Partitioning behavior of chlorine and fluorine in the system apatite-silicate melt-fluid

The partitioning behavior of Cl among apatite, mafic silicate melt, and aqueous fluid and of F between apatite and melt have been determined in experiments conducted at 1066 to 1150 °C and 199-205 MPa. The value of D_Cl^apatite/melt (wt. fraction of Cl in apatite/Cl in melt) ≈0.8 for silicate melt containing less than ∼3.8 wt.% Cl. At higher melt Cl contents, small increases in melt Cl concentration are accompanied by large increases in apatite Cl concentration, forcing D_Cl^apatite/melt to increase as well. Melt containing less than 3.8% Cl coexists with water-rich vapor; that containing more Cl coexists with saline fluid, the salinity of which increases rapidly with small increases in melt Cl content, analogous to the dependency of apatite composition on melt Cl content. This behavior is due to the fact that the solubility of Cl in silicate melt depends strongly on the composition of the melt, particularly its Mg, Ca, Fe, and Si contents. Once the melt becomes “saturated” in Cl, additional Cl must be accommodated by coexisting fluid, apatite, or other phases rather than the melt itself. Because Cl solubility depends on composition, the Cl concentration at which D_Cl^apatite/melt and D_Cl^fluid/melt begin to increase also depends on composition. The experiments reveal that D_F^apatite/melt ≈3.4. In contrast to Cl, the concentration of F in silicate melt is only weakly dependent on composition (mainly on melt Ca contents), so D_F^apatite/melt is constant for a wide range of composition.The experimental data demonstrate that the fluids present in the waning stages of the solidification of the Stillwater and Bushveld complexes were highly saline. The Cl-rich apatite in these bodies crystallized from interstitial melt with high Cl/(F + OH) ratio. The latter was generated by the combined processes of fractional crystallization and dehydration by its reaction with the relatively large mass of initially anhydrous pyroxene through which it percolated.     

Phase relations of a F-enriched peraluminous granite: an experimental study of the Kymi topaz granite stock,southern Finland

Phase relations of F-rich Kymi equigranular topaz granite have been investigated experimentally at 100–500 MPa as a function of water activity and F content. Fluorite and topaz can crystallize as liquidus phases in F-rich peraluminous systems, but the F content of the melt should exceed 2.5–3.0 wt% for the crystallization of topaz. In peraluminous F-bearing melts containing more than 1 wt% F, topaz and muscovite are expected to be the first F-bearing phases to crystallize at high pressure, whereas fluorite and topaz should crystallize first at low pressure. Following reaction models the saturation of fluorite and topaz: CaAl₂Si₂O₈ (plagioclase) + 2[AlF₃]_melt = CaF₂ (fluorite) + 2Al₂SiO₄F₂ (topaz). The obtained partition coefficient for F between biotite and glass D(F)^Bt/glass ranges from 1.89 to 0.80 (average value 1.29) and can be used as an empirical fluormeter to determine the F content of coexisting melts. Combined petrological and experimental studies of the Kymi equigranular topaz granite indicate that plagioclase was the liquidus phase at nearly water-saturated (fluid-saturated) conditions and that the F content of the melt was at least 2 wt%. The mean F content of natural biotite (3.92 wt%) suggests that the late-stage crystallization of biotite occurred in melts containing about 3 wt% F. The early crystallization of biotite and the presence of muscovite in our experiments at 200 MPa contrasts with the late-stage crystallization of biotite and the absence of muscovite in the natural assemblage, indicating that crystallization pressure may have been lower than 200 MPa for the granite. Electronic supplementary material Supplementary material is available in the online version of this article at and is accessible for authorized users.     

Trace element partitioning in plagioclase feldspar

Compilation and interpretation of experimental and natural Nernst partition coefficient (^{plagioclase/melt}D) data show that, with a few exceptions, increases in ^{plagioclase/melt}D correlate with decreasing anorthite-content of plagioclase. In contrast, increases of ^{plagioclase/melt}D for Ga, Sc, Cu, Zn, Zr, Hf and Ti, are better correlated against decreasing melt MgO or increasing melt SiO₂ contents. ^{plagioclase/melt}D for Ti and the rare earth elements (REE) show little dependence on temperature, but increase as the melt water content increases. ^{plagioclase/melt}D for K and Sr are sensitive to pressure. Variations of D₀ (the strain compensated partition coefficient), r₀ (the size of the site into which REE substitute), and E (Young’s Modulus of this site) were parameterized against variations of melt SiO₂, the An-content of plagioclase, and other combinations of variables, allowing ^{plagioclase/melt}D_REE-Y to be calculated from a variety of input parameters. The interrelations of temperature, melt MgO and SiO₂ content, and plagioclase anorthite-content for wet and dry systems were also parameterized to facilitate interpolation where such data are lacking. When combined, these semi-empirical parameterizations yield ^{plagioclase/melt}D results comparable to available experimental and natural data.     

