首页 | 本学科首页   官方微博 | 高级检索  
相似文献
 共查询到20条相似文献，搜索用时 390 毫秒
1.
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   

2.
The critical role of iron on crystal-silicate liquid relationships and melt differentiation is mainly controlled by the redox conditions prevailing in magmas, but the presently available database merely constrains the thermodynamic properties of iron-bearing components in strongly reduced and anhydrous molten silicate where iron is in the ferrous form. This paper provides new standard states for pure ferrous (FeOliq) and ferric (Fe2O3liq) molten iron oxides and extends the experimental database towards oxidizing and water-bearing domains. Iron-iridium, iron-platinum alloys, magnetite or hematite were equilibrated with synthetic silicic liquids at high temperature and high pressure under controlled oxygen fugacity (fO2) to determine activity-composition relationships for FeOliq and Fe2O3liq. Between 1000 and 1300°C, the fO2 ranges from that in air to 3-log units below that of the nickel-nickel oxide buffer (NNO). Experiments were performed on both anhydrous and hydrous melts containing up to 6-wt.% water. Incorporation of water under reducing conditions increases the activity coefficient of FeOliq but has an opposite effect on Fe2O3liq. As calcium is added to system, the effect of water becomes weaker and is inverted for Fe2O3liq. Under oxidizing conditions, water has a negligible effect on both activities of FeOliq and Fe2O3liq. In contrast, changes in redox conditions dominate the activity coefficients of both FeOliq and Fe2O3liq, which increase significantly with increasing fO2. The present results combined with the previous work provide a specific database on the energetics of iron in silicate melts that cover most of the condition prevailing in natural magmas.  相似文献   

3.
Mössbauer spectroscopy was applied to study the valence state of iron in chromite from massive, nodular and disseminated podiform chromitite ores of the Luobasa ophiolite massif of Tibet. The results show that Fe3+/ΣFe = 0.42 in chromite from massive ore, and Fe3+/ΣFe = 0.22 in chromite from nodular and disseminated ores. The massive ore records traces of ultra high pressure mineralogical assemblages, such as diamond inclusions in OsIr alloys, exsolution lamellae of coesite and diopside in chromite, inclusions of metal‐nitrides, native iron and others, which suggests a strongly reducing environment. In contrast, chromite from nodular and disseminated ore contains abundant low‐pressure OH‐bearing mineral inclusions whose formation requires a more oxidizing environment. The high value of Fe3+/ΣFe in the ‘reduced’ massive ore is explained by crystallographic stabilization of Fe3+ in a high‐pressure polymorph of chromite deep in the upper mantle despite low ambient fO2 conditions. The presence of high‐pressure phases within the massive chromitite ore requires that the latter, together with its host peridotite, was transported in the solid state from a highly reduced deep mantle environment to shallow depths beneath an ocean spreading centre. It is suggested that in the low‐pressure environment of the spreading centre, the deep‐seated, reduced, massive chromitites partially reacted with their host peridotite in the presence of hydrous melt, yielding the nodular and disseminated chromitite ores. The preponderance of evidence suggests that the latter interaction involved boninitic melts in a supra‐subduction zone environment as proposed previously.  相似文献   

4.
Enthalpies of dissolution in HF solutions have been measured at 323 K for a series of hydrous trachyte glasses. Enthalpies of mixing between water and molten trachyte have then been calculated from heat capacity data for the same set of samples and available enthalpy for pure water. The moderately negative enthalpies of mixing suggested at 1 bar by the measurements made on glasses almost disappear when trachyte liquids and water are referred to the same temperature, and particularly so when enthalpies of mixing are calculated for a few kbars pressure. As found for albite and phonolite liquids, trachyte melts thus appear to mix nearly ideally as far as enthalpy is concerned. These results imply that the enthalpy of exsolution of water from magmas is very small or negligible under the P-T-X conditions relevant to trachytic volcanism, even for complete degassing of up to 5 wt% H2O. Furthermore, the viscosity increase associated with exsolution-driven cooling is negligible compared to the decrease caused directly by water exsolution.  相似文献   

