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1.
Partitioning of Ca, Mn, Mg, and Fe2+ between olivine and melt has been used to examine the influence of energetically nonequivalent nonbridging oxygen in silicate melts. Partitioning experiments were conducted at ambient pressure in air and 1400°C with melts in equilibrium with forsterite-rich olivine (Fo >95 mol%). The main compositional variables of the melts were NBO/T and Na/(Na+Ca). In all melts, the main structural units were of Q4, Q3, and Q2 type with nonbridging oxygen, therefore, in the Q3 and Q2 units.For melts with high Q3/Q2-abundance ratio (corresponding to NBO/T near 1), increasing Na/(Na+Ca) [and Na/(Na+Ca+Mn+Mg+Fe2+)] results in a systematic decrease of the partition coefficients, KCaol/melt, KMnol/melt, KMgol/melt, and KFe2+ol/melt, because of ordering of the network-modifying Ca, Mn, Mg, and Fe2+ among nonbridging oxygen in Q3 and Q2 structural units. This decrease is more pronounced the smaller the ionic radius of the cation. With decreasing Q3/Q2 abundance ratio (less-polymerized melts) this effect becomes less pronounced.Activity-composition relations among network-modifying cations in silicate melts are, therefore, governed by availability of energetically nonequivalent nonbridging oxygen in individual Qn-species in the melt. As a result, any composition change that enhances abundance of highly depolymerized Qn-species will cause partition coefficients to decrease.  相似文献   

2.
Relationships between mineral/silicate melt partition coefficients and melt structure have been examined by combining Ca and Mn olivine/melt partitioning data with available melt structure information. Compositions were chosen so that melts with olivine on their liquidii range in degree of polymerization, NBO/T, from ∼0.5 to ∼2.5 under near isothermal conditions (1350-1400°C). Olivine/melt Ca-Mn exchange coefficients, Ca(olivine)/CaO(melt)/MnO(olivine)/MnO(melt) (KD Ca-Mnolivine/melt), as a function of melt NBO/T have a parabolic shape with a minimum KD Ca-Mnolivine/melt-value at NBO/T near 1. Notably, published KD Fe2+-Mgolivine/melt versus NBO/T functions are also parabolic with a maximum in KD Fe2+-Mgolivine/melt near 1 (Kushiro and Mysen, 2002).The olivine/melt partitioning data are modeled in terms of structural units (Qn-species) in the melt. The NBO/T-value corresponding to the minimum KD Ca-Mnolivine/melt is near that where the abundance ratio of Qn-species, XQ3/XQ2, has its largest value. Therefore, the activity coefficient ratio in the melt, γCa2+(melt)/γMn2+(melt), attains a minimum where the abundance ratio of XQ3/XQ2 is at maximum. It is inferred from this relationship that Ca2+ in the melts is dominantly bonded to nonbridging oxygen (Ca-NBO) in Q3-species, whereas Mn2+ is bonded to nonbridging oxygen (Mn-NBO) in less polymerized Qn-species such as Q2.  相似文献   

3.
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 (fO2) at 0.1 MPa pressure. Total iron oxide content of the starting materials was ∼20 wt%. The fO2 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 fO2 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 fO2 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).  相似文献   

4.
Precise determination of the partitioning of Mg and Fe2+ between olivine and ultramafic melt has been made at pressures from 5 to 13 GPa using a MA-8 type multi-anvil high-pressure apparatus (PREM) installed at Earthquake Research Institute, University of Tokyo. A very short rhenium capsule (<100 μm sample thickness) was adopted to minimize temperature variation within the sample container. Synthetic gels with the composition of the upper mantle peridotite were used as starting materials to promote the homogeneity. Analyses of quenched melts and coexisting olivines were made with an electron probe microanalyzer. The obtained partition coefficient, KD [=(FeO/MgO)ol/(FeO/MgO)melt], decreases from 0.35 to 0.25 with increasing pressure from 5 to 13 GPa, suggesting a negative correlation between pressure and KD above 5 GPa. Our result is consistent with a parabolic relationship between KD and degree of polymerization (NBO/T) of melts reported by previous studies at lower pressures. The negative correlation between pressure and KD suggests that olivine crystallizing in a magma ocean becomes more Mg-rich with depth and that primary magmas generated in the upper mantle become more Fe-rich with depth than previously estimated.  相似文献   

