The effect of titanium and phosphorus on ferric/ferrous ratio in silicate melts: an experimental study

The effect of TiO₂ and P₂O₅ on the ferric/ferrous ratio in silicate melts was investigated in model silicate melts at air conditions in the temperature range 1,400–1,550 °C at 1-atm total pressure. The base composition of the anorthite–diopside eutectic composition was modified with 10 wt % Fe₂O₃ and variable amounts of TiO₂ (up to 30 wt %) or P₂O₅ (up to 20 wt %). Some compositions also contained higher SiO₂ concentrations to compare the role of SiO₂, TiO₂, and P₂O₅ on the Fe³⁺/Fe²⁺ ratio. The ferric/ferrous ratio in experimental glasses was analyzed using a wet chemical technique with colorimetric detection of ferrous iron. It is shown that at constant temperature, an increase in SiO₂, TiO₂, and P₂O₅ content results in a decrease in the ferric/ferrous ratio. The effects of TiO₂ and SiO₂ on the Fe³⁺/Fe²⁺ ratio was found to be almost identical. In contrast, adding P₂O₅ was found to decrease ferric/ferrous ratio much more effectively than adding silica. The results were compared with the predictions from the published empirical equations forecasting Fe³⁺/Fe²⁺ ratio. It was demonstrated that the effects of TiO₂ are minor but that the effects of P₂O₅ should be included in models to better describe ferric/ferrous ratio in phosphorus-bearing silicate melts. Based on our observations, the determination of the prevailing fO₂ in magmas from the Fe³⁺/Fe²⁺ ratio in natural glasses using empirical equations published so far is discussed critically.     

The role of phosphorus in rhyolitic liquids as determined from the homogeneous iron redox equilibrium

The redox ratio of iron is used as an indicator of solution properties of silicate liquids in the system (SiO–Al₂O₃–K₂O–FeO–Fe₂O₃–P₂O₅). Glasses containing 80–85 mol% SiO₂ with 1 mol% Fe₂O₃ and compositions covering a range of K₂O/Al₂O₃ were synthesized at 1400°C in air (fixed fO₂). Variations in the ratio FeO/FeO_1.5 resulting from the addition of P₂O₅ are used to determine the solution behavior of phosphorus and its interactions with other cations in the silicate melt. In 80 mol% SiO₂ peralkaline melts the redox ratio, expressed as FeO/FeO_1.5, is unchanged relative to the reference curve with the addition of 3 mol% P₂O₅. Yet, the iron redox ratio in the 85 mol% SiO₂ potassium aluminosilicate melts is decreased relative to phosphorus-free liquids even for small amounts of P₂O₅ (0.5 mol%). The redox ratio in peraluminous melts is decreased relative to phosphorus- free liquids at P₂O₅ concentrations of 3 mol%. In peraluminous liquids, complexing of both Fe⁺³–O–P⁺⁵ and Al⁺³–O–P⁺⁵ occur. The activity coefficient of Fe⁺³ is decreased because more ferric iron can be accommodated than in phosphorus-free liquids. In peralkaline melts, there is no evidence that P⁺⁵ is removing K⁺ from either Al⁺³ or Fe⁺³ species. In chargebalanced melts with 3 mol% Fe₂O₃ and very high P₂O₅ concentrations, phosphorus removes K⁺ from K–O–Fe⁺³ complexes resulting in a redox increase. P₂O₅ should be accommodated easily in peraluminous rhyolitic liquids and phosphate saturation may be suppressed relative to metaluminous rhyolites. In peralkaline melts, phosphate solubility may increase as a result of phosphorus complexing with alkalis. The complexing stoichiometry may be variable, however, and the relative influence of peralkalinity versus temperature on phosphate solubility in rhyolitic melts deserves greater attention.     

Effects of strong network modifiers on Fe<Superscript>3+</Superscript>/Fe<Superscript>2+</Superscript> in silicate melts: an experimental study

The effect of CaO, Na₂O, and K₂O on ferric/ferrous ratio in model multicomponent silicate melts was investigated in the temperature range 1450–1550?°C at 1-atm total pressure in air. It is demonstrated that the addition of these network modifier cations results in an increase of Fe³⁺/Fe²⁺ ratio. The influence of network modifier cations on the ferric/ferrous ratio increases in the order Ca?<?Na?<?K. Some old controversial conceptions concerning the effect of potassium on Fe³⁺/Fe²⁺ ratio in simple model liquids are critically evaluated. An empirical equation is proposed to predict the ferric/ferrous ratio in SiO₂–TiO₂–Al₂O₃–FeO–Fe₂O₃–MgO–CaO–Na₂O–K₂O–P₂O₅ melts at air conditions.     

