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1.
A ∼17-m paleosol sequence at Schagen, South Africa, which developed on a serpentinized dunite intrusion in a granite-gneiss terrain ∼2.6 Ga ago, is characterized by an alternating succession of thick (∼1-3 m) carbonate-rich (dolomite and calcite) zones and silicate-rich (serpentines, talc, and quartz) zones; the upper ∼8 m section is especially rich in organic C (up to ∼1.4 wt.%). Petrologic and geochemical data suggest the upper ∼8 m section is composed of at least three soil profiles that developed on: (i) silicate-rich rock fragments (and minerals) that were transported from local sources (serpentinite and granite) by fluvial and/or eolian processes; and (ii) dolomite and calcite zones that formed by locally discharged groundwater. The Mg and Fe in the paleosol sequence were largely supplied from local sources (mostly serpentinite), but the Ca, Sr, and HCO3− were supplied by groundwater that originated from a surrounding granite-gneiss terrain. In the uppermost soil profile, the (Fe is retained, the Fe3+/Fe2+ ratio increases, and ferri-stilpnomelane is abundant. These data suggest the atmospheric pO2 was much greater than ∼10−3.7 atm (>0.1% present atmospheric level [PAL]).The carbonaceous matter in the soils is intimately associated with clays (talc, chlorite, and ferri-stilpnomelane) and occurs mostly as seams (20 μm to 1 mm thick) that parallel the soil horizons. These occurrences, crystallographic structures, H/C ratios, and δ13Corg values (−17.4 to −14.4‰ PDB) suggest that the carbonaceous matter is a remnant of in situ microbial mats, originally ∼1 to ∼20 mm thick. The microbial mats developed: (a) mostly on soil surfaces during the formation of silicate-rich soils, and (b) at the bottom of an evaporating, anoxic, alkaline pond during the precipitation of the Fe-rich dolomite. These δ13Corg values are difficult to be explained by a current popular idea of a methane- and organic haze-rich Archean atmosphere (Pavlov et al., 2001); these values, however, can be easily explained if the microbial mats were composed of cyanobacteria and heterotrophs that utilized the remnants of cyanobacteria in a strongly evaporating environment.  相似文献   

2.
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   

3.
We report the mineral compositions and micro-texture of the isotopically anomalous (δ17,18OSMOW ∼ +180‰) Fe-S-Ni-O material recently discovered in matrix of the primitive carbonaceous chondrite Acfer 094 [Sakamoto N., Seto Y., Itoh S., Kuramoto K., Fujino K., Nagashima K., Krot A. N. and Yurimoto H. (2007) Oxygen isotope evidence for remnants of the early solar system primordial water. Science317, 231-233]. Synchrotron radiation X-ray diffraction and transmission electron microscopy studies indicate that this material consists of the symplectitically intergrown magnetite (Fe3O4) and pentlandite (Fe5.7Ni3.3S8) with magnetite/pentlandite volume ratio of ∼2.3. Magnetite forms column-shaped grains (10-30 nm in diameter and 100-200 nm in length); pentlandite occurs as worm-shaped grains or aggregates of grains 100-300 nm in size between magnetite crystals. Although both the X-ray diffraction and electron energy loss spectra support identification of iron oxide as magnetite, the electron diffraction patterns show that magnetite has a weak 3-fold superstructure, possibly due to ordering of vacancies. We infer that the isotopically anomalous symplectite formed by sulfurization and oxidization of metal grains either in the solar nebula or on an icy planetesimal. The intersite cation distribution of pentlandite suggests that timescale of oxidation was no longer than 1000 years.  相似文献   

4.
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   

5.
Zusammenfassung Der Eisengehalt von Andalusiten und Disthenen aus Quarzknauern im Gebiet des Ötztaler—Stubaier Altkristallins wurde regional untersucht. Der Gehalt and Gesamteisen in primären Disthen liegt zwischen 0,17 und 0,22 Gew.% Fe2O3, während primäre Andalusite zwischen 0,26 und 1,93 Gew.% Fe2O3 schwanken. Dieser Unterschied in den Andalusiten wird auf ein wechselndes Angebot von Fe2O3 aus dem Nachbargestein der Knauern zurückgeführt.Ein Zusammenhang zwischen dem Eisengehalt der Andalusite und den verschiedenen Umwandlungsstadien Andalusit—Disthen konnte nicht nachgewiesen werden.
On the iron content of alumosilicates in quartz nodules
Summary A determination of the regional distribution of the ironcontent of andalusites and kyanites in quartz-segregations of the Oetztal—Stubai crystalline complex gave values of 0.17–0.22% for the total iron in primary kyanite and 0.26–1.93% in andalusite. This difference is probably due to a variation in the Fe2O3-content in the country rocks of the quartz veins. No relationship between the iron-content in andalusite and the different stages of transformation from andalusite to kyanite could be established.
  相似文献   