Solubility behavior of alkali aluminosilicate components in aqueous fluids and silicate melts at high pressure and temperature

The solubility behavior of K₂O, Na₂O, Al₂O₃, and SiO₂ in silicate-saturated aqueous fluid and coexisting H₂O-saturated silicate melts in the systems K₂O-Al₂O₃-SiO₂-H₂O and Na₂O-Al₂O₃-SiO₂-H₂O has been examined in the 1- to 2-GPa pressure range at 1100°C. Glasses of Na- and K-tetrasilicate compositions with 0, 3, and 6 mol% Al₂O₃ were used as starting materials. In both systems, the oxides dissolve incongruently in aqueous fluid and silicate melt. When recalculated to an anhydrous basis, the aqueous fluids are enriched in alkalis and depleted in silica and alumina relative to their proportions in the starting materials. The extent of incongruency is more pronounced in the Na₂O-Al₂O₃-SiO₂-H₂O system than in the K₂O-Al₂O₃-SiO₂-H₂O system.The partition coefficients of the oxides, D_oxide^fluid/melt, are linear and positive functions of the oxide concentration in the fluid for each composition. There is a slight dependence of the partition coefficients on bulk composition. No effect of pressure could be discerned. For alkali metals, the fluid/melt partition coefficients range from 0.06 to 0.8. For Al₂O₃ this range is 0.01 to 0.2, and for SiO₂, it is 0.01 to 0.32. For all compositions, D_K2O^fluid/melt∼D_Na2O^fluid/melt>D_SiO2^fluid/melt>D_Al2O3^fluid/melt for the same oxide concentration in the fluid. D_K2O^fluid/melt, D_Na2O^fluid/melt, and D_SiO2^fluid/melt correlate negatively with the Al₂O₃ content of the systems. This correlation is consistent with a solubility model of alkalis that involve associated KOH°, NaOH°, silicate, and aluminate complexes.     

Distribution of REE,LILE, and HFSE between biotite,feldspar, and the melt in the granulite facies migmatite,nimnyr block,Aldan shield

The behavior of trace elements under conditions of partial melting of granitoid rocks has been studied. The element’s partition coefficients between minerals and the melt D_i^min/melt depends, in the first place, on the composition of the primary melt. In biotite the HREE D_i are a little below 1, while those of LREE, especially D_i for Ce, are 1–3 orders of magnitude less. This leads to an efficient differentiation of REEs in anatexic melts especially when biotite is the main mineral phase of restite. On the contrary, there are feldspars, the D_i of which cannot provide such a magnitude of differentiation. Unlike garnets and pyroxenes, whose stability in restite permits enrichment of anatexic melts produced in migmatization zones with Nb, Ti, and Cr, the presence of biotite in restite causes depletion of melts with those elements as well as with Rb. Feldspars, under conditions of their fractional crystallization or during differentiation of an anatexic melt, deplete the latter with Sr, Ba, and Rb, but enrich it with Nb, Ti, Cr, Y, Zr, and V.     

Experimental study of fluorine and chlorine contents in mica (biotite) and their partitioning between mica,phonolite melt,and fluid

This paper reports the results of a study of the composition of mica (biotite) crystallizing in the system of phonolite melt-Cl- and F-bearing aqueous fluid at T ～ 850°C, P = 200 MPa, and \(f_{O_2 } \) = Ni-NiO, as well as data on F and Cl partitioning between coexisting phases. It was established that Cl content in mica is significantly lower than in phonolite melt and, especially, in fluid. Fluorine shows a different behavior in this system: its content in mica is always higher than in phonolite melt but lower than in fluid. The mica-melt partition coefficients of Cl and F also behave differently. The Cl partition coefficient gradually increases from 0.17 to 0.33 with increasing Cl content in the system, whereas the partition coefficient of F sharply decreases from 3.0 to 1.0 with increasing total F content. The apparent partition coefficients of F between biotite and groundmass (melt) in various magmatic rocks are usually significantly higher than the experimental values. It was supposed that the higher ^Bt/glassD_F values in natural samples could be related to the influence of later oxidation reactions, reequilibration of biotite at continuously decreasing \(f_{H_2 O} \)/f _HF ratio, and an increase in this coefficients with decreasing total F content in the system.     