Source and H2O content of high-MgO magmas in island arc settings: an experimental study of a primitive calc-alkaline basalt from St. Vincent, lesser antilles arc

Liquidus phase relationships have been determined for a high-MgO basalt (STV301: MgO=12.5 wt%, Ni=250 ppm, Cr=728 ppm) from Black Point, St Vincent (Lesser Antilles arc). Piston-cylinder experiments were conducted between 7.5 and 20 kbar under both hydrous and oxidizing conditions. AuPd capsules were used as containers. Compositions of supraliquidus glasses and mass-balance calculations show that Fe loss is < 10% in the majority of experiments. Two series of water concentrations in melt were investigated: (i) 1.5 wt% and (ii) 4.5 wt% H₂O, as determined by SIMS analyses on quenched glasses and with the by difference technique. The Fe³⁺/Fe²⁺ partitioning between Cr-Al spinel and melt and olivine-spinel equilibria show that oxidizing fO₂ were imposed (NNO + 1.5 for the 1.5 wt% H₂O series, NNO + 2.3 for the 4.5 wt% H₂O series). For both series of water concentrations, the liquid is multiply-saturated with a spinel lherzolite phase assemblage on its liquidus, at 1235°C, 11.5 kbar (1.5 wt% H₂O) and 1185°C, 16 kbar (4.5 wt% H₂O). Liquidus phases are homogeneous and comparable to typical mantle compositions. Mineral-melt partition coefficients are generally identical to values under anhydrous conditions. The modal proportion cpx/opx on the liquidus decreases from the 1.5 wt% to the 4.5 wt% H₂O series. The experimental data are consistent with STV301 being a product of partial melting of lherzolitic mantle. Conditions of multiple saturation progressively evolve toward lower temperatures and higher pressures with increasing melt H₂O concentration. Phase equilibria constraints, i.e., the necessity of preserving the mantle signature seen in high-MgO and picritic arc basalts, and glass inclusion data suggest that STV301 was extracted relatively dry (∼ 2 wt% H₂O) from its mantle source. However, not all primary arc basalts are extracted under similarly dry conditions because more hydrous melts will crystallize during ascent and will not be present unmodified at the surface. From degrees of melting calculated from experiments on KLB-1, extraction of a 12.5 wt% MgO melt with ∼ 2 wt% H₂O would require a H₂O concentration of 0.3 wt% in the sub-arc mantle. For mantle sources fluxed with a slab-derived hydrous component, extracted melts may contain up to ∼ 5.5 wt% H₂O.     

The structural role and homogeneous redox equilibria of iron in peraluminous,metaluminous and peralkaline silicate melts

The compositional dependence of the redox ratio (FeO/FeO_1.5) has been experimentally determined in K₂O-Al₂O₃-SiO₂-Fe₂O₃-FeO (KASFF) and K₂O-CaO-Al₂O₃-SiO₂-Fe₂O₃-FeO (KCASFF) silicate melts. Compositions were equilibrated at 1,450° C in air, with 78 mol % SiO₂. KASFF melts have from 1 to 5 mol % Fe₂O₃ and include both peraluminous (K₂O2O₃) and peralkaline (K₂O>Al₂O₃) compositions. KCASFF melts have 1 mol % Fe₂O₃ encompassing peraluminous, metaluminous (CaO+K₂O>Al₂O₃) and peralkaline compositions. Peralkaline KASFF melts with 1 mol % Fe₂O₃ have low and constant values for the redox ratio, whereas in peraluminous melts the redox ratio increases with increasing (K₂O/Al₂O₃). Increasing total iron concentration increases the redox ratio in peraluminous melts and slightly decreases the redox ratio in peralkaline melts. Substituting CaO for K₂O at fixed total iron (1 mol %) increases the redox ratio in both peraluminous and metaluminous KCASFF melts; however, the redox ratio in peralkaline KCASFF melts is not affected by this exchange. These data indicate that Fe³⁺ is in four-fold coordination, with K⁺ or Ca²⁺ providing local charge balance. The tetrahedral ferric species is most stable in peralkaline melts and least stable in peraluminous melts, due to the competition between Al³⁺ and Fe³⁺ for charge balancing cations in the latter melt. Tetrahedral Fe³⁺ is also less stable when Ca²⁺ provides local charge balance. The data are consistent with a network modifying role for Fe²⁺ in the melt.The data are interpreted to reflect the effects of melt composition on the partitioning of K⁺ and Ca²⁺ and Fe³⁺ and Al³⁺ between various species in the melt. These relationships are discussed in terms of homogeneous equilibria between various iron-bearing and iron-free melt species. The results also reflect the effect of liquid composition on the exchange potentials Fe³⁺ Al_–1 and Ca_0.5K_–1. The exchange potentials are relatively constant in peralkaline melts, but decrease in metaluminous and peraluminous melts as both (CaO+K₂O)/(CaO+K₂O+Al₂O₃) and K₂O/CaO decrease. These qualitative observations imply that minerals exhibiting these exchanges will also be similarly affected as liquid composition changes. Present address: Department of Geological Sciences, Virginia Tech, Blacksburg, VA 24061, USA     