6.
 Acid mine drainage (AMD) occurs when sulfide minerals are exposed to an oxidizing environment. Most of the methods for preventing AMD are either short-term or high cost solutions. Coating with iron phosphate is a new technology for the abatement of AMD. It involves treating the sulfide with a coating solution composed of H2O2, KH2PO4, and sodium acetate as a buffer agent. The H2O2 oxidizes the sulfide surface and produces Fe3+ so that iron phosphate precipitates as a coating on the sulfide surface. Experiments performed under laboratory conditions prove that an iron phosphate coating can be established on pyrrhotite surfaces with optimal concentrations of the coating solution in the range of: 0.2M/0.01M H2O2, 0.2M KH2PO4, and 0.2M sodium acetate NaAc, depending on the experimental scale. Iron phosphate coating may be a long-term solution to the problem of AMD. The method would be easy to implement; the reagent cost, however, is not low enough, although it is lower than the conventional treatment with lime. Received: 30 March 1995 · Accepted: 6 September 1995  相似文献   

7.
Ferric iron in mantle-derived garnets   总被引：4，自引：0，他引：4  
The oxidation state of a mantle assemblage may be defined by heterogeneous reactions between oxygen and iron-bearing minerals. In spinel lherzolites, the presence of Fe3+ in spinel allows use of the assemblage olivine-orthopyroxene-spinel to define f O 2 at fixed T and P. As a first step towards establishing an analogous reaction for garnet lherzolites, garnets from mantle-derived xenoliths from South Africa and the USSR have been analyzed with 57Fe Mössbauer spectroscopy at 298 and 77K to determine Fe3+/Fe2+ and the coordination state of iron. Garnets from South African alkremites (pyrope+Mg-spinel) and eclogites, as well as garnet-spinel and low-temperature garnet lherzolites from both South Afica and the USSR, have Fe3+/Fe<0.07. In contrast, garnets from high-temperature garnet lherzolites from within the Kaapvaal craton of South Africa have Fe3+/Fe>0.10. Ferric iron is octahedrally coordinated, and ferrous iron is present in the dodecahedral site in all samples. The occurrence of significant Fe3+ in these garnets necessitates caution in the use of geothermometers and geobarometers that are applied to mantle samples. For example, the presence of 12% of the Fe as Fe3+ in garnets can increase temperatures calculated from existing Fe/Mg geothermometers by>200°C. The concomitant increase in pressures calculated from geobarometers that use the Al content in orthopyroxene coexisting with garnet are 10–15 kbar. Results of calculations based on heterogeneous equilibria between garnet, olivine, and pyroxene are consistent with the derivation of the peridotite samples from source regions that are relatively oxidized, between the f O 2 of the FMQ (quartz-fayalite-magnetite) buffer and that of the WM buffer. No samples yield values of f O 2 as reduced as IW (iron-wüstite buffer).  相似文献   

8.
Poorly crystalline carbonaceous matter was observed in chlorite to sillimanite grade metasediments from the Trois Seigneurs Massif, in contrast to other studies of carbon crystallinity which observed well crystallised graphite under upper greenschist facies conditions. Using transmission electron microscopy four types of carbon particle were identified; globular carbon, composite flakes, homogeneous flakes and crystalline graphite. Globular carbon and composite flakes are poorly crystalline microporous carbon. Homogeneous flakes decompose in the electron beam and are probably composed of heavy volatile hydrocarbons. Graphite is confined to samples from retrograde shear zones and often occurs with globular carbon. The lack of graphitisation in metasediments is probably a consequence of the microporous structure of the carbonaceous matter combined with low f O 2. The preservation of carbonaceous matter in the Trois Seigneurs metasediments is not compatible with the metasediments having been externally buffered by a high X H2O fluid syn-metamorphism. An alternative hypothesis of internal buffering is preferred to explain the carbonaceous matter in the Trois Seigneurs metasediments.  相似文献   