PGE mineralization and melt composition of chromitites in Proterozoic ophiolite complexes of Eastern Sayan,Southern Siberia

The Ospino-Kitoi and Kharanur ultrabasic massifs represent the northern and southern ophiolite branches respectively of the Upper Onot ophiolitic nappe and they are located in the southeastern part of the Eastern Sayan(SEPES ophiolites).Podiform chromitites with PGE mineralization occur as lensoid pods within dunites and rarely in harzburgites or serpentinized peridotites.The chromitites are classified into type I and type Ⅱ based on their Cr~#.Type I(Cr~# = 59-85) occurs in both northern and southern branches,whereas type Ⅱ(Cr~# = 76-90) occurs only in the northern branch.PGE contents range from ∑PGE 88-1189 ppb,Pt/Ir0.04-0.42 to ∑PGE 250-1700 ppb,Pt/Ir 0.03-0.25 for type I chromitites of the northern and southern branches respectively.The type Ⅱ chromitites of the northern branch have ∑PGE contents higher than that of type Ⅰ(468-8617 ppb,Pt/Ir 0.1-0.33).Parental melt compositions,in equilibrium with podiform chromitites,are in the range of boninitic melts and vary in Al_2O_3,TiO_2 and FeO/MgO contents from those of type I and type Ⅱ chromitites.Calculated melt compositions for type Ⅰ chromitites are(Al_2O_3)_(melt) = 10.6—13.5 wt.%,(TiO_2)_(melt) = 0.01-0.44 wt.%,(Fe/Mg)_(melt) = 0.42-1.81;those for type Ⅱ chromitites are:(Al_2O_3)_(melt) = 7.8-10.5 wt.%,(TiO_2)_(melt) = 0.01-0.25 wt.%,(Fe/Mg)_(melt) = 0.5-2.4.Chromitites are further divided into Os-Ir-Ru(Ⅰ) and Pt-Pd(Ⅱ) based on their PGE patterns.The type Ⅰ chromitites show only the Os-Ir-Ru pattern whereas type Ⅱ shows both Os-Ir-Ru and Pt-Pd patterns.PGE mineralization in type Ⅰ chromitites is represented by the Os-Ir-Ru system,whereas in type Ⅱ it is represented by the Os-Ir-Ru-Rh-Pt system.These results indicate that chromitites and PGE mineralization in the northern branch formed in a suprasubduction setting from a fluid-rich boninitic melt during active subduction.However,the chromitites and PGE mineralization of the southern branch could have formed in a spreading zone environment.Mantle peridotites have been exposed in the area with remnants of mantle-derived reduced fluids,as indicated by the occurrence of widespread highly carbonaceous graphitized ultrabasic rocks and serpentinites with up to 9.75 wt.%.Fluid inclusions in highly carbonaceous graphitized ultrabasic rocks contain CO,CO_2,CH4,N_2 and the δ~(13)C isotopic composition(-7.4 to-14.5‰) broadly corresponds to mantle carbon.     

Partitioning of Ru, Rh, Pd, Re, Ir, and Au between Cr-bearing spinel, olivine, pyroxene and silicate melts

A series of high temperature experiments was undertaken to study partitioning of several highly siderophile elements (HSE; Ru, Rh, Pd, Re, Os, Ir, Pt and Au) between Cr-rich spinel, olivine, pyroxene and silicate melt. Runs were carried out on a Hawaiian ankaramite, a synthetic eucrite basalt, and a DiAn eutectic melt, at one bar, 19 kbar, and 20 kbar, respectively, in the temperature range of 1200 to 1300°C, at oxygen fugacities between the nickel-nickel oxide (NNO) and hematite-magnetite (HM) oxygen buffers. High oxygen fugacities were used to suppress the formation of HSE-rich “nuggets” in the silicate melts. The resulting oxide and silicate crystals (<100 μm) were analyzed using both SIMS and LA-ICP-MS, with a spatial resolution of 15 to 50 μm. Rhenium, Au and Pd were all found to be incompatible in Cr-rich spinel (D_Re^sp/melt = 0.0012-0.21, D_Au^sp/melt = 0.076, D_Pd^sp/melt = 0.14), whereas Rh, Ru and Ir were all found to be highly compatible (D_Rh^sp/melt = 41-530, D_Ru^sp/melt = 76-1143, D_Ir^sp/melt = 5-22000). Rhenium, Pd, Au and Ru were all found to be incompatible in olivine (D_Re^oliv/melt = 0.017-0.073, D_Pd^oliv/melt = 0.12, D_Au^oliv/melt = 0.12, D_Ru^oliv/melt = 0.23), Re is incompatible in orthopyroxene and clinopyroxene (D_Re^opx/melt = 0.013, D_Re^cpx/melt = 0.18-0.21), and Pt is compatible in clinopyroxene (D_Pt^cpx/melt = 1.5). The results are compared to and combined with previous work on HSE partitioning among spinel-structured oxides, and applied to some natural magmatic suites to demonstrate consistency.     

