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1.
The fO2 stability relations of ilmenite and ulvöspinel were determined using C-O H-N gas-flow apparatus with fO2 measured by a solid ceramic (calcia-zirconia) oxygen electrolyte cell. For Fe+TiO2 + 1/2 O2 =FeTiO3 (from 850°–1050°C), 1/2 log fO2=(−11,250/T) + 0.98 and for Fe+FeTiO3 + 1/2 O2 =Fe2TiO4 (from 850°–1210°C), 1/2 logfO2 = (−12,170/T) + 1.93. These curves lie at significantly higher values of ?O2 than determined by previous investigators (i.e., 3/4 and1/4 order of magnitude for ilmenite and ulvöspinel, respectively). In addition, for Fe+ 2TiO2 + 1/2 O2 =FeTi2O5 (1210°C), ΔGr0=−45.8 ± 0.6 kcal. The QFI curve crosses the ulvöspinel reduction curve at ∼950°C and is at lower values of fO2 below this temperature. The occurrences of fayalite reduction to SiO2 + Fe in lunar rock 14053, as well as a new finding of this assemblage in 14072, are evidence for extreme sub-solidus reduction, whereas ulvöspinel breakdown alone occurs under less reducing conditions. The ‘complete’ reduction of ulvöspinel to TiO2 + Fe occurs in 2 steps: first, to ilmenite + Fe and then, however more slowly, to rutile + Fe. Thus, the presence of ulvöspinel but lack of ilmenite reduction in lunar rocks cannot be used as evidence that the fO2 was between the associated curves — only upper limits of fO2 can be inferred.  相似文献   

2.
Experimental data have been used to establish the temperature coordinates for Warner's [1] scale of lunar metamorphic grades. A model of an ejecta blanket with a hot base layer overlain by a cold top layer can produce the observed features of the Apollo 14 breccias. The breccia formation process probably encompassed temperatures between 700°C and at least 1100°C and was a reasonably rapid process (hours to days).  相似文献   

3.
The partition coefficients of potassium, DK, between molten sanidine, KAlSi3O8, and molten roedderite, K2Mg5Si12O30, with FeS-rich alloy and pure Fe metal liquids have been investigated in a multi-anvil press, between 5 and 15 GPa, at a temperature of 2173 K, and at an oxygen fugacity between 0.5 and 3 log units below the iron-wüstite (IW) buffer. No pressure dependence of the DK coefficients in sulphur-free and sulphur-bearing systems was found within the investigated pressure range. We also observed minor effect of the silicate melt composition for an nbo/t (non-bridging oxygen to tetrahedral cation ratio) higher than 0.8 ± 0.4. In contrast, the partitioning of potassium varies strongly with the metallic phase composition, with an increase of K-solubility in the metallic liquid for high sulphur and oxygen contents.We review all available high-pressure data to obtain reliable DK coefficients for the interaction between molten silicates and Fe-alloy liquids at pressures and temperatures relevant to those of core formation in a terrestrial magma ocean. The dominant controlling parameters appear to be the temperature and the chemical composition of the metallic phase, with DK coefficients significantly increased with temperature, and with the sulphur and oxygen contents of the Fe-alloy liquid. Our considerations distinguish two extreme cases, with an S-free or S-bearing iron core, which yield K contents of ∼25 or ∼250 ppm, respectively. These two extreme values have very different consequences for thermal budget models of the Earth's core since its formation.  相似文献   