9.
The coordination environment of Fe(II) has been examined in seven anhydrous ferrosilicate glasses at 298 K and 1 bar using 57Fe Mössbauer, Fe K-edge X-ray near edge structure (XANES), and extended X-ray absorption fine structure (EXAFS), UV-Vis-NIR, and magnetic circular dichroism (MCD) spectroscopies. Glasses of the following compositions were synthesized from oxide melts (abbreviation and nonbridging oxygen:tetrahedral cation ratio (NBO/T) in parentheses): Li2FeSi3O8 (LI2: 1.33), Rb2FeSi3O8 (RB2: 1.33), Nal.08Fel.l7Si3.l3O8 (NAl: 1.09), Nal.46Ca0.24Fel.08Si2.97O8 (NC6: 1.38), Nal.09Ca0.51Fe0.72Si3.10O8 (NC2: 1.15), Na0.99Ca0.92Fe0.24 Si3.17O8 (NCl: 1.04), and Na0.29Mg0.53Ca0.52Fe0.56Al0.91Si2.44O8 (BAS: 1.05). Mössbauer, XANES, and EXAFS information suggests that iron is dominantly ferrous in all glasses (<10 atom% Fe(III)) with an average first-neighbor Fe(II) coordination varying from ∼ 4 to 5.2 (±0.2) oxygens. The UV-Vis-NIR spectrum of each sample exhibits intense absorption centered near 8100-9200 cm−1 and weak absorption near 5000 cm−l, which cannot be assigned unambiguously. The MCD spectrum of NC6 glass, which is the first such measurement on a silicate glass, shows three transitions at ∼8500 cm−1, ∼6700 cm−1, and ∼4500 cm−1. The behavior of these MCD bands as a function of temperature (1.6 K to 300 K) and magnetic field strength (1 T to 7 T) indicates that they most likely arise from three distinct Fe(II) sites with different ground states, two of which are 5-coordinated and one of which is 4-coordinated by oxygens.The combined results suggest that Fe(II) predominantly occupies 5- and 4-coordinated sites in each glass, with the ratios differing for the different compositions. Small amounts of 6-coordinated Fe(II) are possible as well, but primarily in the more basic glass compositions such as BAS. The substitution of Li(I) for Rb(I) in the M2FeSi3O8 base glass composition causes a weakening of the average Fe(II)-O bond, as indicated by the longer Fe(II)-O distance in the latter. The basalt composition glass was found to have the largest Fe(II) sites relative to those in the other glasses in this study. A bond valence model that helps predict the coordination number of Fe(II) in silicate glasses is proposed. The structural information extrapolated to Fe(II)-bearing melts is parameterized using bond valence theory, which helps to rationalize the melt-crystal partitioning behavior of ferrous iron in natural and synthetic melt-crystal systems.  相似文献   

10.
We have performed a detailed Mössbauer study of synthetic annites on the (OH, F)-join. Recently developed data treatment and spectral analysis methods were used to extract true intrinsic Fe2+ quadrupole splitting distributions (QSDs) that represent the most information that can be resolved from the spectra. The overall room temperature (RT) QSDs can be consistently interpreted in terms of four QSD contributions (or populations) centered at: QSHH2.55 mm/s for Fe2+O4(OH)2 octahedra (cis and trans not resolved), QSHF 2.35 mm/s for Fe2+O4(OH)F octahedra (cis and trans not resolved), QScFF2.15 mm/s for cis-Fe2+O4F2 octahedra, and QStFF 1.5 mm/s for trans-Fe2+O4F2 octahedra. Each such contribution has a width ( 0.2 mm/s) caused by distortions of the octahedra. Minor contributions due to Fe2+O5(OH) and Fe2+O5F octahedra probably also contribute to the overall Fe2+ QSDs. The ferric iron spectral components were also characterized. Here, two distinct types of octahedral Fe3+ contributions are seen and interpreted as being due mainly to Fe3+O5OH and Fe3+O5F octahedra, respectively. Tetrahedral Fe3+ is seen only in the OH-annite end-member and the total Fe3+ content drops significantly on addition of F. On leave from: Department of Materials Physics, University of Science and Technology Beijing, 100083 Beijing, China  相似文献   