Partitioning behavior of chlorine and fluorine in the system apatite-melt-fluid. II: Felsic silicate systems at 200 MPa

Hydrothermal experiments were conducted to determine the partitioning of Cl between rhyolitic to rhyodacitic melts, apatite, and aqueous fluid(s) and the partitioning of F between apatite and these melts at ca. 200 MPa and 900-924 °C. The number of fluid phases in our experiments is unknown; they may have involved a single fluid or vapor plus saline liquid. The partitioning behavior of Cl between apatite and melt is non-Nernstian and is a complex function of melt composition and the Cl concentration of the system. Values of D_Cl^apat/melt (wt. fraction of: Cl in apatite/Cl in melt) vary from 1 to 4.5 and are largest when the Cl concentrations of the melt are at or near the Cl-saturation value of the melt. The Cl-saturation concentrations of silicate melts are lowest in evolved, silica-rich melts, so with elevated Cl concentrations in a system and with all else equal, the maximum values of D_Cl^apat/melt occur with the most felsic melt. In contrast, values of D_F^apat/melt range from 11 to 40 for these felsic melts, and many of these are an order of magnitude greater than those applying to basaltic melts at 200 MPa and 1066-1150 °C. The Cl concentration of apatite is a simple and linear function of the concentration of Cl in fluid. Values of D_Cl^fluid/apat for these experiments range from 9 to 43, and some values are an order of magnitude greater than those determined in 200-MPa experiments involving basaltic melts at 1066-1150 °C.In order to determine the concentrations and interpret the behavior of volatile components in magmas, the experimental data have been applied to the halogen concentrations of apatite grains from chemically evolved rocks of Augustine volcano, Alaska; Krakatau volcano, Indonesia; Mt. Pinatubo, Philippines; Mt. St. Helens, Washington; Mt. Mazama, Oregon; Lascar volcano, Chile; Santorini volcano, Greece, and the Bishop Tuff, California. The F concentrations of these magmas estimated from apatite-melt equilibria range from 0.06 to 0.12 wt% and are generally equivalent to the concentrations of F determined in the melt inclusions. In contrast, the Cl concentrations of the magmas estimated from apatite-melt equilibria (e.g., ca. 0.3-0.9 wt%) greatly exceed those determined in the melt inclusions from all of these volcanic systems except for the Bishop Tuff where the agreement is good. This discrepancy in estimated Cl concentrations of melt could result from several processes, including the hypothesis that the composition of apatite represents a comparatively Cl-enriched stage of magma evolution that precedes melt inclusion entrapment prior to the sequestration of Cl by coexisting magmatic aqueous and/or saline fluid(s).     

Experimental determination of F and Cl partitioning between lherzolite and basaltic melt

We experimentally determined F and Cl partition coefficients together with that of 19 trace elements (including REE, U-Th, HFSE and LILE) between basaltic melt and lherzolite minerals: olivine, orthopyroxene, clinopyroxene, plagioclase and garnet. Under conditions from 8 to 25 kbars and from 1,265 to 1,430°C, compatibilities of F and Cl are globally ordered as D ^Cpx/melt > D ^Opx/melt > D ^Grt/melt > D ^Ol/melt > D ^Plag/melt, and D _F ^mineral/melt is larger than D _Cl^mineral/melt. Four other major results were brought to light. (1) Chlorine partition coefficients positively correlate with the jadeite component in orthopyroxene, and increase of the CaTs component promotes Cl incorporation in clinopyroxene. (2) Variations of fluorine partition coefficients correlate strongly with melt viscosity. (3) F and Cl partition coefficients correlate with the Young’s modulus (E ₀) of pyroxene octahedral sites (M sites) and with Raman vibrational modes of pyroxenes. This demonstrates a fundamental interaction between the M site of pyroxenes and the incorporation of F and Cl. (4) We also determined the parameters of the lattice-strain model applied to 3+ cation trace elements for the two M sites in orthopyroxene and clinopyroxene: D ₀^M1, D ₀^M2, r ₀^M1, r ₀^M2, E ₀^M1 and E ₀^M2.     

The partitioning of sulfur between multicomponent aqueous fluids and felsic melts