4.
The oxidation state of iron can significantly influence the physical and chemical properties of lower mantle minerals. To improve methods for estimation of Fe3+/∑Fe, synthetic assemblages of (Mg,Fe)(Si,Al)O3 perovskite and (Mg,Fe)O ferropericlase were synthesised from oxide starting mixtures in Re or Fe capsules at 26 GPa and 1650-1850 °C using a multianvil press. (Mg,Fe)(Si,Al)O3 majorite was also present in some of the run products. Both electron energy loss spectra (EELS) and Mössbauer spectra were measured for each run product, and a robust fitting method was developed for Mössbauer spectra using EELS results as a standard that enabled Fe3+/∑Fe of (Mg,Fe)(Si,Al)O3 perovskite to be determined from Mössbauer spectra of multiphase assemblages. There is a close to linear variation between Fe3+/∑Fe and Al concentration in (Mg,Fe)(Si,Al)O3 perovskite, independent of oxygen fugacity. The concentration of Fe3+ in (Mg,Fe)O increases with increasing iron concentration along curves of constant oxygen fugacity, where higher oxygen fugacity stabilises greater Fe3+ concentrations. Fe2+/Mg partition coefficients calculated from chemical composition data corrected for measured Fe3+/∑Fe showed values nearly identical within experimental error for all samples, and independent of Al concentration and oxygen fugacity. Simple empirical relations were derived to calculate Fe3+/∑Fe in (Mg,Fe)(Si,Al)O3 perovskite and (Mg,Fe)O ferropericlase samples for which no Mössbauer or EELS data were available, and tested by applying them to calculation of Fe2+/Mg partition coefficients from literature data for (Mg,Fe)(Si,Al)O3 perovskite-(Mg,Fe)O assemblages where only total iron concentrations had been measured. Results showed Fe2+/Mg partition coefficients that were equal to existing values within experimental error, hence confirming the validity of the empirical relations.  相似文献   

5.
Measurements of the oxygen fugacity (?O2) as a function of temperature (T) were made on an interior bulk sample of the cumulate achondrite, Angra dos Reis. Data clustered between the?O2-T relationship of the iron-wüstite assemblage and 1.2 log atm units above iron-wüstite. Interpretation of the data indicates that, throughout most of the cooling history of the meteorite, ?O2 values were defined by equilibria involving iron-bearing species at values close to the ?O2 of the assemblage iron-wüstite. Measured ?O2 data are compatible with crystallization and cooling at pressures greater than 50 bars.  相似文献   

6.
Reaction coronas of pyroxene ± ilmenite occur around clasts of olivine in Apollo 14 high-grade metamorphic breccias. In experiments of several months duration, there was no evidence of corona formation at 1000°C, but at 1050°, withfO2 at or above Ilm-Ru-Fe and below Fe-Fe1?x O, incipient coronas formed around Fo50–70 in synthetic 14311 matrix. In addition, withfO2 controlled by Ilm-Ru-Fe at 1050°C, the olivines reduced to Fo68, En69 + Fe. Reduction of olivine under these conditions is inconsistent with the calculated stability relations and is attributed to uncertainties in the activity coefficient for olivine or pyroxene. The experiments also suggest that vesicularity in the Apollo 14 high-grade breccias may correlate with the amount of glassy material in their unmetamorphosed precursors. The metamorphic event is attributed to burial in a hot ejecta blanket, such as that of the Imbrium event.  相似文献   

7.
The electrical conductivity of a single crystal of San Carlos olivine (Fo92, 0.16 wt.% Fe2O3) has been measured as a function of temperature and oxygen fugacity (fO2). After heating to 1338°C at fO2 = 10?12 atm., the conductivity at 950°C was 10?5 (ohm-m)?1, almost 3 orders of magnitude less than that measured in air. This decrease is due to the reduction of Fe3+ to Fe2+. Further heating to 1500°C at fO2 = 10?14 atm., decreased the electrical conductivity at 950°C to 10?6 (ohm-m)?1. When recovered at room temperature, the speciment had Fo96 composition and contained small, opaque blebs distributed throughout the crystal. Derivations of temperature profiles for the earth's mantle from conductivity-depth models must take account of the important role played by iron oxidation state in the electrical conductivity of olivine.  相似文献   

8.
Phase equilibrium experiments were performed to determine the pre-eruptive conditions of the phonolitic magma responsible for the last eruption (about 1,150 yr B.P.) of Teide volcano. The Lavas Negras phonolite contains 30 to 40 wt% of phenocrysts, mainly anorthoclase, diopside, and magnetite. We have investigated pressures from 100 to 250 MPa, temperatures from 750 to 925°C, water contents from 1.3 to 10 wt%, at an oxygen fugacity (fO2) of 1 log unit above the Ni-NiO solid buffer. Comparison of the natural and experimental phase proportions and compositions indicates that the phonolite was stored at 900 ± 20°C, 150 ± 50 MPa, 3 ± 0.5 wt% dissolved H2O in the melt. The fO2 was probably close to the fayalite-magnetite-quartz solid buffer judging from results of other experimental studies. These conditions constrain the magma storage depth at about 5 ± 1 km below current summit of Teide volcano. Given that the island has not suffered any major structural or topographic changes since the Lavas Negras eruption, any remaining magma from this event should still be stored at such depth and probably with a similar thermal and rheological state.  相似文献   

