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.     

Isotopic (Sm–Nd,Pb–Pb,and δ<Superscript>34</Superscript>S) and Geochemical Characteristics of the Metasedimentary Rocks of the Baikal–Patom Belt (Northern Transbaikalia) and Evolution of the Sedimentary Basin in the Neoproterozoic

This paper reports the results of a detailed isotopic (Sm–Nd, Pb–Pb, and δ³⁴S) and geochemical studies of Neoproterozoic metasedimentary rocks from the Patom and Bodaibo domains of the Baikal–Patom belt (northern Transbaikalia). It was shown that the metasedimentary rocks of these domains are strongly variable in their geochemical and isotope geochemical characteristics. Regular variations in these characteristics were observed, and their correlation with the main stages of the evolution of the sedimentary paleobasin in the Neoproterozoic was established.     

Phase equilibria in the KFeS<Subscript>2</Subscript>–Fe–S system at 300–600 °C and bartonite stability

The article deals with phase relations in the KFeS₂–Fe–S system studied by the dry synthesis method in the range of 300–600 °C and at a pressure of 1 bar. At the temperature below 513?±?3 °C, pyrite coexists with rasvumite and there are pyrite–rasvumite–KFeS₂ and pyrite–rasvumite–pyrrhotite equilibria established. Above 513?±?3 °C pyrite and rasvumite react to form KFeS₂ and pyrrhotite, limiting the pyrite–rasvumite association to temperatures below this in nature. The experiments also outline the compositional stability range of the copper-free analog of murunskite (K _x Fe_2?yS₂) and suggest that mineral called bartonite is not stable in the Cl-free system, at least at atmospheric pressure and the temperature in the experiments. Chlorbartonite could be easily produced after adding KCl in the experiment. Possible parageneses in the quaternary K–Fe–S–Cl system were described based on the data obtained in this research and found in the previous studies. The factors affecting the formation of potassium–iron sulfides in nature were discussed.     

Synthesis of monticellite–forsterite and merwinite–forsterite symplectites in the CaO–MgO–SiO<Subscript>2</Subscript> model system: influence of temperature and water content on microstructure evolution

Homogeneous single crystals of synthetic monticellite with the composition \({\text{Ca}}_{0.88}{\text{Mg}}_{1.12}{\text{SiO}}_4\) (Mtc I) were annealed in a piston-cylinder apparatus at temperatures between 1000 and \(1200\,^{\circ }\hbox {C}\), pressures of 1.0–1.4 GPa, for run durations from 10 min to 24 h and applying bulk water contents ranging from 0.0 to 0.5 wt% of the total charge. At these conditions, Mtc I breaks down to a fine-grained, symplectic intergrowth. Thereby, two types of symplectites are produced: a first symplectite type (Sy I) is represented by an aggregate of rod-shaped forsterite immersed in a matrix of monticellite with end-member composition (Mtc II), and a second symplectite type (Sy II) takes the form of a lamellar merwinite–forsterite intergrowth. Both symplectites may form simultaneously, where the formation of Sy I is favoured by the presence of water. Sy I is metastable with respect to Sy II and is successively replaced by the latter. For both symplectite types, the characteristic spacing of the symplectite phases is independent of run duration and is only weeakly influenced by the water content, but it is strongly temperature dependent. It varies from about 400 nm at \(1000\,^{\circ }\hbox {C}\) to 1200 nm at \(1100\,^{\circ }\hbox {C}\) in Sy I, and from 300 nm at \(1000\,^{\circ }\hbox {C}\) to 700 nm at \(1200\,^{\circ }\hbox {C}\) in Sy II. A thermodynamic analysis reveals that the temperature dependence of the characteristic spacing of the symplectite phases is due to a relatively high activation energy for chemical segregation by diffusion within the reaction front as compared to the activation energy for interface reactions at the reaction front. The temperature dependence of the characteristic lamellar spacing and the temperature-time dependence of overall reaction progress have potential for applications in geo-thermometry and geo-speedometry.     