5.
Consideration of experimental data on the distribution of Mg2+ between olivine and silicate liquid clearly demonstrates that the distribution coefficient (KMg) is dependent upon variations in temperature, pressure and melt composition, largely because these variables control the solubility of Mg2+ in the melt phase. Attempts to minimize composition dependence of KMg, utilizing various activity-composition models for silicate melts, have been partially successful. Composition-related effects do not appear to be large, however, for melts of restricted range in composition (e.g., tholeiitic or lunar basalts) as long as the contents of alkalis and the alkali/alumina ratio are relatively small (on a molar basis). For such melts, KMg may be used as a reliable geothermometer. By analogy, these conclusions can be extended to the distribution of other divalent cation such as Fe2+, Mn2+, Ni2+ and Co2+.  相似文献   

6.
The origin and the relationships between the high potassic (HKS) and potassic (KS) suites of the Roman Comagmatic Province and the nature of their primary magmas have been intensively debated over the past 35 years. We have addressed these problems by a study of mineralogy (olivine Fo92-87, Cr-spinel and diopside) and melt inclusions in olivine phenocrysts from a scoria sample of Montefiascone (Vulsini area). This rock is considered as one of the most primitive (MgO=13.5 wt%, NiO=340 ppm; Cr=1275 ppm) in the northern part of the Roman Comagmatic Province. The compositions of both the olivine and their melt inclusions are controlled by two main processes. In the case of the olivine Fo<90.5, fractional crystallization (olivine + diopside + minor spinel) was the principal mechanism of the magma evolution. The olivine (Fo92-90.5) and the Cr-spinel (Cr#=100. Cr/(Cr+Al)=63-73) represent a near-primary liquidus assemblage and indicate the mantle origin of their parental magmas. The compositions of melt inclusions in these olivine phenocrysts correspond to those of poorly fractionated H2O-rich ( 1 wt%) primary melts (MgO=8.4-9.7 wt%,FeOtotal=6-7.5 wt%). They evidence a wide compositional range (in wt%: SiO2=46.5-50, K2O=5.3-2.8, P2O5=0.4-0.2, S=0.26-0.12; Cl=0.05-0.03, and CaO/Al2O3= 0.8-1.15), with negative correlations between SiO2 and K2O, Al2O3 and CaO, as well as positive correlations between K2O, and P2O5, S, Cl, with nearly constant ratios between these elements. These results are discussed in terms of segregation of various mantle-derived melts. The high and constant Mg# [100.Mg/(Mg+Fe2+)] 73-75 of studied melts and their variable Si, K, P, Ca, Al, S contents could be explained by the melting of a refractory lithospheric mantle source, heterogeneously enriched in phlogopite and clinopyroxene (veined mantle source).  相似文献   

7.
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.  相似文献   

8.
This paper reports experiments carried out at 1-atm under conditions of controlled oxygen fugacity, using natural andesites and andesite mixed with augite+synthetic pigeonite or augite+orthopyroxene. The experimental results are used (1) to investigate the controls of Mg# (Mg/[Mg+Fe2+]) and temperature on low-Ca pyroxene stability (pigeonite vs orthopyroxene), (2) to quantify the effects of variations in bulk composition on the position of multiple saturation boundaries in mineral component projection schemes and (3) to develop a thermodynamic model for silica activity for melts saturated with olivine and pyroxene. Over the Mg# range of 0.80–0.30 the minimum temperature of pigeonite stability in natural compositions is equivalent to the Lindsley (1983) boundary determined for pure Ca-Mg-Fe pigeonites. For the low variance, 5-phase assemblage oliv-aug-low-Ca pyroxene-plag-liquid, expressions involving liquid (Na2O+K2O)/(Na2O+K2O+CaO),Mg# and TiO2 content predict temperature and the movement of multiple saturation boundaries in pseudoternary projections in response to changing melt composition. The equilibrium for the low pressure melting of low-Ca pyroxene to olivine+liquid is formulated as a geothermometer and monitor of silica activity. Equilibrium constants estimated from thermochemical data and activities calculated for experimentally produced olivine and pyroxenes are used to develop a model for silica activity in liquid.  相似文献   