5.
The analysis of available data on the Fe3+/Fe2+ ratio of impact-produced glasses showed that tektites and some other types of impact glasses are reduced compared with the precursor target material. Possible reasons for the change in the degree of iron oxidation in the impact process are still debatable. Based on the analysis of redox reactions in relatively simple systems with iron in different oxidation states (Fe-O and SiO2-FeO-Fe2O3) and the available data on the influence of temperature, oxygen partial pressure (pO2), and total pressure (P tot) on the Fe3+/Fe2+ ratio of silicate melts, a model was proposed suggesting that the lower Fe3+/Fe2+ values of tektites formed in the impact process compared with the initial target material could be related to the characteristics of oxygen regime during the decompression stage following shock compression. One of the main prerequisites for the occurrence of reduction reactions involving iron and other elements is the attainment of high temperatures (>1800–2000°C) at a certain stage of decompression, providing the complete melting and partial evaporation of the material. When the vapor pressure in the system becomes equal to the total pressure during adiabatic decompression, a further decrease in P tot will be inevitably accompanied by a decrease in pO2 and, correspondingly, partial reduction of Fe3+ to Fe2+ in the melt. The reactions of decompression reduction occur under closed-system conditions and do not require oxygen removal from the system. The higher the temperature and Fe3+/Fe2+ ratio of the melt, the more extensive iron reduction can be observed during the final stages of decompression. If the temperatures attained during decompression after an impact event are sufficient (>2500–3000°C) for the complete evaporation of the material, the melt produced during subsequent condensation must be significantly more reduced than the initial material. The final stage of the impact process is characterized by a catastrophic expansion of the explosion cloud, condensation, and rapid cooling. During this stage, the system is already not closed. The quenched glasses of this stage record the redox state of earlier melts. In addition, they can contain microinclusions of the products of nonequilibrium vapor condensation with iron compounds of different oxidation states, including metallic iron and iron oxides (wüstite, magnetite, and hematite).  相似文献   

6.
Crystal-structure modeling of experimental Ca-rich clinopyroxenes [Ca + Na > 0.5 apfu; Mg/(Mg + Fe2+) > 0.7] coexisting with basic and ultrabasic melts was utilized for calibration of geobarometers based on unit-cell volume (Vcell) vs M1-site volume (VM1). The clinopyroxene database includes over one hundred experiments from literature and sixteen previously unpublished experiments on basanite and picrobasalt starting materials. The coexisting melts span a wide range of petrologically relevant anhydrous and hydrous compositions (from quartz-normative basalt to nephelinite, excluding high-Al basalts and melts coexisting with garnet or melilite) at pressure conditions pertinent to the earth's crust and uppermost mantle (P= 0–24 kbar) in a variety of fO 2 conditions (from CCO-buffered to air-buffered) and mineral assemblages (Cpx ± Opx ± Pig ± Ol ± Plag ± Lc ± Ne ± Spl ± Amp ± Ilm). As previously found for near-liquidus products of basaltic melts, the experimental clinopyroxenes follow two distinct trends: (i) at a given P, Vcell is linearly and negatively correlated with VM1. This corresponds with the extent of Tschermak-type substitutions, which depends strongly on aSiO2 and a CaO; (ii) for a fixed melt composition, Vcell and VM1 decrease linearly as P increases, due to a combination of M1, M2 and T site exchanges. Despite the chemical complexity of these relationships, P could be modeled as a linear function of Vcell and VM1. A simplified solution for anhydrous magmas reproduced the experimental pressures with an uncertainty of 1.75 kbar (=1 ; max. dev. = 5.5 kbar; N = 135). An expanded T-dependent solution capable of recovering the measured pressures of both anhydrous and hydrous experiments with an uncertainty of 1.70 kbar (=1 ; max. dev. = 5.4 kbar; N = 157) was obtained by correcting unit-cell and M1-site volumes for thermal expansivity and compressibility. The corrected formulation is more resistant to the effects of temperature variations and is therefore recommended. Nevertheless, it requires an independent, accurate estimate of crystallization T. Underestimating T by 20 °C propagates into a 1-kbar increase of calculated P. The applicability of the T-dependent formulation was tested on hydrous ultramafic to gabbroic rocks of the southern Adamello batholith for which P-T evolution could independently be constrained by field observation, petrography and experimentally determined phase relations. The pressure estimates obtained by clinopyroxene structural geobarometry closely matched those predicted by phase equilibria of a picrobasaltic melt parental to the investigated magmatic rocks. To facilitate application of the present geobarometers, both anhydrous and corrected solutions were implemented as MS-DOS® and UNIX® software programs (CpxBar) designed to permit retrieval of the pressure of crystallization directly from a chemical analysis or from uncorrected unit-cell and M1-site volume X-ray data.  相似文献   