9.
We derive experimental constraints on the interior structure and mineralogy of large icy satellites by reacting material of chondritic chemistry with water at a pressure of 1.5 GPa, temperatures between 300°C and 800°C and a range of oxygen fugacities. Our results document the existence of three chemical processes that probably occur in large icy satellites as a result of high pressure hydrothermal processing: (1) the formation of low-density hydrated silicates, (2) the alloying of iron and sulfur to form FeS-dominated cores, and (3) the instability of organic material relative to carbonates. We construct new internal models of the thermal and structural state of Ganymede, and infer that the magnetic field of this body arises from convection within a mostly iron sulfide core. Simple thermochemical calculations are conducted to further explore the likely effects of composition and oxygen fugacity on the high pressure chemistry undergone by organic material within icy satellites. Both experimental and calculated results show that primordial organics are likely to have been largely oxidized to carbonates through hydrothermal processing early in Ganymede’s history, potentially sterilizing Ganymede’s H2O layer.  相似文献   

10.
Results of electrical conductivity measurments on synthetic olivines of the system Mg2SiO4Fe2SiO4 and on minerals of Dreiser Weiher peridotite nodule Ib-8 (Eifel, Germany) are discussed in relation to the measuring procedure and to the variation of thermodynamic parameters.The measurements were performed in solid state high-pressure vessels between 340 and 1100°C and at a pressure of 10 kbar. It is shown that for ternary olivines and for pyroxenes, the control of two further variables, like the chemical activities of the components, is needed besides temperature and pressure control. The experimental set-up for the control of chemical activities and oxygen partial pressure is shown. From the slopes of the lines of log σ against 1/T the activation energies were calculated. Though in most cases the same oxygen fugacity ?O2 is applied, the results reveal different values for synthetic and natural samples since the chemical activities of SiO2 are different.  相似文献   

11.
Some of the factors which control the solubility of ferrous iron and olivine in basaltic liquids have been determined from experiments conducted in equilibrium with metallic iron at temperatures of 1150° to 1306°C and oxygen fugacities of log?O2 = ?12.5to?14.5atm. In order to insure that the samples were in equilibrium with metallic iron and the gas atmosphere during the experiment, the samples were continuously mixed (60 r.p.m.) for at least 90 hours with a metallic iron mixing rod.The solubility of ferrous iron and olivine in basaltic liquid was found to decrease as the alkali and alumina content of the liquid increased. The activity coefficient of ferrous iron in the liquid was calculated from the oxygen fugacity and mole fraction of ferrous oxide in the liquid and varied from 0.79 to 2.00. The ferrous iron/magnesium ratio in the liquid relative to olivine was insensitive to the changing alkali content as measured by the constant distribution coefficient of0.30 ± 0.03 (SD). The calculated silica activity of these liquids varied from 0.11 to 0.50 and the distribution coefficient of ferrous iron-manganese between olivine and liquid was found to be1.4 ± 0.2 (SD). It was found that the major element content of olivine does not exert a strong structural control on the manganese content of olivine.The magnitude of depletion in the liquid of the metal oxides by the crystallization of olivine is in the order Ni > Mg > Co > Fe > Mn, which reflects the relative octahedral site preference of these elements. The composition of the crystallizing olivine reflects the ratio of the above elements in the liquid and is relatively insensitive to temperature, variation of the other elements in the liquid or to the changing magnesium/ferrous iron ratio in the olivine.  相似文献   

12.
Summary The photolysis of ozone in the u.v. Hartley Band produces metastable oxygen atoms and molecules. At wavelengths shorter than 3100 Å the primary quantum yield is probably unity but greater uncertainty exists about its value at longer wavelengths. At 2500 Å, O2(1g) is produced with near unit efficiency and there is some evidence that singlet O2 is also a primary prduct at the short wavelenght end of the Huggins band. O2(1 g + ) is not a primary photolytic product at 2500 Å but is produced as a secondary product from the rapid reaction of O(1D) with ground state O2. O(1D) reacts rapidly with O3 although the nature of the products of this reaction has not been unequivocally established and there is now strong evidence against the occurrence of energy chains in dry ozone. The reaction of O(3P) atoms with O3 has been found to have an activation energy of 4.4 kcal mole–1.  相似文献   