Sulfur partitioning between melt and fluid phase largely controls the environmental impact of volcanic eruptions. Fluid/melt partitioning data also provide the physical basis for interpreting changes in volcanic gas compositions that are used in eruption forecasts. To better constrain some variables that control the behavior of sulfur in felsic systems, in particular the interaction between different volatiles, we studied the partitioning of sulfur between aqueous fluids and haplogranitic melts at 200 MPa and 750–850 °C as a function of oxygen fugacity (Ni–NiO or Re–ReO₂ buffer), melt composition (Al/(Na?+?K) ratio), and fluid composition (NaCl and CO₂ content). The data confirm a first-order influence of oxygen fugacity on the partitioning of sulfur. Under “reducing conditions” (Ni–NiO buffer), D^fluid/melt is nearly one order of magnitude larger (323?±?14 for a metaluminous melt) than under “oxidizing conditions” (Re–ReO₂ buffer; 74?±?5 for a metaluminous melt). This effect is likely related to a major change in sulfur speciation in both melt and fluid. Raman spectra of the quenched fluids show the presence of H₂S and HS^? under reducing conditions and of SO₄^2? and HSO₄^? under oxidizing conditions, while SO₂ is undetectable. The latter observation suggests that already at the Re–ReO₂ buffer, sulfur in the fluid is almost completely in the S⁶⁺ state and, therefore, more oxidized than expected according to current models. CO₂ in the fluid (up to x_CO2?=?0.3) has no effect on the fluid/melt partitioning of sulfur, neither under oxidizing nor under reducing conditions. However, the effect of NaCl depends on redox state. While at oxidizing conditions, D^fluid/melt is independent of x_NaCl, the fluid/melt partition coefficient strongly decreases with NaCl content under reducing conditions, probably due to a change from H₂S to NaSH as dominant sulfur species in the fluid. A decrease of D^fluid/melt with alkali content in the melt is observed over the entire compositional range under reducing conditions, while it is prominent only between the peraluminous and metaluminous composition in oxidizing experiments. Overall, the experimental results suggest that for typical oxidized, silicic to intermediate subduction zone magmas, the degassing of sulfur is not influenced by the presence of other volatiles, while under reducing conditions, strong interactions with chlorine are observed. If the sulfur oxidation state is preserved during an explosive eruption, a large fraction of the sulfur released from oxidized magmas may be in the S⁶⁺ state and may remain undetected by conventional methods that only measure SO₂. Accordingly, the sulfur yield and the possible climatic impact of some eruptions may be severely underestimated.     

A possible effect of melt structure on the Mg-Fe partitioning between olivine and melt

Partitioning of Mg and Fe²⁺ between olivine and mafic melts has been determined experimentally for eight different synthetic compositions in the temperature range between 1335 and 1425°C at 0.1 MPa pressure and at fo₂ ∼1 log unit below the quartz-fayalite-magnetite buffer. The partition coefficient [K_D = (Fe²⁺/Mg)^ol/(Fe²⁺/Mg)^melt] increases from 0.25 to 0.34 with increasing depolymerization of melt (NBO/T of melt from 0.25-1.2), and then decreases with further depolymerization of melt (NBO/T from 1.2-2.8). These variations are similar to those observed in natural basalt-peridotite systems. In particular, the variation in NBO/T ranges for basaltic-picritic melts (0.4-1.5) is nearly identical to that obtained in the present experiments. Because the present experiments were carried out at constant pressure (0.1 MPa) and in a relatively small temperature range (90°C), the observed variations of Mg and Fe²⁺ partitioning between olivine and melt must depend primarily on the composition or structure of melt. Such variations of K_D may depend on the relative proportions of four-, five-, and six-coordinated Mg²⁺ and Fe²⁺ in melt as a function of degree of NBO/T.     

A theoretical approach to understanding the isotopic heterogeneity of mid-ocean ridge basalt

We have developed an idealized mathematical model to understand the isotopic variability of the mantle and its relation to the observed variations in isotopic ratios ¹⁴³Nd/¹⁴⁴Nd, ⁸⁷Sr/⁸⁶Sr, ¹⁷⁶Hf/¹⁷⁷Hf, ²⁰⁸Pb/²⁰⁴Pb, ²⁰⁶Pb/²⁰⁴Pb, and ²⁰⁷Pb/²⁰⁴Pb measured on mid-ocean ridge basalt (MORB). We consider a simple box model of mantle processes. A single melt region produces a melt fraction F of melt, and the average time since a given parcel of mantle material last visited this region is given by the time scale τ_melt. The melt region fractionates the parent/daughter ratios. Over time this leads to variations in the mantle isotopic ratios as the parent decays to the daughter. Key assumptions are that the half-life of the parent isotope is large compared with τ_melt, that the flow is strongly stirring, and that the mantle has reached a statistical steady state. This enables us to neglect the specifics of the underlying flow. Sampling from our model mantle is dealt with by averaging over a large number N of samples to represent the mixing after melting.The model predicts a probability density for isotopic ratios in MORB which, with exception of the Pb isotopes, are consistent with measurements. Fitting the MORB data to this model gives estimates of the model parameters F, τ_melt, and N. Small melt fractions with F around 0.5% are essential for a good fit, whereas τ_melt and N are less well constrained. τ_melt is estimated at around 1.4 to 2.4 Ga, and N is of the order of hundreds. The model predicts a larger variability for the Pb isotopes than that observed. As has been stated by many previous authors, it appears that fundamental differences exist between the dynamics of Pb isotopes and those of Nd, Sr and Hf isotopes.     