9.
Solubility and solution mechanisms in silicate melts of oxidized and reduced C-bearing species in the C-O-H system have been determined experimentally at 1.5 GPa and 1400 °C with mass spectrometric, NMR, and Raman spectroscopic methods. The hydrogen fugacity, fH2, was controlled in the range between that of the iron-wüstite-H2O (IW) and the magnetite-hematite-H2O (MH) buffers. The melt polymerization varied between those typical of tholeiitic and andesitic melts.The solubility of oxidized (on the order of 1-2 wt% as C) and reduced carbon (on the order of 0.15-0.35 wt% as C) is positively correlated with the NBO/Si (nonbridging oxygen per silicon) of the melt. At given NBO/Si-value, the solubility of oxidized carbon is 2-4 times greater than under reducing conditions. Oxidized carbon dioxide is dissolved as complexes, whereas the dominant reduced species in melts are CH3-groups forming bonds with Si4+ together with molecular CH4. Formation of complexes results in silicate melt polymerization (decreasing NBO/Si), whereas solution of reduced carbon results in depolymerization of melts (increasing NBO/Si).Redox melting in the Earth’s interior has been explained with the aid of the different solution mechanisms of oxidized and reduced carbon in silicate melts. Further, effects of oxidized and reduced carbon on melt viscosity and on element partitioning between melts and minerals have been evaluated from relationships between melt polymerization and dissolved carbon combined with existing experimental data that link melt properties and melt polymerization. With total carbon contents in the melts on the order of several mol%, mineral/melt element partition coefficients and melt viscosity can change by several tens to several hundred percent with variable redox conditions in the range of the Earth’s deep crust and upper mantle.  相似文献   

10.
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)/∂XH2O, 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.  相似文献   

11.
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 KD(m−Mg) with NBO/Si(Ca) for the exchange equilibrium, mmelt + Mgolivine ? molivine + Mgmelt, is linear. KD(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 ∂KD(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.  相似文献   

12.
The solubility behavior of H2O in melts in the system Na2O-SiO2-H2O was determined by locating the univariant phase boundary, melt = melt + vapor in the 0.8-2 GPa and 1000°-1300°C pressure and temperature range, respectively. The NBO/Si-range of the melts (0.25-1) was chosen to cover that of most natural magmatic liquids. The H2O solubility in melts in the system Na2O-SiO2-H2O (XH2O) ranges between 18 and 45 mol% (O = 1) with (∂XH2O/∂P)T∼14-18 mol% H2O/GPa. The (∂XH2O/∂P)T is negatively correlated with NBO/Si (= Na/Si) of the melt. The (∂XH2O/∂T)P is in the −0.03 to +0.05 mol% H2O/°C range, and is negatively correlated with NBO/Si. The [∂XH2O/∂(NBO/Si)]P,T is in the −3 to −8 mol% H2O/(NBO/Si) range. Melts with NBO/Si similar to basaltic liquids (∼0.6-∼1.0) show (∂XH2O/∂T)P<0, whereas more polymerized melts exhibit (∂XH2O/∂T)P>0. Complete miscibility between hydrous melt and aqueous fluid occurs in the 0.8-2 GPa pressure range for melts with NBO/Si ≤0.5 at T >1100°C. Miscibility occurs at lower pressure the more polymerized the melt.  相似文献   

13.
Summary Microprobe analyses and X-ray crystal structure refinement of terrestrial and lunar olivines are compared, in order to investigate the influence of temperature and composition on Mg-Fe2+ distribution between M1 and M2 sites.Quenching and heating experiments show that, for the same composition, a temperature increase causes an increase in the (Fe2+/Mg)M1/(Fe2+/Mg)M2 ratio (KD. Such experiments also demonstrate that the intracrystalline Mg-Fe2+ ordering in Ml and M2 sites is very fast and the calculated KD values therefore depend on cooling rate (C.R.), i.e., high KD values = high CR.. On the other hand, for the same cooling rate and temperature, Fe-rich olivine has a KD value higher than that of Mg-rich olivine, since Fe2+ is preferentially ordered in M1 site. Oxygen fugacity variations (QFI and QFM buffers) do not appreciably influence KD.The closure temperature of Mg-Fe2+ ordering between M1-M2 sites of olivine is probably lower than that estimated for orthopyroxene (c. 550–600°C; Saxena et al., 1989), owing to a lesser degree of non-equivalence between MI and M2 sites. The highest temperature that can be detected by KD values of natural olivines is 700–800 °C.
Einfluß von Temperatur und Zusammensetzung auf die Mg-Fe2+ Verteilung in Olivin
Zusammenfassung Mikrosondenuntersucbungen und Strukturverfeinerungen an terrestrischen und lunaren Olivinen werden verglichen, um den Einfluß von Temperatur und Zusammensetzung auf die Mg-Fe2+ Verteilung in der MI und M2 Position zu untersuchen. Experimentelle Untersuchungen belegen, daß bei gleichbleibender chemischer Zusamensetzung, eine Temperaturzunahme eine Zunahme im KD Verhältnis (Fe2+ /Mg)M1/(Fe2+/M9)M2 bedingt. Diese Experimente zeigen weiters, daß die Ordnung der Mg-Fe2+ Kationen im Gitter in den M 1 und M2 Positionen sehr rasch erfolgt und die berechnete KD Werte daher von der Abkühlungsrate (C.R.) abhängen; z. B. hohe KD-Werte = hohe C. R.Andererseits hat bei gleicher Abkühlungsrate und Temperatur Fe-reicher Olivin einen höheren KD Wert als Mg-reicher Olivin, da Fe2+ bevorzugt in die M1 Position eingebaut wird. änderungen in der Sauerstoff-Fugazität (QFI und QFM Buffer) beeinflussen die KD Werte unwesentlich.Die Schließungstemperaturen für die Mg-Fe2+ Ordnung zwischen der M1 und M2 Position in Olivin sind wahrscheinlich niedriger als die von Orthopyroxen (ca. 550–600°C;Saxena et al., 1989); dies wird mit einem niedrigeren Grad an non-equivalence von Ml und M2 erklärt. Die höchsten Temperaturen, die an Hand der KD-Werte an natürlichen Olivinen bestimmt wurden liegen bei 700–800°C.