11.
We have carried out an in situ synchrotron X-ray diffraction study on iron and an iron-silicon alloy Fe0.91Si0.09 at simultaneously high pressure and temperature. Unit-cell volumes, measured up to 8.9 GPa and 773 K on the bcc phases of iron and Fe0.91Si0.09, are analyzed using the Birch-Murnaghan equation of state and thermal pressure approach of Anderson. Equation of state parameters on iron are found to be in agreement with results of previous studies. For both iron and Fe0.91Si0.09, thermal pressures show strong dependence on volume; the (∂KT/∂T)V values are considerably larger than those previously reported for other solids. The present results, in combination with our previous results on ɛ-FeSi, suggest a small dependency of the room-temperature bulk modulus upon the silicon content, less than 0.3 GPa for 1 wt.% silicon. We also find that substitution of silicon in iron would not appreciably change the thermoelastic properties of iron-rich Fe−Si alloys. If this behavior persists over large pressure and temperature ranges, the relative density contrast between iron and iron-rich Fe−Si alloys at conditions of the outer core of the Earth could be close to that measured at ambient conditions, i.e., 0.6% for 1 wt.% Si. Received: 13 January 1998 / Revised, accepted: 8 May 1998  相似文献   

12.
Theoretical models predict a marked increase in atmospheric O2 to ∼35% during the Permo-Carboniferous (∼300 Ma) occurring against a low (∼0.03%) CO2 level. An upper O2 value of 35%, however, remains disputed because ignition data indicate that excessive global forest fires would have ensued. This uncertainty limits interpretation of the role played by atmospheric oxygen in Late Paleozoic biotic evolution. Here, we describe new results from laboratory experiments with vascular land plants that establish that a rise in O2 to 35% increases isotopic fractionation (Δ13C) during growth relative to control plants grown at 21% O2. Despite some effect of the background atmospheric CO2 level on the magnitude of the increase, we hypothesize that a substantial Permo-Carboniferous rise in O2 could have imprinted a detectable geochemical signature in the plant fossil record. Over 50 carbon isotope measurements on intact carbon from four fossil plant clades with differing physiological ecologies and ranging in age from Devonian to Cretaceous reveal a substantial Δ13C anomaly (5‰) occurring between 300 and 250 Ma. The timing and direction of the Δ13C excursion is consistent with the effects of a high O2 atmosphere on plants, as predicted from photosynthetic theory and observed in our experiments. Preliminary calibration of the fossil Δ13C record against experimental data yields a predicted O2/CO2 mixing ratio of the ancient atmosphere consistent with that calculated from long-term models of the global carbon and oxygen cycles. We conclude that further work on the effects of O2 in the combustion of plant materials and the spread of wildfire is necessary before existing data can be used to reliably set the upper limit for paleo-O2 levels.  相似文献   

13.
Rates of organic carbon oxidation in marine sediments were determined for the continental margins of northwest Mexico and Washington State, with the goal of assessing the role of oxygen in the preservation of organic matter on a margin with a strong oxygen-deficient zone and on a typical western continental margin. Total carbon oxidation rates (including rates for individual electron acceptors: O2, NO3−, and SO4=) were determined at depths ranging from 100 to 3000 m on both margins. Carbon oxidation rates were generally higher on the Washington margin than on the Mexican margin. The relative importance of the different electron acceptors varied across the two margins and was related primarily to the availability of O2 and NO3− from the overlying water. The relative contribution of O2 consumption increased in deeper sediments (>2000 m) as aerobic processes began to dominate the total carbon oxidation rate. Denitrification rates were highest in Washington sediments; however, denitrification represented a larger fraction of the total carbon oxidation rate in the Mexican sediments (∼40% for Mexico vs. ∼30% for Washington). Sulfate reduction accounted for as much as 79% of the total carbon oxidation rate in shallow sediments and less than 20% in deep sediments on both margins. The offshore trends in carbon oxidation rate appeared to be related to the organic carbon input rate. Pore-water O2 and NO3− penetration depths were shallowest in nearshore stations and increased offshore. Regeneration ratios of C:N:P reveal “non-Redfield” behavior on both margins. Carbon budgets for the two margins demonstrate that off Mexico, a much greater percentage of the organic matter produced in the surface ocean reached the sediments (>15% vs. <8% for Mexico and Washington, respectively). On the Mexican margin, ∼8% of the primary production escaped oxidation in the surface sediments to be permanently buried, as compared with only ∼1.2% of the primary production on the Washington margin. This suggests that oxygen-deficient conditions on Mexican margin are linked to enhanced carbon preservation.  相似文献   