13.
Polymict samples can be used to establish mass-balance constraints regarding the bulk composition of the lunar crust, and to gauge the degree of regional heterogeneity in the composition of the lunar crust. The most ideally polymict type of sample is finely-mixed regolith (lunar soil), or its lithified equivalent, regolith breccia. Fortunately, lunar regolith breccias can occasionally be found at great distances from their points of origin — most of the known lunar meteorites are regolith breccias. We are searching for examples of exotic regolith samples among the Apollo regolith breccia collection. Most of the 21 Apollo regolith breccias analyzed for this study strongly resemble the local soils over which they were collected. Nine regolith breccias from Apollo 16 are surprisingly mature compared to previously-analyzed Apollo 16 regolith breccias, and six of the seven from Apollo 16 Station 5 have lower, more local-soil-like,mg ratios than previously analyzed regolith breccias from this station. Several of the Apollo 14 regolith breccias investigated show significantly highermg, and lower Al, than the local soils.The most interesting sample we have investigated is 14076,1, from a lithology that constitutes roughly half of a 2.0-g pebble. The presence of spherules indicates a regolith derivation for 14076,1, yet its highly aluminous (30 wt.% Al2O3) composition is clearly exotic to the 1.6-km traverse surface over which the Apollo 14 samples were collected. This sample resembles soils from the Descartes (Apollo 16) highlands far more than it does any other polymict sample from the Fra Mauro (Apollo 14) region. The I/sFeO maturity index is extremely low, but this may be a result of thermal annealing. A variety of siderophile elements occur in 14076,1 at typical regolith concentrations. The chemistry of the second most aluminous regolith sample from Apollo 14, 14315, can only be roughly approximated as a mixture of local regolith and 14076,1-like material. However, the low a priori statistical probability for long-distance horizontal transport by impact cratering, along with the relatively high contents of incompatible elements in 14076,1 (despite its high Al content), suggest that this regolith breccia probably originated within a few hundred kilometers of the Appollo 14 site. If so, its compositional resemblance to ferroan anorthosite tends to suggest that the regional crust is, or originally was, far richer in ferroan anorthosite than implied by the meager statistics for pristine rocks from this site. Thus, 14076,1 tends to strengthen the hypothesis that ferroan anorthosite originated as the flotation crust of a global magmasphere.  相似文献   

14.
We provide two new determinations of the oxygen isotopic composition of seawater during the last glacial maximum (LGM). High-resolution oxygen isotopic measurements were made on interstitial waters from Ocean Drilling Program (ODP) Sites 1168 and 1170 in the southeast Indian Ocean sector of the Southern Ocean. We use a diffusion-advection numerical model to calculate the glacial-interglacial change in bottom-water δ18Osw from the pore water δ18O profiles; the first such determinations from this part of the oceans. Statistical analyses of the model runs indicate that Circumpolar Deep Water (CDW) δ18Osw changed by 1.0-1.1±0.15‰ since the last glacial maximum (LGM). Our results are consistent with a previous calculation from a South Atlantic Southern Ocean location (ODP Site 1093) also situated within CDW. The new values determined in this study, together with previous estimates, are converging on a global average Δδ18Osw of 1.0-1.1‰.Using the calculated bottom-water δ18Osw, we have extracted the temperature component from the benthic foraminiferal δ18O record at Sites 1168 and 1170. Since the LGM, bottom waters at these two sites warmed by 2.6 and 1.9°C, respectively. The absolute temperature estimates for the LGM (−0.5°C [Θ=−0.6°C] at Site 1168 and −0.2°C [Θ=−0.4°C] at Site 1170) are slightly warmer than those reported from previous studies using the same technique, but are consistent with more homogenous deep-ocean temperatures during the LGM relative to the modern.  相似文献   