Coexisting hornblendes and biotites from Precambrian gneisses of the south coast of Western Australia

The compositions of coexisting hornblendes and biotites from amphibolite and granulite facies gneisses from the south coast of Western Australia were controlled by host rock composition, paragenesis, metamophic grade, pressure, and oxygen fugacity. The Mg/(Mg + Fe²⁺) and Mn/Fe²⁺ ratios in both minerals and possibly the Al^vi contents of the hornblendes are related to host rock compositions. Metamorphic grade appears to influence, perhaps only indirectly, the Ti, Mn, and Fe³⁺ contents of both minerals and possibly the hornblende Ca content. The higher Ti and lower Mn contents of the granulite facies hornblendes and biotites are attributed to their coexistence with pyroxenes, whereas their lower Fe³⁺/(Fe²⁺ + Fe³⁺) ratios are probably due to lower oxygen fugacity in the granulite facies environment. Grade-related colour variations in both minerals were controlled by their Ti/Fe²⁺ and Fe³⁺/(Fe²⁺ + Fe³⁺ ratios. The relatively low Al^vi contents of the hornblendes suggest low- to moderate-pressure metamorphism.Variations in element distribution coefficients are related to variations in mineral compositions rather than metamorphic grade. Thus K_{D(Al^iv ?Si)} is related to the Al^iv andedenite alkali contents of the hornblendes, K_{D(Fe²⁺ ?Mg)} to the distributions of Al^iv ?Si and Al^vi + Ti + Fe³⁺, K_D(Mn) to the Mn contents of both minerals, and K_D(Al^vi) to the Al^vi contents of the biotites.     

Experimental study of partitioning of tantalum,niobium, manganese,and fluorine between aqueous fluoride fluid and granitic and alkaline melts

This study presents a new set of quantitative experimental data on the partitioning of Ta, Nb, Mn, and F between aqueous F-bearing fluid and water-saturated, Li- and F-rich haplogranite melts with varying alumina/alkali content at T = 650–850 °C and P = 100 MPa. The starting homogeneous glasses were preliminary obtained by melting of three gel mixtures of K₂O-Na₂O-Al₂O₃-SiO₂ composition with a variable Al₂O₃/(Na₂O+K₂O) ratio, ranging from 0.64 (alkaline) and 1.1 (near-normal) to 1.7 (alumina-rich). Ta, Nb, and Mn were originally present in glass only, whereas F was load in both the glass and the solution. The solutionto-glass weight ratio was 1.5–3.0. The compositions of quenched glass were measured by an electronic microprobe, and those of the aqueous solution, with the ICP-MS and ICP-AES methods. The F concentration in the quenched solution was calculated from the mass balance. Under experimental conditions the partition coefficients of Ta, Nb, and Mn between the fluid and the granitic melt (weight ratio ^fluid C _Ta/^melt C _Ta = ^fluid/melt D _Ta) are shown to be extremely low (0.001–0.008 for Ta, 0.001–0.022 for Nb, and 0.002–0.010 for Mn); thus, these metals partition preferentially into the melt. The coefficients ^fluid/melt D _Ta and ^fluid/melt D _Nb generally increase either with increasing alumina ratio A/NKM in the glass composition, or with rising temperature. The experiments also demonstrated that F preferentially concentrates in the melt; and the partition coefficients of F are below 1, being within the range of 0.1–0.7.

     

Li-bearing, disordered Mg-rich tourmaline from a pegmatite-marble contact in the Austroalpine basement units (Styria, Austria)

Pale-blue to pale-green tourmalines from the contact zone of Permian pegmatites to mica schists and marbles from different localities of the Austroalpine basement units (Rappold Complex) in Styria, Austria, are characterized. All these Mg-rich tourmalines have small but significant Li contents, up to 0.29 wt% Li₂O, and can be characterized as dravite, with FeO contents of ?~?0.9–2.7 wt%. Their chemical composition varies from ^X (Na_0.67Ca_0.19?K_0.02?_0.12) ^Y (Mg_1.26Al_0.97Fe²⁺ _0.36Li_0.19Ti⁴⁺ _0.06Zn_0.01?_0.15) ^Z (Al_5.31?Mg_0.69) (BO₃)₃ Si₆O₁₈ ^V (OH)₃? ^W [F_0.66(OH)_0.34], with a?=?15.9220(3), c?=?7.1732(2) Å to ^X (Na_0.67Ca_0.24?K_0.02?_0.07) ^Y (Mg_1.83Al_0.88Fe²⁺ _0.20Li_0.08Zn_0.01Ti⁴⁺ _0.01?_0.09) ^Z (Al_5.25?Mg_0.75) (BO₃)₃ Si₆O₁₈ ^V (OH)₃? ^W [F_0.87(OH)_0.13], with a?=?15.9354(4), c?=?7.1934(4) Å, and they show a significant Al-Mg disorder between the Y and the Z sites (R1?=?0.013–0.015). There is a positive correlation between the Ca content and?<?Y-O?>?distance for all investigated tourmalines (r?≈?1.00), which may reflect short-range order configurations including Ca and Fe²⁺, Mg, and Li. The tourmalines have X_Mg (X_Mg?=?Mg/Mg?+?Fe_total) values in the range 0.84–0.95. The REE patterns show more or less pronounced negative Eu and positive Yb anomalies. In comparison to tourmalines from highly-evolved pegmatites, the tourmaline samples from the border zone of the pegmatites of the Rappold Complex contain relatively low amounts of total REE (~8–36 ppm) and Th (0.1–1.8 ppm) and have low La_N/Yb_N ratios. There is a positive correlation (r?≈?0.91) between MgO of the tourmalines and the MgO contents of the surrounding mica schists. We conclude that the pegmatites formed by anatectic melting of mica schists and paragneisses in Permian time. The tourmalines crystallized from the pegmatitic melt, influenced by the metacarbonate and metapelitic host rocks.     