With 2 Figures  相似文献   

14.
The compositional dependence of the redox ratio (FeO/FeO1.5) 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 Ca0.5K–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  相似文献   

15.
The interdiffusion coefficient of Mg–Fe in olivine (D Mg–Fe) was obtained at 1,400–1,600 °C at the atmospheric pressure with the oxygen fugacity of 10?3.5–10?2 Pa using a diffusion couple technique. The D Mg–Fe shows the anisotropy (largest along the [001] direction and smallest along the [100] direction), and its activation energy (280–320 kJ/mol) is ~80–120 kJ/mol higher than that estimated at lower temperatures. The D Mg–Fe at temperatures of >1,400 °C can be explained by the cation-vacancy chemistry determined both by the Fe3+/Fe2+ equilibrium and by the intrinsic point defect formation with the formation enthalpy of 220–270 kJ/mol depending on the thermodynamical model for the Fe3+/Fe2+ equilibrium in olivine. The formation enthalpy of 220–270 kJ/mol for the point defect (cation vacancy) in olivine is consistent with that estimated from the Mg self-diffusion in Fe-free forsterite. The increase in the activation energy of D Mg–Fe at >1,400 °C is thus interpreted as the result of the transition of diffusion mechanism from the transition metal extrinsic domain to the intrinsic domain at the atmospheric pressure.  相似文献   

16.
The apparent equilibrium constant for the exchange of Fe and Ni between coexisting olivine and sulfide liquid (KD = (XNiS/XFeS)liquid/(XNiSi12O2/XFeSi12O2)olivine; Xi = mole fraction) has been measured at controlled oxygen and sulfur fugacities (fO2 = 10−8.1 to 10−10 and fS2 = 10−0.9 to 10−1.7) over the temperature range 1200 to 1385°C, with 5 to 37 wt% Ni and 7 to 18 wt% Cu in the sulfide liquid. At log fO2 of −8.7 ± 0.1, and log fS2 of −0.9 to −1.7, KD is relatively insensitive to sulfur fugacity, but comparison with previous results shows that KD increases at very low sulfur fugacities. KD values show an increase with the nickel content of the sulfide liquid, but this effect is more complex than found previously, and is greatest at log fO2 of −8.1, lessens with decreasing fO2, and KD becomes independent of melt Ni content at log fO2 ≤ −9.5. The origin of this variation in KD with fO2 and fS2 is most likely the result of nonideal mixing of Fe and Ni species in the sulfide liquid. Such behavior causes activity coefficients to change with either melt oxygen content or metal/sulfur ratio, effects that are well documented for metal-rich sulfide melts.Application of these experimental results to natural samples shows that the relatively large dispersion that exists in KD values from different olivine + sulfide-saturated rock suites can be interpreted as arising from variations in fO2, fS2, and the nickel content of the sulfide liquid. Estimates of fO2 based on KD and sulfide melt composition in natural samples yields a range from fayalite-magnetite-quartz (FMQ)-1 to FMQ-2 or lower, which is in good agreement with previous values determined for oceanic basalts that use glass ferric/ferrous ratios. Anomalously high KD values recorded in some suites, such as Disko Island, probably reflect low fS2 during sulfide saturation, which is consistent with indications of low fO2 for those samples. It is concluded that the variation in KD values from natural samples reflects olivine-sulfide melt equilibrium at conditions within the T-fO2-fS2 range of terrestrial mafic magmas.  相似文献   