15.
Summary This study is a follow up of the investigation of some magnetic properties and metastability of greigite in samples obtained from Miocene claystones in the Kruné hory (Erzgebirge) Piedmont basins (Bohemia). Three different methods of upgrading the smythite were applied; the magnetic properties of the concentrates are compared. The thermal conversion of smythite sets in at 200°C while greigite converts at 250°C. The first intermediate products to be formed are iron sulphides, marcasite clearly dominating over pyrite and pyrrhotite. Apart from a Fe3+ sulphate with a composition of Fe2(SO4)3, oxidation of these sulphides gives rise to -Fe2O3. The result of the subsequent decomposition of the mentioned sulphate is the formation of -Fe2O3, which retains the sulphate structure. The final product of the thermal decomposition at 800°C is -Fe2O3. In the smythite concentrate the conversion to Fe3+ sulphate and -Fe2O3 is about twice as intensive as in greigite. No direct conversion to -Fe2O3 was found. During the thermal process self-reversals of remanence were observed, in various samples as many as four reversals in the temperature interval from 340 to 590°C. The occurrences of self-reversals of remanence were only observed at high degrees of thermal demagnetization, of the order of 10–2 down to 10–3 in the temperature interval of sulphide origin (below 400°C), and of the order of 10–4 down to 10–6 in the temperature interval of Fe-oxides origin (above 400°C).Presented at the 3rd Conference on New Trends in Geomagnetism, Castle of Smolenice, Czechoslovakia, June 22–29, 1992  相似文献   

16.
The eruption of Redoubt Volcano in Alaska produced a moderate sulfur emission (estimated at 1 × 10 tons SO2), but relatively small volume of lava (0.11 km ) with pre-eruption estimates of 840–950 °C and fO21.5 to 2.0 log units above NNO (Swanson, S.E., Nye, C.J., Miller, T.P., Avery, V.F., 1994. Magma mixing in the 1989–1990 eruption of Redoubt Volcano: Part II. Evidence from mineral and glass chemistry. Journal of Volcanology and Geothermal Research 62, 453–468). Petrologic estimates of sulfur production (Sigurdsson, H., Devine, J.D.,Davis, A.N., 1985. The petrologic estimation of volcanic degassing. Jokull 35, 1–8) from this eruption (Gerlach, T., Westrich, H.R., Casadevall, T.J., Finnegan, D.L., 1994. Vapor Saturation and accumulation in magmas of the 1989–1990 eruption of Redoubt Volcano, Alaska. Journal of Volcanology and Geothermal Research 62, 317–337) are considerably less than the measured sulfur emission, leading workers to propose the existence of a pre-eruption vapor phase to explain the “excess” sulfur.  相似文献   

17.
FAMOUS basalt 527-1-1 (a high-Mg oceanic pillow basalt) has three generations of spinel which can be distinguished petrographically and chemically. The first generation (Group I) have reaction coronas and are high in Al2O3. The second generation (Group II) have no reaction coronas and are high in Cr2O3 and the third generation (Group III) are small, late-stage spinels with intermediate Al2O3 and Cr2O3. Experimental synthesis of spinels from fused rock powder of this basalt was carried out at temperatures of 1175–1270°C and oxygen fugacities of 10?5.5 to 10?10 atm at 1 atm pressure. Spinel is the liquidus phase at oxygen fugacities of 10?8.5 atm and higher but it does not crystallize at any temperature at oxygen fugacities less than 10?9.5. The composition of our spinels synthesized at 1230–1250°C and 10?9 atmfO2 are most similar to the high-Cr spinels (Group II) found in the rock. Spinels synthesized at 1200°C and 10?8.5 atmO2 are chemically similar to the Group III spinels in 527-1-1. We did not synthesize spinel at any temperature or oxygen fugacity that are similar to the high-Al (Group I) spinel found in 527-1-1. These results indicate that the high-Cr (Group II) spinel is the liquidus phase in 527-1-1 at low pressure and Group III spinel crystallize below the liquidus (~1200°C) after eruption of the basalt on the sea floor. The high-Al spinel (Group I) could have crystallized at high pressure or from a magma enriched in Al and perhaps Mg compared to 527-1-1.  相似文献   