14.
The influence of aqueous silica on the hydrolysis of iron(III) nitrate and chloride salts in dilute aqueous solutions (mFe ∼ 0.01 mol/kg) was studied at ambient temperature using X-ray absorption fine structure (XAFS) spectroscopy at the Fe K-edge. Results show that in Si-free iron nitrate and chloride solutions at acid pH (pH < 2.5), Fe is hexa-coordinated with 6 oxygens of H2O- and/or OH-groups in the first coordination sphere of the metal, at an Fe-O distance of 2.00 ± 0.01 Å. With increasing pH (2.7 < pH < 13), these groups are rapidly replaced by bridging hydroxyls (-OH-) or oxygens (-O-), and polymerized Fe hydroxide complexes form via Fe-(O/OH)-Fe bonds. In these polymers, the first atomic shell of iron represents a distorted octahedron with six O/OH groups and Fe-O distances ranging from 1.92 to 2.07 Å. The Fe octahedra are linked together by their edges (Fe-Fe distance 2.92-3.12 Å) and corners (Fe-Fe distance ∼3.47 ± 0.03 Å). The Fe-Fe coordination numbers (Nedge = 1-2; Ncorner = 0.5-0.7) are consistent with the dominant presence of iron dimers, trimers and tetramers at pH 2.5 to 2.9, and of higher-polymerized species at pH > 3.At pH > 2.5 in the presence of aqueous silica, important changes in Fe(III) hydrolysis are detected. In 0.05-m Si solutions (pH ∼ 2.7-3.0), the corner linkages between Fe octahedra in the polymeric complexes disappear, and the Fe-Fe distances corresponding to the edge linkages slightly increase (Fe-Feedge ∼ 3.12-3.14 Å). The presence of 1 to 2 silicons at 3.18 ± 0.03 Å is detected in the second atomic shell around iron. At basic pH (∼12.7), similar structural changes are observed for the iron second shell. The Fe-Si and Fe-Fe distances and coordination numbers derived in this study are consistent with (1) Fe-Si complex stoichiometries Fe2Si1-2 and Fe3Si2-3 at pH < 3; (2) structures composed of Fe-Fe dimers and trimers sharing one or two edges of FeO6-octahedra; and (3) silicon tetrahedra linked to two neighboring Fe octahedra via corners. At higher Si concentration (0.16 m, polymerized silica solution) and pH ∼ 3, the signal of the Fe second shell vanishes indicating the destruction of the Fe-Fe bonds and the formation of different Fe-Si linkages. Moreover, ∼20 mol.% of Fe is found to be tetrahedrally coordinated with oxygens in the first coordination shell (RFe-O = 1.84 Å). This new finding implies that Fe may partially substitute for Si in the tetrahedral network of the silica polymers in Si-rich solutions.The results of this study demonstrate that aqueous silica can significantly inhibit iron polymerization and solid-phase formation, and thus increase the stability and mobility of Fe(III) in natural waters. The silica “poisoning” of the free corner sites of iron-hydroxide colloids should reduce the adsorption and incorporation of trace elements by these colloids in Si-rich natural waters.  相似文献   

15.
Interest in the pyroxenes has increased since the realization that their alteration products could carry a stable remnant magnetization which is possibly related to the earth's magnetic field and would therefore be of great geophysical importance.In the present work, the oxidation of artificial samples of the (Mg,Fe)SiO3 pyroxene series was studied thermogravimetrically at the constant oxygen pressure of air and temperatures up to 1350°C. The resulting alteration products were determined after complete oxidation by a specific technique which is here reported as a new quantitative analytical method. This method could be applied to many other silicate groups, provided that iron is the only transitional element. Using natural samples, the accurate measure of the ratio Fe3+Fe2+ provides a basis for a possible quantitative magnetic analytical method and for a geothermometer. Factors affecting the results, i.e., (a) the volatiles and (b) the contamination of transitional elements other than iron, were recognized but could be eliminated by using specific techniques.A large region of metastable solid solution of hematite (Fe2O3) in the spinel phase was found. The resulting oxides, after complete oxidation and precipitation of the Fe2O3 phase from the metastable spinel phase, were studied by thermogravimetric analysis and X-ray diffraction.  相似文献   