Test of the Ballhaus–Berry–Green <Emphasis Type="Italic">Ol–Opx–Sp</Emphasis> oxybarometer and calibration of a new equation for estimating the redox state of melts saturated with olivine and spinel

Testing the Ballhaus–Berry–Green Ol–Opx–Sp oxybarometer (BBG) on independent experimental data indicates that it overestimates the oxygen fugacity by 0.6–1.3 log units under mildly reduced conditions (near the C–CO buffer) and by as much as 2–3 log units under reduced conditions (at the IW buffer and below it). A newly developed oxibarometer is suggested to minimize this effect and enhance the capabilities of redoxometry of low-pressure mineral associations, including magmatic melts undersaturated with respect to orthopyroxene (Opx). The new empirical equation of the oxybarometer is applicable to a wide range of mafic–ultramafic magmas of normal alkalinity, including terrestrial, lunar, and meteoritic systems under pressures of 0.001–25 kbar and oxygen fugacity ranging from IW–3 to NNO + 1. The derived regression fits the ΔQFM values of the calibration dataset (154 experiments) accurate to ~0.5 log units. The new oxybarometer eliminates systematic errors when redox parameters are evaluated for the reduced region (from IW–3 to C–CO) and for crystallization of magmas without Opx on the liquidus. The efficiency of the suggested model is demonstrated by its application to natural rocks: (1) low-Ti lunar basalts, (2) tholeiites from the Shatsky Rise, (3) Siberian flood basalts, (4) rocks of the layered series of the Yoko-Dovyren intrusion, and (5) mantle xenoliths collected in southern Siberia, Mongolia, China, and the southern Russian Far East. The values yielded by such oxybarometers for intrusive rocks, which underwent long-lasting cooling and postcumulus reequilibration, should be regarded with reserve.     

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.     

Rb–Sr and <Superscript>147</Superscript>Sm–<Superscript>143</Superscript>Nd systematics of gabbro and dolerites from fragments of ophiolite complexes of the Middle Urals

The Rb–Sr and ¹⁴⁷Sm–¹⁴³Nd age data obtained for sheeted dolerite dykes and rocks of the Platinum Belt of the Urals within the Tagil segment of the paleoceanic spreading structure (Middle Urals) are discussed. The study of the Rb–Sr isotope systematics of gabbro allowed us to reveal errochronous dependencies, which yielded ages of 415 and 345 Ma at (⁸⁷Sr/⁸⁶Sr)₀ = 0.70385 ± 0.00068 and 0.7029 ± 0.0010, correspondingly. The ¹⁴⁷Sm–¹⁴³Nd isotope age data demonstrate a specific coincidence of the chronometric ages of the sheeted dolerite dyke complex (426 ± 54, 426 ± 34, and 424 ± 19 Ma) and gabbro from the Revda gabbro–ultramafic massif (431 ± 27 Ma) and from screens between dolerite dykes in the sheeted dyke complex (427 ± 32 Ma, 429 ± 26 Ma). The proximity of the ¹⁴⁷Sm–¹⁴³Nd ages of gabbro and dolerite can be explained by the thermal effect of the basaltic melt, which is the protolith for the dyke complex, on the hosting gabbro.     

Rb–Sr and Sm–Nd study of granite–charnockite association in the Pudukkottai region and the link between metamorphism and magmatism in the Madurai Block

Pudukkottai region in the northeastern part of the Madurai Block exposes the garnetiferous pink granite that intruded the biotite gneiss. Charnockite patches are associated with both the rock types. Rb–Sr biotite and Sm–Nd whole-rock isochron ages indicate a regional uplift and cooling at ～550 Ma. The initial Nd isotope ratios (\(\varepsilon _{\text {Nd}}^{\mathrm {t}}=-20\) to ?22) and Nd depleted-mantle model ages (T_DM = 2.25 to 2.79 Ga) indicate a common crustal source for the pink-granite and associated charnockite, while the biotite gneiss and the charnockite within it represent an older crustal source (\(\varepsilon _{\text {Nd}}^{\mathrm {t}}= -29\) and T_DM = > 3.2 Ga). The Rb–Sr whole-rock data and initial Sr–Nd isotope ratios also help demonstrate the partial but systematic equilibration of Sr isotope and Rb/Sr ratios during metamorphic mineral-reactions resulting in an ‘apparent whole-rock isochron’. The available geochronological results from the Madurai Block indicate four major periods of magmatism and metamorphism: Neoarchaean–Paleoproterozoic, Mesoproterozoic, mid-Neoproterozoic and late-Neoproterozoic. We suggest that the high-grade and ultrahigh-temperature metamorphism was preceded by magmatism which ‘prepared’ the residual crust to sustain the high P–T conditions. There also appears to be cyclicity in the tectono-magmatic events and an evolutionary model for the Madurai Block should account for the cyclicity in the preserved records.     