7.
Ferric-ferrous ratios have been measured in 22 experiments on three natural compositions equilibrated at known temperature (950°–1100° C) and oxygen fugacity, and at water-saturated conditions over a pressure range from 0.05 to 0.2 GPa. There does not appear to be any reaction between the melt and the capsule material that affects the redox state of the iron in the melt. An empirical expression for the anhydrous behavior of the redox state of iron in each of these compositions has also been determined at 1 bar as a function of temperature and oxygen fugacity. A direct comparison of the hydrous ferric-ferrous values with the calculated anhydrous values shows that the dissolution of water in a per-alkaline rhyolite, andesite, and an augite minette has no effect on the redox state of the iron in these melts. This result parallels the effect of water on sulfide speciation in basaltic melts, and confirms published results on experimental hydrous basalts.  相似文献   

8.
The influence of oxygen fugacity (fO2) and temperature on the valence and structural state of iron was experimentally studied in glasses quenched from natural aluminosilicate melts of granite and pantellerite compositions exposed to various T-fO2 conditions (1100–1420°C and 10?12–10?0.68 bar) at a total pressure of 1 atm. The quenched glasses were investigated by Mössbauer spectroscopy. It was shown that the effect of oxygen fugacity on the redox state of iron at 1320–1420°C can be described by the equation log(Fe3+/Fe2+) = k log(fO2) + q, where k and q are constants depending on melt composition and temperature. The Fe3+/Fe2+ ratio decreases with decreasing fO2 (T = const) and increasing temperature (fO2 = const). The structural state of Fe3+ depends on the degree of iron oxidation. With increasing Fe3+/Fe2+ ≥ 1, the dominant coordination of Fe3+ changes from octahedral to tetrahedral. Ferrous iron ions occur in octahedral (and/or five-coordinated) sites independent of Fe3+/Fe2+.  相似文献   

9.
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   

10.
Quaternary volcanism in the Mt. Shasta region has produced primitive magmas [Mg/(Mg+Fe*)>0.7, MgO>8 wt% and Ni>150 ppm] ranging in composition from high-alumina basalt to andesite and these record variable extents ofmelting in their mantle source. Trace and major element chemical variations, petrologic evidence and the results of phase equilibrium studies are consistent with variations in H2O content in the mantle source as the primary control on the differences in extent of melting. High-SiO2, high-MgO (SiO2=52% and MgO=11 wt%) basaltic andesites resemble hydrous melts (H2O=3 to 5 wt%) in equilibrium with a depleted harzburgite residue. These magmas represent depletion of the mantle source by 20 to 30 wt% melting. High-SiO2, high-MgO (SiO2=58% and MgO=9 wt%) andesites are produced by higher degrees of melting and contain evidence for higher H2O contents (H2O=6 wt%). High-alumina basalts (SiO2=48.5% and Al2O3=17 wt%) represent nearly anhydrous low degree partial melts (from 6 to 10% depletion) of a mantle source that has been only slightly enriched by a fluid component derived from the subducted slab. The temperatures and pressures of last equilibration with upper mantle are 1200°C and 1300°C for the basaltic andesite and basaltic magmas, respectively. A model is developed that satisfies the petrologic temperature constraints and involves magma generation whereby a heterogeneous distribution of H2O in the mantle results in the production of a spectrum of mantle melts ranging from wet (calc-alkaline) to dry (tholeiitic).  相似文献   

