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1.
Enthalpies of solution of synthetic pentlandite Fe4.5Ni4.5S8, natural violarite (Fe0.2941Ni0.7059)3S4 from Vermillion mine, Sudbury, Ontario, synthetic pyrrhotite, FeS, synthetic high temperature NiS, synthetic vaesite, NiS2, synthetic pyrite, FeS2, Ni and Fe have been measured in a Ni0.6S0.4 melt at 1,100 K. Using these data and the standard enthalpies of formation of binary sulfides, given in literature, standard enthalpies of formation of pentlandite and violarite were calculated. The following values are reported: ΔH f o, Pent =?837.37±14.59 kJ mol?1 and ΔH f o, Viol =?378.02±11.81 kJ mol?1. While there are no thermo-chemical data for pentlandite with which our new value can be compared, an equilibrium investigation of stoichiometric violarite by Craig (1971) gives a significantly less negative enthalpy of formation. It is suggested that the difference may be due to the higher degree of order in the natural sample.  相似文献   

2.
Although pseudomorphic mineral replacement reactions are common in all geological environments, and have long been considered important to many geological processes such as metamorphism, metasomatism, diagenesis, and chemical weathering, their mechanisms are still not well known. We present a combined textural and kinetic study of the replacement of pentlandite, (Fe,Ni)9S8, by violarite (NiFe)3S4, and describe the mechanisms and kinetic behavior of this reaction by considering the role of the fluid phase, the causes of coupling between pentlandite dissolution and violarite precipitation, the rate-limiting steps controlling the kinetic behavior, and the origin of the length scale of the features preserved during pseudomorphism.The experiments were conducted under mild hydrothermal conditions (80-210 °C, vapor saturated pressures). Reaction kinetics shows a complex behavior depending on various physical and chemical parameters including temperature, pH, concentrations of various reaction species, solid-weight-to-fluid-volume-ratio and specific surface area. The rate of replacement (i) increases with temperature from 80 to 125 °C, then decreases as temperature further increases to 210 °C, (ii) first increases then decreases with decreasing pH from pH 6 to 1, (iii) increases with increasing concentration of oxidants such as O2(aq), H2O2, and KMnO4, but decreases with increasing concentration of Ni2+ and Fe3+, and with increasing solid-weight-to-fluid-volume ratio, (iv) increases linearly with the specific surface area. This kinetic behavior as well as the resulting textures revealed a coupled dissolution-reprecipitation reaction mechanism.Nanometer-scale pseudomorphic replacement, through which the crystallographic orientation of pentlandite is inherited by violarite, occurs only between 1 < pH < 6, and spatial coupling between dissolution and reprecipitation is controlled by the local solution chemistry as well as by epitaxial nucleation mediated by the pentlandite substrate. The kinetic results show that pentlandite dissolution is rate-limiting under mild acidic to neutral conditions (1 < pH < 6), while violarite precipitation is rate-limiting under strong acidic conditions (pH 1). The difference in rate-limiting steps influences the coupling mechanism and causes the different degrees of preservation (length scale of pseudomorphism) and different morphologies observed at high and low pHs: pentlandite dissolution being rate-limiting results in nanoscale coupling between dissolution and precipitation and thus nanoscale pseudomorphism (length scale <20 nm), in which the replacement precisely preserves the morphology and internal details, resembling remarkably the natural pentlandite/violarite assemblages. In contrast, violarite precipitation being rate-limiting results in microscale pseudomorphism (length scale ∼10 μm): the morphology of the pentlandite grains is only roughly preserved and internal details are not preserved.This case study illustrates some general principles of replacement reactions proceeding via the coupled dissolution-reprecipitation mechanism: (i) primary mineral dissolution needs to be rate-limiting compared to the secondary mineral precipitation in order to achieve a high degree pseudomorphic replacement; (ii) the effects of solution composition on reaction kinetics can be qualitatively rationalized by considering the rate-limiting step reaction.  相似文献   

3.
The Acoje massif is part of a mafic-ultramafic complex, the Zambales ophiolite, and is a fragment of Mesozoic oceanic crust. This paper documents the occurrence and phase relations of sulfides and associated phases in the critical zone of the Acoje massif. The Acoje critical zone (ACZ) forms the basal cumulate sequence of the massif and consists of a variably serpentinized lower ultramafic zone and a relatively less altered upper mafic zone. Two distinct sulfide associations have been identified: (1) a troilite (±pyrrhotite)-dominated group hosted by the mafic zone and (2) a pentlandite-dominated group hosted by the ultramafic zone. Troilite-dominated assemblages represent the original mineralogy of magmatically precipitated sulfides in the entire cumulate sequence. The pentlandite-dominated group appears to have evolved from the primary magmatic sulfides during low-temperature re-equilibration. The paragenetic evolution from the magmatic assemblage to the low-temperature assemblage appears to have proceeded as follows: (1) S-rich hexagonal pyrrhotite+pentlandite+chalcopyrite (or cubanite)+magnetite, (2) S-poor hexagonal pyrrhotite+pentlandite+intermediate solid solution (iss) phase (and/or cubanite)+magnetite, (3) troilite (or mackinawite)+pentlandite+iss+magnetite, (4) troilite (or mackinawite)+pentlandite+iss+native Cu+magnetite, (5) pentlandite+native Cu+magnetite, and (6) pentlandite+native Cu+Fe-Ni alloy+magnetite. This evolutionary trend, in conjunction with the observed textural, chemical, and sulfur-isotopic relations, indicates that the native metal and alloy phases in the ACZ were produced by low-temperature reduction of the primary magmatic sulfides. Correlations between sulfide assemblages and coexisting silicate-hydrosilicate-oxide assemblages further indicate that this alteration occurred during retrograde serpentinization of the Acoje massif. Two end-member models that could explain the inferred low-temperature mineralogic evolution of the ACZ sulfides are described: (1) an isothermal reduction model and (2) a non-isothermal equilibration model. Both isothermal and non-isothermal effects apparently were involved in the development of variably reduced sulfide-oxide-metal assemblages from the initial magmatic sulfides.  相似文献   