16.
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   

17.
《Chemical Geology》2004,203(1-2):153-168
The importance of the magnetic iron sulfide minerals, greigite (Fe3S4) and pyrrhotite (Fe7S8), is often underappreciated in geochemical studies because they are metastable with respect to pyrite (FeS2). Based on magnetic properties and X-ray diffraction analysis, previous studies have reported widespread occurrences of these magnetic minerals along with magnetite (Fe3O4) in two thick Plio-Pleistocene marine sedimentary sequences from southwestern Taiwan. Different stratigraphic zones were classified according to the dominant magnetic mineral assemblages (greigite-, pyrrhotite-, and magnetite-dominated zones). Greigite and pyrrhotite are intimately associated with fine-grained sediments, whereas magnetite is more abundant in coarse-grained sediments. We measured total organic carbon (TOC), total sulfur (TS), total iron (FeT), 1N HCl extractable iron (FeA), and bulk sediment grain size for different stratigraphic zones in order to understand the factors governing the formation and preservation of the two magnetic iron sulfide minerals. The studied sediments have low TS/FeA weight ratios (0.03–0.2), far below that of pyrite (1.15), which indicates that an excess of reactive iron was available for pyritization. Observed low TS (0.05–0.27%) is attributed to the low organic carbon contents (TOC=0.25–0.55%), which resulted from dilution by rapid terrigenous sedimentation. The fine-grained sediments also have the highest FeT and FeA values. We suggest that under conditions of low organic carbon provision, the high iron activity in the fine-grained sediments may have removed reduced sulfur so effectively that pyritization was arrested or retarded, which, in turn, favored preservation of the intermediate magnetic iron sulfides. The relative abundances of reactive iron and labile organic carbon appear to have controlled the transformation pathway of amorphous FeS into greigite or into pyrrhotite. Compared to pyrrhotite-dominated sediments, greigite-dominated sediments are finer-grained and have higher FeA but lower TS. We suggest that diagenetic environments with higher supply of reactive iron, lower supply of labile organic matter, and, consequently, lower sulfide concentration result in relatively high Eh conditions, which favor formation of greigite relative to pyrrhotite.  相似文献   

18.
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   

19.
Iron-hydroxide-rich and plant litter-containing sediments from natural sites contaminated with uranium mine tailing leachates were examined for their ability to adsorb arsenic. The samples with high contents of iron hydroxides (Fetotal concentration, >300 g kg−1) exhibited remarkable fixation of arsenic (up to 40 g As kg−1). This value corresponded approximately to the supersaturation point for natural iron hydroxides under the present conditions, and it was significantly lower than the value found for synthetic iron hydroxides. There was a strong correlation (R=0.8999) between the concentration of iron and that of arsenic at low arsenic contents, indicating adsorption on strong binding sites. Although all the samples had noticeable contents of organic carbon (plant litter), calcium, and manganese, no obvious effect of these elements on arsenic fixation could be detected. The amount of iron hydroxides was found the only fixation-controlling parameter immediately below a leaching water source.  相似文献   

20.
A geological survey carried out in the Yaoundé (Cameroon) region has revealed the presence of homogeneous clayey laterite in the upper part of a laterite cover on interfluves, thickest on hills (780–800 m altitude) where ferricrete is absent, and clayey heterogeneous hydromorphic material in valleys. We present in this paper the physical, mineralogical and geochemical properties of these occurrences and discuss their potential as raw material for pottery, manufacture of bricks and tiles. These clayey raw materials are mostly made up of fine particles (ranging from 55 to 60% clay + silt in the clayey laterite, more than 70% clay + silt in the clayey hydromorphic material). Their chemical composition is characterized by silica (<60% SiO2), alumina (<35% Al2O3) and iron (ranging from 3 to 14% Fe2O3). Their main clay minerals are disorganized and poorly crystallized kaolinites. The average limits of liquidity (44.56% versus 91.58%) and limits of plasticity (22.4 versus 45.93) revealed that clayey hydromorphic material has the greatest plasticity. The studied raw materials are suitable for making pottery as well as the manufacture of bricks and tiles. However, the high iron content in the clayey laterite (between 11 and 12% Fe2O3) prevents their efficient use in the manufacture of ceramics.  相似文献   

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