität der Röntgendaten gab die Verfeinerung nach der Methode der kleinsten Quadrate keine sehr guten Ergebnissebesonders nicht für die leichten Atome. Deshalb wurden zur Festlegung der endgültigen Atomkoordinaten auch sterische Überlegungen und Informationen aus Fouriersynthesen herangezogen. Hervorstechende Züge der Struktur sind Gruppen Fe ₃ ³⁺ O(H₂O)₃(SO₄)₆ mit Fe³⁺ in oktaedrischer Koordination sowie Fe²⁺(H₂O)₆-Oktaeder. Die Na⁺-Ionen zeigen oktaedrische Koordination, die K⁺-Ionen unregelmäßige 9-Koordination.

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With 4 Figures