Melt production during granulite-facies anatexis: experimental data from “primitive” metasedimentary protoliths

We conducted fluid-absent partial melting experiments, at 0.5 and 1.0?GPa in the temperature range 750 to 1000?°C, to investigate the influence of bulk rock Mg ? [100Mg/(Mg+Fe)] and the effects of additional TiO₂ on the granulite-grade anatectic evolution of relatively magnesian metapelites and metagreywackes. In these experiments, melting began between 780 and 830?°C by the incongruent breakdown of biotite to produce quartz-saturated, granulite-facies residual mineral assemblages in equilibrium with H₂O-undersaturated granitic melt. The glass (quenched melt) compositions produced in this study vary little. Generally, the glasses have compositions similar to those of many natural strongly peraluminous leucogranites. The solidus temperatures in both rock types increase with increasing Mg ?, but are unaffected by the presence or absence of a TiO₂ component. At 0.5?GPa the metapelites melted at temperatures up to 50?°C lower than the equivalent metagreywackes, but at 1?GPa there was no discernible difference. This study suggests that the fluid-absent solidus has a steep positive dP/dT slope in metapelites and steep negative dP/dT slope in metagreywackes. The pattern of melt production with increasing temperature is strongly controlled by the upper limit of biotite stability. In TiO₂-free compositions this was found to increase by 15 to 20?°C in the metapelites and by 30 to 40?°C in the metagreywackes, as a function of increasing Mg ? from 49 to 81. The presence of a TiO₂ component increases the upper limit of biotite stability by ～50?°C in the metapelites and by ～80?°C in the metagreywackes, over that observed in the equivalent TiO₂-free compositions. In consequence, in the TiO₂-free samples large pulses of melt (up to 35 wt%) are produced over narrow temperature ranges (as little as 15?°C in these experiments) between 830 and 875?°C. In the TiO₂-bearing samples the major pulse of melt production occurs more gradually between 830 and >900?°C.     

Hydrogen-alkali exchange between silicate melts and two-phase aqueous mixtures: an experimental investigation

Experiments were performed in the three-phase system high-silica rhyolite melt + low-salinity aqueous vapor + hydrosaline brine, to investigate the exchange equilibria for hydrogen, potassium, and sodium in magmatic-hydrothermal systems at 800 °C and 100 MPa, and 850 °C and 50 MPa. The K ^aqm/melt _H,Na and K ^aqm/melt _H,K for hydrogen-sodium exchange between a vapor + brine mixture and a silicate melt are inversely proportional to the total chloride concentration (ΣCl) in the vapor + brine mixture indicating that HCl/NaCl and HCl/KCl are higher in the low-salinity aqueous vapor relative to high-salinity brine. The equilibrium constants for vapor/melt and brine/melt exchange were extracted from regressions of K ^{a q m / m e l t} _{H , N a} and K ^{a q m / m e l t} _{H , K} versus the proportion of aqueous vapor relative to brine in the aqueous mixture (F^aqv) at P and T, expressed as a function of ΣCl. No significant pressure effect on the empirically determined exchange constants was observed for the range of pressures investigated. Model equilibrium constants are: K ^aqv/melt _H,Na(vapor/melt)=26(±1.3) at 100 MPa (800 °C), and 19( ± 7.0) at 50 MPa (850 °C); K ^aqv/melt _H,K=14(±1.1) at 100 MPa (800 °C), and 24(±12) at 50 MPa (850 °C); K ^aqb/melt _H,b(brine/melt)= 1.6(±0.7) at 100 MPa (800 °C), and 3.9(±2.3) at 50 MPa (850 °C); and K ^aqb/melt _H,K=2.7(±1.2) at 100 MPa (800 °C) and 3.8(±2.3) at 50 MPa (850 °C). Values for K ^aqv/melt _H,K and K ^aqb/melt _H,K were used to calculate KCl/HCl in the aqueous vapor and brine as a function of melt aluminum saturation index (ASI: molar Al₂O₃/(K₂O+Na₂O+CaO) and pressure. The model log KCl/HCl values show that a change in melt ASI from peraluminous (ASI = 1.04) to moderately metaluminous (ASI = 1.01) shifts the cooling pathway (in temperature-log KCl/HCl space) of the aqueous vapor toward the andalusite+muscovite+K-feldspar reaction point. Received: 22 August 1996  / Accepted: 5 February 1997     