18.
Examination of glass and crystal chemistry in the Rotoiti Pyroclastics (>100 km3 of magma) demonstrates that compositional diversity was produced by mingling of the main rhyolite magma body with small volumes of other magmas that had been crystallizing in separate stagnant magma chambers. Most (>90%) of the Rotoiti deposits were derived from a low-K2O, cummingtonite-bearing, rhyolitic magma (T1) discharged throughout the eruption sequence. T1 magma is homogeneous in composition (melt SiO2=77.80±0.28 wt.%), temperature (766±13 °C) and oxygen fugacity (NNO+0.92±0.09). Most T1 phenocrysts formed in a shallow (∼200 MPa), near water-saturated (awater=0.8) storage chamber shortly before eruption. Basaltic scoria erupted immediately before the rhyolites, and glass-bearing microdiorite inclusions within the rhyolite deposits, suggest that basalt emplaced on the floor of the chamber drove vigorous convection to produce the well-mixed T1 magma. Lithic lag breccias contain melt-bearing biotite granitoid inclusions that are compositionally distinct from T1 magma. The breccias which overlie the voluminous T1 pyroclastic flow deposits resulted from collapse of the syn-Rotoiti caldera. Post-collapse Rotoiti pumices contain T1 magma mingled with another magma (T2) that is characterized by high-K glass and biotite, and was cooler and less oxidised (712±16 °C; NNO−0.16±0.16). The mingled clasts contain bimodal disequilibrium populations of all crystal phases. The granitoid inclusions and the T2 magma are interpreted as derived from high-K magma bodies of varying ages and states of crystallization, which were adjacent to but not part of the large T1 magma body. We demonstrate that these high-K magmas contaminated the erupting T1 magma on a single pumice clast scale. This contamination could explain the reported wide range of zircon U–Th ages in Rotoiti pumices, rather than slow crystallization of a single large magma body.  相似文献   

19.
The mechanism responsible for the formation of finely divided metallic iron in lunar samples has been the subject of considerable debate. A review of the data currently available from laboratory simulation studies would appear to favour an origin involving preferential sputtering of oxygen atoms by the solar wind.Using a model presented here we find that it is thermodynamically predictable that preferential sputtering would lead to the formation of free iron. Likewise titanium should be enriched in particle surfaces due to the formation of Ti2O3 from TiO2. Other major elements will be fractionated according to the ratio of their heat of sublimation to the heat of dissociation of their oxide. The changes induced in the surfaces of fine grains will be of considerable importance when these particles are incorporated into complex grains. Thus, we suggest that preferential sputtering may be implicated in the major element fractionations observed for glassy agglutinates. A 1% component of Fe∮ is able to account easily for the enrichment in the total iron observed.If sufficient exposure time is available preferential sputtering may be able to produce metallic iron-rich layers ca. 40Åthick on the surfaces of lunar grains. Most of this metal would derive from helium sputtering rather than hydrogen bombardment. Provided reduction takes place predominantly in fine particles with a mean grain size <10 μm diameter which are subsequently incorporated into glassy agglutinates, preferential sputtering could account for all the free iron in the lunar soil.For elements of atomic number ca. Z = 30 and above, thermodynamic effects become insignificant compared to momentum transfer considerations. Heavy (Pb, Hg) and medium heavy elements (Rb, Sr) could all be enriched by preferential sputtering. Monovalent elements (e.g. K, Rb) in silicates will have a lower binding energy and knock-on collisions with incoming solar wind atoms could cause their increased abundance in fine fractions of lunar soil.  相似文献   

20.
Hazardous electric arc furnace dust containing dioxins/furans and heavy metals is blended with harbor sediment, fired at 950–1100 °C to prepare lightweight aggregates. Dust addition can lower the sintering temperature by about 100 °C, as compared to a typical industrial process. After firing at 950 °C and 1050 °C, more than 99.85% of dioxins/furans originally present in the dust have been removed and/or destructed in the mix containing a dust/sediment ratio of 50:100. The heavy metals leached from all fired mixes are far below Taiwan EPA legal limits. The particle density of the lightweight aggregates always decreases with increasing firing temperature. Greater addition of the dust results in a considerably lower particle density (mostly <2.0 g cm−3) fired at 1050 °C and 1100 °C. However, firing at temperatures lower than 1050 °C produces no successful bloating, leading to a denser particle density (>2.0 g cm−3) that is typical of bricks.  相似文献   

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