Pioneers of Jamaican geology and the Jamaica Group of the Geologists’ Association (1955–1959)

The formation of a geological society in Jamaica was dependent upon attaining a sufficient number of interested geologists on the island. Although the earliest study of Jamaican geology dated to the 1820s (De la Beche), few major geologists worked on the island in the 19th (Barrett, Sawkins, Hill) and early 20th centuries (Matley, Trechmann). A ‘critical mass’ of geologists was only attained in the 1950s after foundation of the third Geological Survey of the island, when, for the first time, the island had a resident geological intelligentsia. The director, V.A. Zans (1904–1961), was a Latvian geologist appointed from a camp for displaced persons. His staff included L.J. Chubb (1887–1971), who popularised geology in Jamaica. Chubb and his colleagues devised a three part plan for geological education in Jamaica: high schools were encouraged to introduce geology as an examination subject; introduction of geology as a part of the Natural Sciences curriculum at the University College of the West Indies was supported; and a local geological society for both amateurs and professionals was established. This society, the Jamaica Group of the Geologists’ Association, was established in 1955 and was the only such overseas group ever founded; Chubb was elected President. The first field trip was led by Zans and A.D. Foster in November 1955. The Group was reformed as the independent Geological Society of Jamaica (GSJ) in late 1959, again with Chubb as the first President. The GSJ remembers the name of its first President in the prestigious L.J. Chubb Award.     

Trace element partitioning between orthopyroxene and anhydrous silicate melt on the lherzolite solidus from 1.1 to 3.2 GPa and 1,230 to 1,535°C in the model system Na<Subscript>2</Subscript>O–CaO–MgO–Al<Subscript>2</Subscript>O<Subscript>3</Subscript>–SiO<Subscript>2</Subscript>

We determined experimentally the Nernst distribution coefficient between orthopyroxene and anhydrous silicate melt for trace elements i in the system Na₂O–CaO–MgO–Al₂O₃–SiO₂ (NCMAS) along the dry model lherzolite solidus from 1.1 GPa/1,230°C up to 3.2 GPa/1,535°C in a piston cylinder apparatus. Major and trace element composition of melt and orthopyroxene were determined with a combination of electron microprobe and ion probe analyses. We provide partitioning data for trace elements Li, Be, B, K, Sc, Ti, V, Cr, Co, Ni, Rb, Sr, Y, Zr, Nb, Cs, Ba, La, Ce, Sm, Nd, Yb, Lu, Hf, Ta, Pb, U, and Th. The melts were chosen to be boninitic at 1.1 and 2.0 GPa, picritic at 2.3 GPa and komatiitic at 2.7 and 3.2 GPa. Orthopyroxene is Tschermakitic with 8 mol% Mg-Tschermaks MgAl[AlSiO₆] at 1.1 GPa while at higher pressure it has 18–20 mol%. The rare earth elements show a continuous, significant increase in compatibility with decreasing ionic radius from D _La^opx−melt ∼ 0.0008 to D _Lu^opx−melt ∼ 0.15. For the high-field-strength elements compatibility increases from D _Th^opx−melt ∼ 0.001 through D _Nb^opx−melt ∼ 0.0015, D _U^opx−melt ∼ 0.002, D _Ta^opx−melt ∼ 0.005, D _Zr^opx−melt ∼ 0.02 and D _Hf^opx−melt ∼ 0.04 to D _Ti^opx−melt ∼ 0.14. From mathematical and graphical fits we determined best-fit values for D ₀^M1, D ₀^M2, r ₀^M1, r ₀^M2, E ₀^M1, and E ₀^M2 for the two different M sites in orthopyroxene according to the lattice strain model and calculated the intracrystalline distribution between M1 and M2. Our data indicate extreme intracrystalline fractionation for most elements in orthopyroxene; for the divalent cations D _i ^M2−M1 varies by three orders of magnitude between D _Co^M2−M1 = 0.00098–0.00919 and D _Ba^M2−M1 = 2.3–28. Trivalent cations Al and Cr almost exclusively substitute on M1 while the other trivalent cations substitute on M2; D _La^M2−M1 reaches extreme values between 6.5 × 10⁷ and 1.4 × 10¹⁶. Tetravalent cations Ti, Hf, and Zr almost exclusively substitute on M1 while U and Th exclusively substitute on M2. Our new comprehensive data set can be used for polybaric-polythermal melting models along the Earth’s mantle solidus. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

U–Pb,Re–Os,and <Superscript>40</Superscript>Ar/<Superscript>39</Superscript>Ar geochronology of the Nambija Au-skarn and Pangui porphyry Cu deposits,Ecuador: implications for the Jurassic metallogenic belt of the Northern Andes