The influence of pressure and composition on the viscosity of andesitic melts

The effect of pressure and composition on the viscosity of both anhydrous and hydrous andesitic melts was studied in the viscosity range of 10⁸ to 10^11.5 Pa · s using parallel plate viscometry. The pressure dependence of the viscosity of three synthetic, iron-free liquids (andesite analogs) containing 0.0, 1.06, and 1.96 wt.% H₂O, respectively, was measured from 100 to 300 MPa using a high-P-T viscometer. These results, combined with those from Richet et al. (1996), indicate that viscosities of anhydrous andesitic melts are independent of pressure, whereas viscosities of hydrous melts slightly increase with increasing pressure. This trend is consistent with an increased degree of depolymerization in the hydrous melts. Compositional effects on the viscosity were studied by comparing iron-free and iron-bearing compositions with similar degrees of depolymerization. During experiments at atmospheric and at elevated pressures (100 to 300 MPa), the viscosity of iron-bearing anhydrous melts preequilibrated in air continuously increased, and the samples became paramagnetic. Analysis of these samples by transmission electron microscopy showed a homogeneous distribution of crystals (probably magnetite) with sizes in the range of 10 to 50 nm. No significant difference in the volume fractions of crystals was found in samples after annealing for 170 to 830 min at temperatures ranging from 970 to 1122 K. An iron-bearing andesite containing 1.88 wt.% H₂O, which was synthesized at intrinsic fO₂ conditions in an internally heated pressure vessel, showed a similar viscosity behavior as the anhydrous melts. The continuous increase in viscosity at a constant temperature is attributed to changes of the melt structure due to exsolution of iron-rich phases. By extrapolating the time evolution of viscosity down to the time at which the run temperature was reached, for both the anhydrous (at 1055 K) and the hydrous (at 860 K) iron-bearing andesite, the viscosity is 0.7 log units lower than predicted by the model of Richet et al. (1996). This may be explained by differences in structural properties of Fe²⁺ and Fe³⁺ and their substitutes Mg²⁺, Ca²⁺, and Al³⁺, which were used in the analogue composition.The effect of iron redox state on the viscosity of anhydrous, synthetic andesite melts was studied at ambient pressure using a dilatometer. Reduced iron-bearing samples were produced by annealing melts in graphite crucibles in an Ar/CO atmosphere for different run times. In contrast to the oxidized sample, no variation of viscosity with time and no exsolution of iron oxide phases was observed for the most reduced glasses. This indicates that trivalent iron promotes the exsolution of iron oxide in supercooled melts. With decreasing Fe³⁺/ΣFe ratio from 0.58 to 0.34, the viscosity decreases by ∼1.6 log units in the investigated temperature range between 964 and 1098 K. A more reduced glass with Fe³⁺/ΣFe = 0.21 showed no additional decrease in viscosity. Our conclusion from these results is that the viscosity of natural melts may be largely overestimated when using data obtained from samples synthesized in air.     

Formation and stability of schwertmannite in acidic mining lakes

Schwertmannite (ideal formula: Fe₈O₈(OH)₆SO₄) is typically found as a secondary iron mineral in pyrite oxidizing environments. In this study, geochemical constraints upon its formation are established and its role in the geochemical cycling of iron between reducing and oxidizing conditions are discussed. The composition of surface waters was analyzed and sediments characterized by X-ray diffraction, FTIR spectroscopy and determination of the Fe:S ratio in the oxalate extractable fraction from 18 acidic mining lakes. The lakes are exposed to a permanent supply of pyritegenous ferrous iron from adjacent ground water. In 3 of the lakes the suspended matter was fractionated using ultra filtration and analyzed with respect to their mineral composition. In addition, stability experiments with synthetic schwertmannite were performed. The examined lake surface waters were O₂-saturated and have sulfate concentrations (10.3 ± 5.5 mM) and pH values (3.0 ± 0.6) that are characteristic for the stability window of schwertmannite. Geochemical modeling implied that i) the waters were saturated with respect to schwertmannite, which controlled the activity of Fe³⁺ and sulfate, and ii) a redox equilibrium exists between Fe²⁺ and schwertmannite. In the uppermost sediment layers (1 to 5 cm depth), schwertmannite was detectable in 16 lakes—in 5 of them by all three methods. FTIR spectroscopy also proved its occurrence in the colloidal fraction (1-10 kDa) in all of the 3 investigated lake surface waters. The stability of synthetic schwertmannite was examined as a function of pH (2-7) by a 1-yr experiment. The transformation rate into goethite increased with increasing pH. Our study suggests that schwertmannite is the first mineral formed after oxidation and hydrolysis of a slightly acidic (pH 5-6), Fe(II)-SO₄ solution, a process that directly affects the pH of the receiving water. Its occurrence is transient and restricted to environments, such as acidic mining lakes, where the coordination chemistry of Fe³⁺ is controlled by the competition between sulfate and hydroxy ions (i.e. mildly acidic).     