Olivine/melt transition metal partitioning, melt composition, and melt structure—Melt polymerization and Q-speciation in alkaline earth silicate systems

The two most abundant network-modifying cations in magmatic liquids are Ca²⁺ and Mg²⁺. To evaluate the influence of melt structure on exchange of Ca²⁺ and Mg²⁺ with other geochemically important divalent cations (m-cations) between coexisting minerals and melts, high-temperature (1470-1650 °C), ambient-pressure (0.1 MPa) forsterite/melt partitioning experiments were carried out in the system Mg₂SiO₄-CaMgSi₂O₆-SiO₂ with ?1 wt% m-cations (Mn²⁺, Co²⁺, and Ni²⁺) substituting for Ca²⁺ and Mg²⁺. The bulk melt NBO/Si-range (NBO/Si: nonbridging oxygen per silicon) of melt in equilibrium with forsterite was between 1.89 and 2.74. In this NBO/Si-range, the NBO/Si(Ca) (fraction of nonbridging oxygens, NBO, that form bonds with Ca²⁺, Ca²⁺-NBO) is linearly related to NBO/Si, whereas fraction of Mg²⁺-NBO bonds is essentially independent of NBO/Si. For individual m-cations, rate of change of K_D(m−Mg) with NBO/Si(Ca) for the exchange equilibrium, m^melt + Mg^olivine ? m^olivine + Mg^melt, is linear. K_D(m−Mg) decreases as an exponential function of increasing ionic potential, Z/r² (Z: formal electrical charge, r: ionic radius—here calculated with oxygen in sixfold coordination around the divalent cations) of the m-cation. The enthalpy change of the exchange equilibrium, ΔH, decreases linearly with increasing Z/r² [ΔH = 261(9)-81(3)·Z/r² (Å⁻²)]. From existing information on (Ca,Mg)O-SiO₂ melt structure at ambient pressure, these relationships are understood by considering the exchange of divalent cations that form bonds with nonbridging oxygen in individual Qⁿ-species in the melts. The negative ∂K_D(m−Mg)/∂(Z/r²) and ∂(ΔH)/∂(Z/r²) is because increasing Z/r² is because the cations forming bonds with nonbridging oxygen in increasingly depolymerized Qⁿ-species where steric hindrance is decreasingly important. In other words, principles of ionic size/site mismatch commonly observed for trace and minor elements in crystals, also govern their solubility behavior in silicate melts.     

On the stability of magmatic cordierite and new thermobarometric equations for cordierite-saturated liquids

In this work, we have reviewed a large compositional dataset (571 analyses) for natural and experimental glasses to understand the physico-chemical and compositional conditions of magmatic cordierite crystallization. Cordierite crystallizes in peraluminous liquids (A/CNK ≥1) at temperatures ≥750 °C, pressures ≤700 MPa, variable H₂O activity (0.1–1.0) and relatively low fO₂ conditions (≤NNO ? 0.5). In addition to A/CNK ratio ≥1, a required condition for cordierite crystallization is a Si + Al cation value of the rhyolite liquid of 4 p8O (i.e. calculated on the 8 oxygen anhydrous basis), which is consistent with low Fe³⁺ contents and the absence or low content of non-bridging oxygens (NBO). This geochemical condition is strongly supported by the rare, if not unique, structure of cordierite where the tetrahedral framework is composed almost exclusively of Si and Al cations the sum of which is equal to 4 p8O [i.e. (Mg,Fe)_8/9Al_16/9Si_20/9O₈], indicating that aluminium (and cordierite) saturation is limited by rhyolite liquids with Al = 4 ? Si. Indeed, synthetic or natural systems with Al > 4 ? Si always show metastable glass-in-glass separation or crystallization of refractory minerals such as corundum (Al_16/3O₈) and aluminosilicates (Al_16/5Si_8/5O₈). Multivariate regression analyses of literature data for experimental glasses coexisting with magmatic cordierite produced two empirical equations to independently calculate the T (±13 °C; ME, maximum error = 29 °C) and P (±16 %; ME% = 27 %) conditions of cordierite saturation. The greatest influence on the two equations is exerted by H₂O_melt and Al concentrations, respectively. Testing of these equations with other thermobarometric constraints (e.g. feldspar-liquid, GASP, Grt–Bt and Grt–Crd equilibria) and thermodynamic models (NCKFMASHTO and NCKFMASH systems) was successfully performed for Crd-bearing rhyolites and residual enclaves from San Vincenzo (Tuscany, Italy), Morococala Field (Bolivia) and El Hoyazo (Spain). The reliability of each calculated P–T pair was graphically evaluated using the minimum and maximum P–T–H₂O relationships for peraluminous rhyolite liquids modified after the metaluminous relationships in this work. Both P–T calculations and checking can be easily performed with the attached user-friendly spreadsheet (i.e. Crd-sat_TB).