New U–Pb, Re–Os, and ⁴⁰Ar/³⁹Ar dates are presented for magmatic and hydrothermal mineral phases in skarn- and porphyry-related ores from the Nambija and Pangui districts of the Subandean zone, southeastern Ecuador. Nambija has been one of the main gold-producing centers of Ecuador since the 1980s due to exceptionally high-grade ores (average 15 g/t, but frequently up to 300 g/t Au). Pangui is a recently discovered porphyry Cu–Mo district. The geology of the Subandean zone in southeastern Ecuador is dominated by the I-type, subduction-related, Jurassic Zamora batholith, which intrudes Triassic volcanosedimentary rocks. The Zamora batholith is in turn cut by porphyritic stocks, which are commonly associated with skarn formation and/or porphyry-style mineralization. High precision U–Pb and Re–Os ages for porphyritic stocks (U–Pb, zircon), associated prograde skarn (U–Pb, hydrothermal titanite), and retrograde stage skarn (Re–Os, molybdenite from veins postdating gold deposition) of the Nambija district are all indistinguishable from each other within error (145 Ma) and indicate a Late Jurassic age for the gold mineralization. Previously, gold mineralization at Nambija was considered to be Early Tertiary based on K–Ar ages obtained on various hydrothermal minerals. The new Jurassic age for the Nambija district is slightly younger than the ⁴⁰Ar/³⁹Ar and Re–Os ages for magmatic–hydrothermal minerals from the Pangui district, which range between 157 and 152 Ma. Mineralization at Nambija and Pangui is associated with porphyritic stocks that represent the last known episodes of a long-lived Jurassic arc magmatism (∼190 to 145 Ma). A Jurassic age for mineralization at Nambija and Pangui suggests that the Northern Andean Jurassic metallogenic belt, which starts in Colombia at 3° N, extends down to 5° S in Ecuador. It also adds a new mineralization style (Au-skarn) to the metal endowment of this belt. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Mechanisms and rates of quartz dissolution in melts in the CMAS (CaO–MgO–Al<Subscript>2</Subscript>O<Subscript>3</Subscript>–SiO<Subscript>2</Subscript>) system

The dissolution rate of minerals in silicate melts is generally assumed to be a function of the rate of mass transport of the released cations in the solvent. While this appears to be the case in moderately to highly viscous solvents, there is some evidence that the rate-controlling step may be different in very fluid, highly silica undersaturated melts such as basanites. In this study, convection-free experiments using solvent melts with silica activity from 0.185–0.56 and viscosity from 0.03–4.6 Pa s show that the dissolution rate is strongly dependent on the degree of superheating, silica activity and the viscosity of the solvent. Dissolution rates increase with increasing melt temperature and decreasing silica activity and viscosity. Quartz dissolution in melts with viscosity <0.59–1.9 Pa s and silica activity <0.47 is controlled by the rate of interface reaction as shown by the absence of steady state composition and silica saturation in the interface melts. Only in the most viscous melt with the highest silica activity is quartz dissolution controlled by the rate of diffusion in the melt and only after a long initiation time. The results of this study indicate that although a diffusion-based model may be applicable to dissolution in viscous magmas, a different approach that combines the interplay between the degree of undersaturation of the melt and its viscosity is required in very fluid melts.This revised version was published online September 2004 with a correction to Figure 8.     

Phase equilibria in the MgO–SiO<Subscript>2</Subscript>–ZrO<Subscript>2</Subscript> system

The results of study of phase equilibria in the MgO–SiO₂–ZrO₂ system at 1450–1550°C are reported. The studied system contains two eutectic points and six fields: (I) MgSiO₃ + SiO₂; (II) MgSiO₃ + ZrO₂; (III) ZrSiO₄ + SiO₂; (IV) MgSiO₃ + Mg₂SiO₄; (V) ZrO₂ + MgO; (VI) ZrSiO₄ + ZrO₂. The presence of fields (II) and (III) on the diagram shows that zircon in equilibrium with olivine and pyroxene crystallizes at very low concentrations of ZrO₂ in the system. This provides a solution for one of the most important problems in zirconology of dunites: the probability of the formation and preservation of zircon in the course of the formation and evolution of dunite.     