Calcic amphiboles in calc-alkaline and alkaline magmas: thermobarometric and chemometric empirical equations valid up to 1,130°C and 2.2 GPa

The following article presents constraints of the stability of Mg-rich (Mg/(Mg + Fe²⁺) > 0.5) calcic amphibole in both calc-alkaline and alkaline magmas, testing of previous thermobarometers, and formulation of new empirical equations that take into consideration a large amount of literature data (e.g. more than one thousand amphibole compositions among experimental and natural crystals). Particular care has been taken in choosing a large number of natural amphiboles and selecting quality experimental data from literature. The final database of experimental data, composed of 61 amphiboles synthesized in the ranges of 800–1,130°C and 130–2,200 MPa, indicates that amphibole crystallization occurs in a horn-like P–T stability field limited by two increasing curves (i.e. the thermal stability and an upper limit), which should start to bend back to higher pressures. Among calcic amphiboles, magnesiohornblendes and tschermakitic pargasites are only found in equilibrium with calc-alkaline melts and crystallize at relatively shallow conditions (P up to ~1 GPa). Kaersutite and pargasite are species almost exclusively found in alkaline igneous products, while magnesiohastingsite is equally distributed in calc-alkaline and alkaline rocks. The reliability of previous amphibole applications was checked using the selected experimental database. The results of this testing indicate that none of the previous thermobarometers can be successfully used to estimate the P, T and fO₂ in a wide range of amphibole crystallization conditions. Multivariate least-square analyses of experimental amphibole compositions and physico-chemical parameters allowed us to achieve a new thermobarometric model that gives reasonably low uncertainties (T ± 23.5°C, P ± 11.5%, H₂O_melt ± 0.78wt%) for calc-alkaline and alkaline magmas in a wide range of P–T conditions (up to 1,130°C and 2,200 MPa) and ∆NNO values (±0.37 log units) up to 500 MPa. The ^AK-^[4]Al relation in amphibole can be readily used to distinguish crystals of calc-alkaline liquids from those of alkaline magmas. In addition, several chemometric equations allowing to estimate the anhydrous composition of the melts in equilibrium with amphiboles of calc-alkaline magmas were derived.     

Iron weathering products in a CO2 + (H2O or H2O2) atmosphere: Implications for weathering processes on the surface of Mars

Various iron-bearing primary phases and rocks have been weathered experimentally to simulate possible present and past weathering processes occurring on Mars. We used magnetite, monoclinic and hexagonal pyrrhotites, and metallic iron as it is suggested that meteoritic input to the martian surface may account for an important source of reduced iron. The phases were weathered in two different atmospheres: one composed of CO₂ + H₂O, to model the present and primary martian atmosphere, and a CO₂ + H₂O + H₂O₂ atmosphere to simulate the effect of strong oxidizing agents. Experiments were conducted at room temperature and a pressure of 0.75 atm. Magnetite is the only stable phase in the experiments and is thus likely to be released on the surface of Mars from primary rocks during weathering processes. Siderite, elemental sulfur, ferrous sulfates and ferric (oxy)hydroxides (goethite and lepidocrocite) are the main products in a water-bearing atmosphere, depending on the substrate. In the peroxide atmosphere, weathering products are dominated by ferric sulfates and goethite. A kinetic model was then developed for iron weathering in a water atmosphere, using the shrinking core model (SCM). This model includes competition between chemical reaction and diffusion of reactants through porous layers of secondary products. The results indicate that for short time scales, the mechanism is dominated by a chemical reaction with second order kinetics (k = 7.75 × 10⁻⁵ g⁻¹/h), whereas for longer time scales, the mechanism is diffusion-controlled (De_A = 2.71 × 10⁻¹⁰ m²/h). The results indicate that a primary CO₂- and H₂O-rich atmosphere should favour sulfur, ferrous phases such as siderite or Fe²⁺-sulfates, associated with ferric (oxy)hydroxides (goethite and lepidocrocite). Further evolution to more oxidizing conditions may have forced these precursors to evolve into ferric sulfates and goethite/hematite.     

The effect of water activity on the oxidation and structural state of Fe in a ferro-basaltic melt

Experimental investigations have been performed at T = 1200°C, P = 200 MPa and fH₂ corresponding to H₂O-MnO-Mn₃O₄ and H₂O-QFM redox buffers to study the effect of H₂O activity on the oxidation and structural state of Fe in an iron-rich basaltic melt. The analysis of Mössbauer and Fe K-edge X-ray absorption nearedge structure (XANES) spectra of the quenched hydrous ferrobasaltic glasses shows that the Fe³⁺/ΣFe ratio of the glass is directly related to aH₂O in a H₂-buffered system and, consequently, to the prevailing oxygen fugacity (through the reaction of water dissociation H₂O ↔ H₂ + 1/2 O₂). However, water as a chemical component of the silicate melt has an indistinguishable effect on the redox state of iron at studied conditions. The experimentally obtained relationship between fO₂ and Fe³⁺/Fe²⁺ in the hydrous ferrobasaltic melt can be adequately predicted in the investigated range by the existing empiric and thermodynamic models. The ratio of ferric and ferrous Fe is proportional to the oxygen fugacity to the power of ∼0.25 which agrees with the theoretical value from the stoichiometry of the Fe redox reaction (FeO + ¼ O₂ = FeO_1.5). The mean centre shifts for Fe²⁺ and Fe³⁺ absorption doublets in Mössbauer spectra show little change with increasing Fe³⁺/ΣFe, suggesting no significant change in the type of iron coordination. Similarly, XANES preedge spectra indicate a mixed (C3h, Td, and Oh, i.e., 5-, 4-, and sixfold) coordination of Fe in hydrous basaltic glasses.     