11.
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   

12.
Mössbauer spectroscopy has been used widely to characterize the ferric (Fe3+) and ferrous (Fe2+) proportions and coordination of solid materials. To obtain these accurately, the recoilless fraction is indispensible. The recoilless fractions (f) of iron-bearing minerals, including oxides, oxyhydroxides, silicates, carbonates, phosphates and dichalcogenides, and silicate glasses were evaluated from the temperature dependence of their center shifts or absorption area with the Debye model approximation. Generally, the resolved Debye temperature (θD) of ferric iron in minerals, except dichalcogenides, through their center shifts ranging from 400 to 550 K, is significantly larger than ferrous iron ranging from 300 to 400 K, which is consistent with the conclusion from previous work. The resolved f (Fe3+)RT with the center shift model (CSM) ranges from 0.825 to 0.925, which is larger than that obtained for f(Fe2+)RT, which ranges from 0.675 to 0.750. Meanwhile, the θD and f resolved from temperature-dependence of absorption are generally lower than from center shifts, especially for ferric iron. The significant difference between f(Fe3+) and f(Fe2+) indicates the necessity of recoilless fraction correction on the Fe3+/(Fe3++Fe2+) resolved from Mössbauer spectra.  相似文献   

13.
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   

14.
Iron-57 resonant absorption Mössbauer spectroscopy was used to describe the redox relations and structural roles of Fe3+ and Fe2+ in meta-aluminosilicate glasses. Melts were formed at 1500 °C in equilibrium with air and quenched to glass in liquid H2O with quenching rates exceeding 200 °C/s. The aluminosilicate compositions were NaAlSi2O6, Ca0.5AlSi2O6, and Mg0.5AlSi2O6. Iron oxide was added in the form of Fe2O3, NaFeO2, CaFe2O4, and MgFe2O4 with total iron oxide content in the range ∼0.9 to ∼5.6 mol% as Fe2O3. The Mössbauer spectra, which were deconvoluted by assuming Gaussian distributions of the hyperfine field, are consistent with one absorption doublet of Fe2+ and one of Fe3+. From the area ratios of the Fe2+ and Fe3+ absorption doublets, with corrections for differences in recoil-fractions of Fe3+ and Fe2+, the Fe3+/ΣFe is positively correlated with increasing total iron content and with decreasing ionization potential of the alkali and alkaline earth cation. There is a distribution of hyperfine parameters from the Mössbauer spectra of these glasses. The maximum in the isomer shift distribution function of Fe3+, δFe3+, ranges from about 0.25 to 0.49 mm/s (at 298 K relative to Fe metal) with the quadrupole splitting maximum, ΔFe3+, ranging from ∼1.2 to ∼1.6 mm/s. Both δFe3+ and δFe2+ are negatively correlated with total iron oxide content and Fe3+/ΣFe. The dominant oxygen coordination number Fe3+ changes from 4 to 6 with decreasing Fe3+/ΣFe. The distortion of the Fe3+-O polyhedra of the quenched melts (glasses) decreases as the Fe3+/ΣFe increases. These polyhedra do, however, coexist with lesser proportions of polyhedra with different oxygen coordination numbers. The δFe2+ and ΔFe2+ distribution maxima at 298 K range from ∼0.95 to 1.15 mm/s and 1.9 to 2.0 mm/s, respectively, and decrease with increasing Fe3+/ΣFe. We suggest that these hyperfine parameter values for the most part are more consistent with Fe2+ in a range of coordination states from 4- to 6-fold. The lower δFe2+-values for the most oxidized melts are consistent with a larger proportion of Fe2+ in 4-fold coordination compared with more reduced glasses and melts.  相似文献   

15.
The production of metallic iron in silicate melts by the chemical reactions, 2Ti3+(melt) + Fe2+(melt) → 2Ti4+(melt) + Fe0(crystal)2Cr2+(melt) + Fe2+(melt) → 2Cr3+(melt) + Fe0(crystal)2Eu2+(melt)+ Fe2+(melt) → 2Eu3+(melt) + Fe0(crystal) has been demonstrated under experimental conditions in a simplified basaltic liquid, Such reactions may occur in lunar basalts and other reduced systems, and, thus, may aid in the understanding of the reduced nature of lunar basalts. The reactions were studied in a glass-forming Na-Ca-Mg-Al-silicate composition at a melt temperature of 1250°C and an imposed oxygen fugacity at the C/CO buffer (1 atm total pressure). Microtitrations of individually-doped samples were used in the quantitative assessment of their redox ratios and for the calibration of visible and near-infrared spectral absorptions. These spectral absorptions were then applied to the evaluation of the mutual redox interactions in dual-doped samples.  相似文献   