17.
We report results of experiments constraining oxygen isotope fractionations between CO2 vapor and Na-rich melilitic melt at 1 bar and 1250 and 1400°C. The fractionation factor constrained by bracketed experiments, 1000.lnαCO2-Na melilitic melt, is 2.65±0.25 ‰ (±2σ; n=92) at 1250°C and 2.16±0.16 ‰ (2σ; n=16) at 1400°C. These values are independent of Na content over the range investigated (7.5 to 13.0 wt. % Na2O). We combine these data with the known reduced partition function ratio of CO2 to obtain an equation describing the reduced partition function ratio of Na-rich melilite melt as a function of temperature. We also fit previously measured CO2-melt or -glass fractionations to obtain temperature-dependent reduced partition function ratios for all experimentally studied melts and glasses (including silica, rhyolite, albite, anorthite, Na-rich melilite, and basalt). The systematics of these data suggest that reduced partition function ratios of silicate melts can be approximated either by using the Garlick index (a measure of the polymerization of the melt) or by describing melts as mixtures of normative minerals or equivalent melt compositions. These systematics suggest oxygen isotope fractionation between basalt and olivine at 1300°C of approximately 0.4 to 0.5‰, consistent with most (but not all) basalt glass-olivine fractionations measured in terrestrial and lunar basalts.  相似文献   

18.
The diffusion coefficients of Fe2+ and Mg in aluminous spinel at ∼20 kb, 950 to 1325°C, and at 30 kb, 1125°C have been determined via diffusion couple experiments and numerical modeling of the induced diffusion profiles. The oxygen fugacity, fO2, was constrained by graphite encapsulating materials. The retrieved self-diffusion coefficients of Fe2+ and Mg at ∼20 kb, 950 to 1325°C, fit well the Arrhenian relation, D = D0exp(−Q/RT), where Q is the activation energy, with D0(Fe) = 1.8 (±2.8) × 10−5, D0(Mg) = 1.9 (±1.4) × 10−5 cm2/s, Q(Fe) = 198 ± 19, and Q(Mg) = 202 ± 8 kJ/mol. Comparison with the data at 30 kb suggests an activation volume of ∼5 cm3/mol. From analysis of compositional zoning in natural olivine-spinel assemblages in ultramafic rocks, previous reports concluded that D(Fe-Mg) in spinel with Cr/(Cr + Al) ≤0.5 is ∼10 times that in olivine. The diffusion data in spinel and olivine have been applied to the problems of preservation of Mg isotopic inhomogeneity in spinel within the plagioclase-olivine inclusions in Allende meteorite and cooling rates of terrestrial ultramafic rocks.  相似文献   

19.
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 = FeO1.5). 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.  相似文献   

20.
The chemical compositions of melt inclusions in a primitive and an evolved basalt recovered from the mid-Atlantic ridge south of the Kane Fracture Zone (23°–24°N) are determined. The melt inclusions are primitive in composition (0.633–0.747 molar Mg/(Mg+Fe2+), 1.01–0.68 wt% TiO2) and are comparable to other proposed parental magmas except in having higher Al2O3 and lower CaO. The primitive melt inclusion compositions indicate that the most primitive magmas erupted in this region are not near primary magma compositions. Olivine and plagioclase microphenocrysts are close to exchange equilibrium with their respective basalt glasses, whose compositions are displaced toward olivine from 1 atm three phase saturation. The most primitive melt inclusion compositions are close to exchange equilibrium with the anorthitic cores of zoned plagioclases (An78.3-An83.1; the hosts for the melt inclusions in plagioclase) and with olivines more forsteritic (Fo89-Fo91) than the olivine microphenocrysts (the hosts for the melt inclusions in olivine). Xenocrystic olivine analyzed is Fo89 but contains no melt inclusions. These observations indicate that olivines have exchanged components with the melt after melt inclusion entrapment, whereas plagioclase compositions have remained the same since melt inclusion entrapment. Common denominator element ratio diagrams and oxide versus oxide variation diagrams show that the melt inclusion compositions, which represent liquids higher along the liquid line of descent, are related to the glass compositions by the fractionation of olivine, plagioclase and clinopyroxene (absent from the mincral assemblage), probably occurring at elevated pressures. A model is proposed whereby clinopyroxene segregates from the melt at elevated pressures (to account for its absence in the erupted lavas that have the chemical imprint of clinopyroxene fractionation). Zoned plagioclases in the erupted lavas are thought to be survivors of decompressional melting during magma ascent. Since similar primitive melt inclusions occur in olivine microphenocrysts and in the cores of zoned plagioclases, any model must account for all phases present.  相似文献   

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