Differentiation and crystallization conditions of basalts from the Kerguelen large igneous province: an experimental study

Phase relations of basalts from the Kerguelen large igneous province have been investigated experimentally to understand the effect of temperature, fO₂, and fugacity of volatiles (e.g., H₂O and CO₂) on the differentiation path of LIP basalts. The starting rock samples were a tholeiitic basalt from the Northern Kerguelen Plateau (ODP Leg 183 Site 1140) and mildly alkalic basalt evolved from the Kerguelen Archipelago (Mt. Crozier on the Courbet Peninsula), representing different differentiation stages of basalts related to the Kerguelen mantle plume. The influence of temperature, water and oxygen fugacity on phase stability and composition was investigated at 500 MPa and all experiments were fluid-saturated. Crystallization experiments were performed at temperatures between 900 and 1,160°C under oxidizing (log fO₂ ~ ΔQFM + 4) and reducing conditions (log fO₂ ~ QFM) in an internally heated gas-pressure vessel equipped with a rapid quench device and a Pt-Membrane for monitoring the fH₂. In all experiments, a significant influence of the fO₂ on the composition and stability of the Mg/Fe-bearing mineral phases could be observed. Under reducing conditions, the residual melts follow a tholeiitic differentiation trend. In contrast, melts have high Mg# [Mg²⁺/(Mg²⁺ + Fe²⁺)] and follow a calk-alkalic differentiation trend at oxidizing conditions. The comparison of the natural phenocryst assemblages with the experimental products allows us to constrain the differentiation and pre-eruptive conditions of these magmas. The pre-eruptive temperature of the alkalic basalt was about 950–1,050°C. The water content of the melt was below 2.5 wt% H₂O and strongly oxidizing conditions (log fO₂ ~ ΔQFM + 2) were prevailing in the magma chamber prior to eruption. The temperature of the tholeiitic melt was above 1,060°C, with a water content below 2 wt% H₂O and a log fO₂ ~ ΔQFM + 1. Early fractionation of clinopyroxene is a crucial step resulting in the generation of silica-poor and alkali-rich residual melts (e.g., alkali basalt). The enrichment of alkalis in residual melts is enhanced at high fO₂ and low aH₂O.     

Partitioning of Ni2+, Co2+, Fe2+, Mn2+ and Mg2+ between olivine and silicate melts: compositional dependence of partition coefficient

Partitioning of Ni²⁺, Co²⁺, Fe²⁺, Mn²⁺ and Mg²⁺ between olivine and silicate melts has been determined near the join (Mg_0.5·-Fe_0.5)₂SiO₄-K₂O 4SiO₂ and for seven different basaltic compositions. The experiments were made at 1 atm total pressure, 1500-1100°C, and under moderate to reducing oxygen fugacities. The concentration factor, defined as K^MO = (MO)^ol/(MO)^liq (molar ratio), increases markedly for all the cations studied as the olivine component of the liquid decreases. Much of the increase in K^MO is considered as due to the compositional effect of the coexisting liquid: the temperature effect on K^MO is probably opposite to the compositional effect (K^MO decreases as temperature decreases).The partition coefficient K^MO-MgO = (MO/MgO)^ol/(MO/MgO)^liq for the reaction, M_ol²⁺ + Mg_liq²⁺ = M_liq²⁺ + Mg_ol²⁺. is relatively constant over a wide range of SiO₂ content of the liquid, except in the case of Ni²⁺. The partition coefficients have similar ranges both in synthetic and natural rock systems: K^NiO-MgO = 1.8–3.0, K^CoO-MgO = 0.6–0.8, K^FeO-MgO = 0.27–0.38, and K^MnO-MgO = 0.23–0.32. There is a systematic variation in the partition coefficient K^MO-MgO with the composition of liquid; K^MO-MgO increases with increasing SiO₂ content of melt. The partition coefficients for Co²⁺, Fe²⁺ and Mn²⁺ are useful to test the equilibration of olivine with magma of a wide compositional range.     