16.
This study examines hydration–diffusion in the metaluminous haplogranite system at 200 MPa H2O and 800–300°C. At 800°C hydration is accompanied by melting and uphill diffusion of sodium from anhydrous glass toward the region of hydration and melting, whereas potassium diffuses away from the hydration front and into anhydrous glass. Silicon and aluminum are simply diluted upon hydration. There is no change in molecular Al/(Na + K) throughout the entire hydration-diffusion aureole and, therefore, (1) there is no loss of alkalis to the vapor, and (2) K migrates to replace Na in order to maintain local charge balance required by IVAl. Alkali diffusion occurs over a viscosity contrast from 104.1 Pa s in hydrous liquid to 1011.8–1013.5 Pa s in anhydrous glass. From these results, we interpret that: (1) Na is structurally or energetically favored over K as a charge-balancing cation for IVAl in hydrous granitic liquids, whereas the opposite behavior has been observed for anhydrous melts, and (2) the diffusion of alkalis through silicate melts is largely independent of viscosity. Results from 600°C are similar to those at 800°C, but hydration at 300°C involves a loss of Na and concomitant increase in molar Al/(Na + K) in the hydration zone due to hydrogen-alkali exchange between fluid and glass. Hydration behavior at 400°C is transitional between those at 300°C and 600°C, suggesting that the change in hydration mechanism occurs near the glass transition.  相似文献   

17.
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.  相似文献   

18.
In this study potential iron isotope fractionation by magmatic processes in the Earth's crust was systematically investigated. High precision iron isotope analyses by MC-ICP-MS were performed on a suite of rock samples representative for the volcanic evolution of the Hekla volcano, Iceland. The whole series of Hekla's rocks results from several processes. (i) Basaltic magmas rise and induce partial melting of meta-basalts in the lower part of the Icelandic crust. The resulting dacitic magma evolves to rhyolitic composition through crystal fractionation. During this differentiation the δ56/54FeIRMM-014 values increase successively from 0.051 ± 0.021‰ for the primitive dacites to 0.168 ± 0.021‰ for the rhyolites. This increase can be described by a Rayleigh fractionation model using a constant bulk fractionation factor between all mineral phases (M) and the silicate liquid (L) of Δ56/54FeM–L = ? 0.1‰. (ii) The basaltic magma itself differentiates by crystal fractionation to basaltic andesite composition. No Fe isotope fractionation was found in this series. All basalts and basaltic andesites have an average δ56/54FeIRMM-014 value of 0.062 ± 0.042‰ (2SD, n = 9), identical to mean terrestrial basaltic values reported in previous studies. This observation is consistent with the limited removal of iron from the remaining silicate melt through crystal fractionation and small mineral-melt Fe isotope fractionation factors expected at temperatures in excess of 1050 °C. (iii) Andesites are produced by mixing of basaltic andesite with dacitic melts. The iron isotope composition of the andesites is matching that of the basaltic andesites and the less evolved dacites, in agreement with a mixing process. In the Hekla volcanic suite Li concentrations are positively correlated with indicators of magma differentiation. All Hekla rocks have δ7Li values typical for the upper mantle and demonstrate the absence of resolvable Li isotope fractionation during crystal fractionation. As a fluid-mobile trace element, Li concentrations and isotopes are a potential tracer of magma/fluid interaction. At Hekla, Li concentrations and isotope compositions do not indicate any extensive fluid exsolution. Hence, the heavy Fe isotope composition of the dacites and rhyolites can be predominately attributed to fractional crystallisation. Iron isotope analyses on single samples from other Icelandic volcanoes (Torfajökull, Vestmannaeyjar) confirm heavy Fe isotope enrichment in evolving magmas. Our results suggest that the iron isotope composition of highly evolved crust can be slightly modified by magmatic processes.  相似文献   