Heat capacity and thermodynamic properties of GdPO<Subscript>4</Subscript> in the temperature range 0–1600 K

The heat capacity of gadolinium orthophosphate (GdPO₄) measured in the temperature range 11.15–344.11 K by adiabatic calorimetry and available literature data were used to calculate its thermodynamic functions at 0–1600 K. At 298.15 K, these functions are as follows: C _p ⁰(298.15 K) = 101.85 ± 0.05 J K⁻¹ mol⁻¹, S ⁰(298.15 K) = 123.82 ± 0.18 J K⁻¹ mol⁻¹, H ⁰(298.15 K)–H ⁰(0) = 17.250 ± 0.012 kJ mol⁻¹, and Φ ⁰(298.15 K) = 65.97 ± 0.18 J K⁻¹ mol⁻¹ The calculated Gibbs free energy of formation from the elements of GdPO₄ is Δ _f G ⁰ (298.15 K) = −1844.3 ± 4.7 kJ mol⁻¹.     

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–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.     

Solid solutions in the system acanthite (Ag<Subscript>2</Subscript>S)–naumannite (Ag<Subscript>2</Subscript>Se) and the relationships between Ag-sulfoselenides and Se-bearing polybasite from the Kongsberg silver district,Norway, with implications for sulfur–selenium fractionation

Sulfoselenides [Ag₂(S,Se)] and Se-bearing polybasite have been discovered at the Kongsberg silver district. The selenium-bearing minerals occur in two samples from the northern part of the district, forming either single or polyphase inclusions together with chalcopyrite within native silver. The Ag-sulfoselenides show large chemical variations, covering nearly the complete compositional range between acanthite (Ag₂S) and naumannite (Ag₂Se). For the data presented here, there is no local maximum at the composition Ag₄SSe attributed to the distinct phase called aguilarite, suggesting that this composition can be considered as one of many possible along the monoclinic Ag₂S–Ag₂S_0.4Se_0.6 solid solution series rather than a specific mineral phase. We present a model explaining the variations in the Se-content of Ag₂(S,Se) as a result of gradual de-sulfidization of the rock under oxidizing conditions. During this process, sulfur from the Ag₂S-component of Ag₂(S,Se) oxidized and dissolved in the fluid phase as SO₄^2?, resulting in the formation of native silver. The activity ratio \({a_{{{\text{S}}^{2 - }}}}/{a_{{\text{S}}{{\text{e}}^{2 - }}}}\) of the system gradually decreased due to the removal of SO₄^2?, which resulted in the stabilization of a sulfoselenide with higher selenium content. As a result of reaction progress, grains of Ag₂(S,Se) became gradually enclosed in newly formed native silver, and therefore isolated from further reactions with the grain-boundary fluid. Grains isolated early during the process show low content of Se reflecting high \({a_{{{\text{S}}^{2 - }}}}/{a_{{\text{S}}{{\text{e}}^{2 - }}}}\) of the equilibrium fluid, while grains showing high Se reflect the composition of late low \({a_{{{\text{S}}^{2 - }}}}/{a_{{\text{S}}{{\text{e}}^{2 - }}}}\) fluids. Analyses of Se-bearing polybasite show that selenium is preferentially partitioned into Ag₂(S,Se) compared to polybasite. The model presented here demonstrates how oxidation of sulfoselenides leads to fractionation of sulfur and selenium.     

La–SiO<Subscript>2</Subscript> and Yb–SiO<Subscript>2</Subscript> systematics in mid-ocean ridge magmas: implications for the origin of oceanic plagiogranite

Analytical expressions for the variation in D _La and D _Yb with increasing liquid SiO₂ for olivine, plagioclase, augite, hornblende, orthopyroxene, magnetite and ilmenite (Brophy in Contrib Mineral Petrol 2008, online first) have been combined with numerical models of hydrous partial melting, of mid-ocean ridge (MOR) cumulate gabbro melting, and fractional crystallization of slightly hydrous mid-ocean ridge basalt (MORB) magma to assess a melting versus fractionation origin for oceanic plagiogranite. For felsic magmas (>63 wt.% SiO₂) the modeling predicts the following. MOR cumulate gabbro melting should yield constant or decreasing La and constant Yb abundances with increasing liquid SiO₂. The overall abundances should be similar to those in associated mafic magmas. MORB fractional crystallization should yield steadily increasing La and Yb abundances with increasing SiO₂ with overall abundances significantly higher than those in associated mafic magmas. Application to natural occurrences of oceanic plagiogranite indicate that both MOR cumulate gabbro melting and MORB fractionation are responsible. Application of the model results to Icelandic rhyolites strongly support a fractional crystallization rather than a crustal melting origin.     

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.