Iron-bearing silicate melts: Relations between pressure and redox equilibria

Mossbauer spectroscopy has been used to determine the redox equilibria of iron and structure of quenched melts on the composition join Na₂Si₂O₅-Fe₂O₃ to 40 kbar pressure at 1400° C. The Fe³⁺/ΣFe decreases with increasing pressure. The ferric iron appears to undergo a gradual coordination transformation from a network-former at 1 bar to a network-modifier at higher (≧10 kbar) pressure. Ferrous iron is a network-modifier in all quenched melts. Reduction of Fe³⁺ to Fe²⁺ and coordination transformation of remaining Fe³⁺ result in depolymerization of the silicate melts (the ratio of nonbridging oxygens per tetrahedral cations, NBO/T, increases). It is suggested that this pressure-induced depolymerization of iron-bearing silicate liquids results in increasing NBO/T of the liquidus minerals. Furthermore, this depolymerization results in a more rapid pressure-induced decrease in viscosity and activation energy of viscous flow of iron-bearing silicate melts than would be expected for iron-free silicate melts with similar NBO/T.     

Time-dependent changes of the electrical conductivity of basaltic melts with redox state

The electrical conductivity of basaltic melts has been measured in real-time after fO₂ step-changes in order to investigate redox kinetics. Experimental investigations were performed at 1 atm in a vertical furnace between 1200 and 1400 °C using air, pure CO₂ or CO/CO₂ gas mixtures to buffer oxygen fugacity in the range 10⁻⁸ to 0.2 bars. Ferric/ferrous ratios were determined by wet chemical titrations. A small but detectable effect of fO₂ on the electrical conductivity is observed. The more reduced the melt, the higher the conductivity. A modified Arrhenian equation accounts for both T and fO₂ effects on the electrical conductivity. We show that time-dependent changes in electrical conductivity following fO₂ step-changes monitor the rate of Fe²⁺/Fe³⁺ changes. The conductivity change with time corresponds to a diffusion-limited process in the case of reduction in CO-CO₂ gas mixtures and oxidation in air. However, a reaction at the gas-melt interface probably rate limits oxidation of the melt under pure CO₂. Reduction and oxidation rates are similar and both increase with temperature. Those rates range from 10⁻⁹ to 10⁻⁸ m²/s for the temperature interval 1200-1400 °C and show activation energy of about 200 kJ/mol. The redox mechanism that best explains our results involves a cooperative motion of cations and oxygen, allowing such fast oxidation-reduction rates.     

Solution mechanisms of H2O in depolymerized peralkaline melts

Solubility mechanisms of water in depolymerized silicate melts quenched from high temperature (1000°-1300°C) at high pressure (0.8-2.0 GPa) have been examined in peralkaline melts in the system Na₂O-SiO₂-H₂O with Raman and NMR spectroscopy. The Na/Si ratio of the melts ranged from 0.25 to 1. Water contents were varied from ∼3 mol% and ∼40 mol% (based on O = 1). Solution of water results in melt depolymerization where the rate of depolymerization with water content, ∂(NBO/Si)/∂X_H2O, decreases with increasing total water content. At low water contents, the influence of H₂O on the melt structure resembles that of adding alkali oxide. In water-rich melts, alkali oxides are more efficient melt depolymerizers than water. In highly polymerized melts, Si-OH bonds are formed by water reacting with bridging oxygen in Q⁴-species to form Q³ and Q² species. In less polymerized melts, Si-OH bonds are formed when bridging oxygen in Q³-species react with water to form Q²-species. In addition, the presence of Na-OH complexes is inferred. Their importance appears to increase with Na/Si. This apparent increase in importance of Na-OH complexes with increasing Na/Si (which causes increasing degree of depolymerization of the anhydrous silicate melt) suggests that water is a less efficient depolymerizer of silicate melts, the more depolymerized the melt. This conclusion is consistent with recently published ¹H and ²⁹Si MAS NMR and ¹H-²⁹Si cross polarization NMR data.     

Redox equilibria of iron and silicate melt structure: Implications for olivine/melt element partitioning

Olivine/melt partitioning of ΣFe, Fe²⁺, Mg²⁺, Ca²⁺, Mn²⁺, Co²⁺, and Ni²⁺ has been determined in the systems CaO-MgO-FeO-Fe₂O₃-SiO₂ (FD) and CaO-MgO-FeO-Fe₂O₃-Al₂O₃-SiO₂ (FDA3) as a function of oxygen fugacity (f_O2) at 0.1 MPa pressure. Total iron oxide content of the starting materials was ∼20 wt%. The f_O2 was to used to control the Fe³⁺/ΣFe (ΣFe: total iron) of the melts. The Fe³⁺/ΣFe and structural roles of Fe²⁺ and Fe³⁺ were determined with ⁵⁷Fe resonant absorption Mössbauer spectroscopy. Changes in melt polymerization, NBO/T, as a function of f_O2 was estimated from the Mössbauer data and existing melt structure information. It varies by ∼100% in melts coexisting with olivine in the FDA3 system and by about 300% in the FD system in the Fe³⁺/ΣFe range of the experiments (0.805-0.092). The partition coefficients ( in olivine/wt% in melt) are systematic functions of f_O2 and, therefore, NBO/T of the melt. There is a -minimum in the FDA3 system at NBO/T-values corresponding to intermediate Fe³⁺/ΣFe (0.34-0.44). In the Al-free system, FD, where the NBO/T values of melts range between ∼1 and ∼2.9, the partition coefficients are positively correlated with NBO/T (decreasing Fe³⁺/ΣFe). These relationships are explained by consideration of solution behavior in the melts governed by Qⁿ-unit distribution and structural changes of the divalent cations in the melts (coordination number, complexing with Fe³⁺, and distortion of the polyhedra).     