19.
Almandine, although decomposing in the presence of metallic iron into the anhydrous subsolidus assemblage fayalite + ferrocordierite + hercynite solid solution at low pressures, melts incongruently to hercynitess + quartz + liquid at 10 kb. At pressures between about 12 and 20 kb the products of incongruent melting are hercynitess + liquid only, and at still higher pressures almandine melts congruently. For the intermediate pressures between 2 and 10 kb not investigated a sequence of probable breakdown and melting relations involving the phases ferrocordierite, fayalite, hercynitess, quartz, and liquid is derived through Schreinemakers' analyses.The lower temperature stability limit of almandine in the presence of water at low oxygen fugacities and pressures of 15 to 20 kb lies between 550° and 600° C as at low pressures. It is marked, however, by the breakdown to a hydrous assemblage involving chloritoid and the new phase aluminous deerite. Since the anhydrous melting at these pressures occurs between 1300° and 1400° C, the thermal stability range of almandine increases drastically with pressure. Its upper breakdown limit shows in principle a similar behavior as those of other garnet end members.  相似文献   

20.
The Adam-Gibbs equations describing relaxation in silicate melts are applied to diffusion of trace components of multicomponent liquids. The Adam-Gibbs theory is used as a starting point to derive an explicit relation between viscosity and diffusion including non-Arrhenian temperature dependence. The general form of the equation is Diη = Aiexp{Δ(scEi)/TSc}, where D is diffusivity, η is melt viscosity, T is absolute temperature, Δ(scEi) is the difference between the products of activation energies and local configurational entropies for viscous and diffusive relaxation, Ai is a constant that depends on the characteristics of the diffusing solute particles, and Sc is configurational entropy of the melt. The general equation will be impractical for most predictive purposes due to the paucity of configurational entropy data for silicate melts. Under most magmatic conditions the proposed non-Arrhenian behaviour can be neglected, allowing the general equation to be simplified to a generalized form of the Eyring equation to describe diffusion of solutes that interact weakly with the melt structure: Diη/T = Qiexp{ΔEi/RT}, where Qi and ΔEi depend on the characteristics of the solute and the melt structure. If the diffusing solute interacts strongly with the melt structure or is a network-forming cation itself, then ΔEi = 0, and the relation between viscosity and diffusion has the functional form of the classic Eyring and Stokes-Einstein equations; Diη/T = Qi. If the diffusing solute can make diffusive jumps without requiring cooperative rearrangement of the melt structure, the diffusivity is entirely decoupled from melt viscosity and should be Arrhenian, i.e., Di = Qiexp{Bi/T}. A dataset of 594 published diffusivities in melts ranging from the system CAS through diopside, basalt, andesite, anhydrous rhyolite, hydrous rhyolite, and peralkaline rhyolite to albite, orthoclase, and jadeite is compared with the model equations. Alkali diffusion is completely decoupled from melt viscosity but is related to melt structure. Network-modifying cations with field strength Zi2/r between 1 and 10 interact weakly with the melt network and can be modelled with the extended form of the Eyring equation. Diffusivities of cations with high field strength have activation energies essentially equal to that of viscous flow and can be modelled with a simple reciprocal Eyring-type dependence on viscosity. The values of Qi, ΔEi and Bi for each cation are different and can be related to the cation charge and radius as well as the composition of the melt through the parameters Zi2/r, M/O, and Al/(Na + K + H). I present empirical fit parameters to the model equations that permit prediction of cation diffusivities given only charge and radius of the cation and temperature, composition and viscosity of the melt, for the entire range of temperatures accessible to magmas near to or above their liquidus, for magmas ranging in composition from basalt through andesite to hydrous or anhydrous rhyolite. Pressure effects are implicitly accounted for by corrections to melt viscosity. Ninety percent of diffusivities predicted by the models are within 0.6 log units of the measured values.  相似文献   

设为首页 | 免责声明 | 关于勤云 | 加入收藏

Copyright©北京勤云科技发展有限公司  京ICP备09084417号