Ferric-ferrous ratio and oxygen fugacity calculations for primitive mantle-derived melts: calibration of an empirical technique

Summary Several experimentally-based, empirical calibrations of the fO₂ of natural silicate melts at atmospheric pressure as a function of melt composition, melt Fe²⁺/Fe³⁺, and crystallization temperature have been developed (e.g.Sack et al., 1980;Kilinc et al., 1983;Kress andCarmichael, 1988;Borisov andShapkin, 1990). Cr-Al spinel is a liquidus phase of primitive mantle-derived melts, and is commonly found as inclusions in near-liquidus phenocrysts (mainly olivine). The established atmospheric pressure correlation between Fe²⁺/Fe³⁺ values in spinel and coexisting melts over a broad range of basaltic compositions (Maurel andMaurel, 1982) can be used to calculate the Fe²⁺/Fe³⁺ value of a melt if the composition of the equilibrium spinel is known. Compositions and crystallization temperatures of primitive melts can be determined by experimental studies of melt inclusions trapped by early-formed refractory phenocrysts. Thus, the association of spinel and melt inclusions in early liquidus phenocrysts can be used to estimate fO₂ conditions at the time of their crystallization.In this paper, we present a calibration of this method and discuss its applications. We conclude that combination of the equations ofMaurel andMaurel (1982) andBorisov andShapkin (1990) can be used to calculate fO₂ with an accuracy of ±0.71og units, when liquidus spinels have TiO₂ <2.5 wt% and Cr₂O₃ > 13 wt.%, and melt compositions are in the range from basaltic to picritic with H₂O contents <6 wt.%.Using this technique we find NNO fO₂ values of –0.8 to –1.4 for MORB dredged at the VEMA Fracture Zone in the Atlantic, and 0 to + 1 for Tongan high-Ca boninites.

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Die Berechnung von Fe²⁺/Fe³⁺ und der Sauerstoff-Fugazitäten für primitive Mantelschmelzen: Kalibration einer empirischen Methode

Zusammenfassung Empirische, auf Experimenten basierende, Kalibrationen zur Berechnung von fO₂ natürlicher Silikatschmelzen bei atmosphärischem Druck in Abhängigkeit von der Schmelzzusammensetzung, des Fe²⁺/Fe³⁺ Verhältnisses und der Kristallisationstemperatur wurden z.B. vonSack et al. (1980),Kilinc et al. (1983),Kress undCarmichael (1988) undBorisov undShapkin (1980) entwickelt. Cr-Al-Spinell ist eine Liquidusphase primitiver Mantelschmelzen und kommt üblicherweise als Einschluß in near-liquidus Phänokristallen (hauptsächlich in Olivin) vor. Die Korrelation des Atmosphärendruckes zwischen Fe²⁺/Fe³⁺ in Spinell und koexistierender Schmelze kann dazu verwendet werden, das Verhältnis von Fe²⁺/Fe³⁺ der Schmelze für einen weiten Bereich basaltischer Zusammensetzungen zu berechnen, wenn die Zusammensetzung des im Gleichgewicht gebildeten Spinells bekannt ist (Maurel undMaurel, 1982). Die Zusammensetzungen und Kristallisationstemperaturen primitiver Schmelzen können durch experimentelle Studien von Schmelzeinschlüssen, die in früh gebildeten refraktären Phänokristallen eingeschlossen wurden, ermittelt werden. Daher lassen sich Spinelle und assoziierte Schmelzeinschlüsse in frühen Liquidus-Phänokristallen dazu benützen, die fO₂-Bedingungen während der Kristallisation abzuschätzen.In dieser Arbeit präsentieren wir eine neue Kalibration dieser Methode und diskutieren ihre Anwendungen. Wir schlußfolgern, daß unter Kombination der verwendeten Gleichungen vonMaurel undMaurel (1982) sowie vonBorisov undShapkin (1990) fO₂ mit einer Genauigkeit von ±0.7 log Einheiten berechnet werden kann, soferne die Liquidus-Spinelle < 2.5 Gew.% TiO₂ und > 13 Gew.% Cr₂O₃ haben und die Schmelzzusammensetzungen von basaltisch bis pikritisch, mit maximal 6 Gew.% H₂O, reichen.Unter Verwendung dieser Technik wurden die NNO fO₂ Werte für die von der VEMA Fracture Zone im Atlantik stammenden MORB Proben mit 0.8 bis - 1.4, die der der High-Ca Boninite von Tonga mit 0 bis + 1 bestimmt.

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With 7 Figures     

Experiments on liquid immiscibility in silicate melts with H2O, P, S, F and Cl: implications for natural magmas

Isobaric (200 MPa) experiments have been performed to investigate the effects of H₂O alone or in combination with P, S, F or Cl on liquid-phase separation in melts in the systems Fe₂SiO₄–Fe₃O₄–KAlSi₂O₆–SiO₂, Fe₃O₄–KAlSi₂O₆–SiO₂ and Fe₃O₄–Fe₂O₃–KAlSi₂O₆–SiO₂ with or without plagioclase (An₅₀). Experiments were heated in a rapid-quench internally heated pressure vessel at 1,075, 1,150 or 1,200 °C for 2 h. Experimental fO₂ was maintained at QFM, NNO or MH oxygen buffers. H₂O alone or in combination with P, S or F increases the temperature and composition range of two-liquid fields at fO₂ = NNO and MH buffers. P, S, F and Cl partition preferentially into the Fe-rich immiscible liquid. Two-liquid partition coefficients for Fe, Si, P and S correlate well with the degree of polymerization of the SiO₂-rich liquid and plot on similar but distinct power-law curves compared with equivalent anhydrous or basaltic melts. The addition of 2 wt% S to the system Fe₃O₄–Fe₂O₃–KAlSi₂O₆–SiO₂ stabilizes three immiscible melts with Fe-, FeS- and Si-rich compositions. H₂O-induced suppression of liquidus temperatures in the experimental systems, considered with the effects of pressure on the temperature and composition ranges of two-liquid fields in silicate melts, suggests that liquid-phase separation may be stable in some H₂O-rich silicate magmas at pressures in excess of 200 MPa.     

Iron in monticellite as an oxygen barometer for kimberlite magmas

Monticellite is a common magmatic mineral in the groundmass of kimberlites. A new oxygen barometer for kimberlite magmas is calibrated based on the Fe content of monticellite, CaMgSiO₄, in equilibrium with kimberlite liquids in experiments at 100 kPa from 1,230 to 1,350°C and at logfO₂ from NNO-4.1 to NNO+5.3 (where NNO is the nickel–nickel oxide buffer). The XFe_Mtc/XFe_liq was found to decrease with increasing fO₂, consistent with only Fe²⁺ entering the monticellite structure. Although the XFe-in-monticellite varies with temperature and composition, these dependencies are small compared to that with fO₂. The experimental data were fitted by weighted least square regression to the following relationship: \Updelta \textNNO = \frac{ log[ 0.858( ±0.021)\fracX_\textFe^\textLiq X_\textFe^\textMtc ] - 0.139( ±0.022) }0.193( ±0.004) \Updelta {\text{NNO}} = \frac{{\left\{ {\log \left[ {0.858( \pm 0.021)\frac{{X_{\text{Fe}}^{\text{Liq}} }}{{X_{\text{Fe}}^{\text{Mtc}} }}} \right] - 0.139( \pm 0.022)} \right\}}}{0.193( \pm 0.004)} where ΔNNO is the fO₂ relative to that of the Nickel-bunsenite (NNO) buffer and XFe_liq/XFe_Mtc is the ratio of mole fraction of Fe in liquid and Fe-in-monticellite (uncertainties at 2σ). The application of this oxygen barometer to natural kimberlites from both the literature and our own investigations, assuming the bulk rock FeO is that of their liquid FeO, revealed a range in fO₂ from NNO-3.5 to NNO+1.7. A range of Mg/(Mg + Fe²⁺) (Mg#) for kimberlite melts of 0.46–0.88 was derived from the application of the experimentally determined monticellite-liquid Kd Fe²⁺–Mg to natural monticellites. The range in Mg# is broader and less ultramafic than previous estimates of kimberlites, suggesting an evolution under a wide range of petrologic conditions.     

Mineral-solution equilibria—IV. Solubilities and the thermodynamic properties of FeCl20 in the system Fe2O3-H2-H2O-HCl

The solubility of hematite in chloride-bearing hydrothermal fluids was determined in the temperature range 400–600°C and at 1000 and 2000 bars using double-capsule, rapid-quench hydrothermal techniques and a modification of the Ag + AgCl buffer method (Frantz and Popp, 1979). The changes in the molalities of associated hydrogen chloride () as a function of the molality of total iron in the fluid at constant temperature and pressure were used to identify the predominant species of iron in the hydrothermal fluid. The molality of associated HCl varied from 0.01 to 0.15. Associated FeCl₂⁰ was found to be the most abundant species in equilibrium with hematite. Determination of Cl/Fe in the fluid in equilibrium with hematite yields values approximately equal to 2.0 suggesting that ferrous iron is the dominant oxidation state.The equilibrium constant for the reaction Fe₂O₃ + 4HCl⁰ + H₂ = 2FeCl₂⁰ + 3H₂O was calculated and used to estimate the difference in Gibbs free energy between FeCl₂⁰ and HCl⁰ in the temperature range 400–600°C at 1000 and 2000 bars pressure.