4.
A refined Avrami method, that assumes that the activation energy is a function of reaction extent y, was used to analyze the kinetics of the exsolution of pentlandite from mss/pyrrhotite (bulk composition, (Fe0.77Ni0.19)S) over the temperature range 473 to 573 K. The experimental results show the reaction rates vary from 1.6 × 10−5 to 5.0 × 10−7 s−1 at 473 K and from 9.4 × 10−5 to 4.1 × 10−7 s−1 at 573 K. Examination of exsolution textures indicated that the mechanism of exsolution did not change significantly over the temperature range investigated. The activation energy (Ea) decreases from 49.6 to 20.7 kJ mol−1 over the course of the reaction. The decrease in Ea with y is related to the change in the dominant factor of pentlandite exsolution, from nucleation dominant at the beginning to metal ion diffusion dominant at the end. The classic Avrami method provides average values of kinetic parameters for the overall solid-state reaction while the refined Avrami method provides more a detailed indication of the variation of kinetic parameters over the course of the reaction. Previously published kinetic data for the exsolution of pentlandite from mss/pyrrhotite are reevaluated using the refined Avrami method.  相似文献   

5.
The electronic absorption spectra of three biotites with largely differing Fe2+/Fe3+ ratios were studied before and after thermal dehydration and oxidation of divalent iron. Three absorption bands near 17,100, 20,500 and 24,100 cm?1 and an absorption edge at slightly higher energies are assigned to trivalent iron present in clusters of strongly interacting ions. The presence of additional broad absorption bands due to intervalence transfer between Fe2+ and Fe3+ or Ti4+ in this region cannot be excluded for biotites with high Fe2+ concentrations. Three bands at lower energies show a satisfactory correlation with concentration of divalent iron and decrease in the same proportions with oxidation. We therefore assign them to split components of the spin-allowed ligand field transition of Fe2+ at the M 1 and M 2 sites. This contradicts the assignment of one of these bands to an intervalence charge transfer between Fe2+ and Fe3+ by previous authors. It is shown that there is no indisputable evidence against our assignment.  相似文献   

6.
To better understand the role of aqueous alteration on the CI1 parent body, we have analyzed the texture, composition and mineral associations of iron nickel sulfides in four of the five known CI1 chondrites.The most commonly-occurring sulfide present in the CI1 chondrites is the iron-deficient Fe,Ni sulfide pyrrhotite ([Fe,Ni]1−xS), that has a composition close to that of stoichiometric troilite (FeS). Three of the CI1s (Alais, Ivuna and Tonk) also contain pentlandite ([Fe,Ni]9S8), although pentlandite is a rare phase in Ivuna. Cubanite (CuFe2S3) was found in both Alais and Ivuna in this study, although it has also been reported in Orgueil (MacDougall and Kerridge, 1977). The pyrrhotite grains in all four chondrites form hexagonal, rectangular or irregular shapes, and show no evidence of Ni or Co zoning. The pyrrhotite grains in Orgueil and Ivuna are, in general, smaller, and show more “corrosions,” or “embayments,” than those in Alais or Tonk.We suggest that the precursor sulfide present in the CI1 chondrites was troilite which, during brecciation and oxidation on the parent body at a temperature of 100°C or less, converted the troilite to magnetite and pyrrhotite with pentlandite inclusions. Subsequently, continued alteration on the parent body removed pentlandite—partially from Alais, Tonk and Ivuna, completely from Orgueil—leaving behind pyrrhotite with spaces (“corrosions”) where the pentlandite had been. Ni derived from the pentlandite was incorporated into ferrihydrite, onto the surface of which the Ni,Na sulfate Ni-bloedite formed.Based on the size and abundant “corrosions” within pyrrhotite grains, combined with observations from other authors, we conclude that Orgueil and Ivuna have undergone a greater degree of alteration than Alais and Tonk. Further work is needed to assess the conditions under which pentlandite would be dissolved preferentially to pyrrhotite, as the study of terrestrial literature indicates that the latter mineral is preferentially removed.  相似文献   

7.
《Applied Geochemistry》1993,8(6):569-586
Crude oil floating on the water table in a sand and gravel aquifer provides a constant source of hydrocarbons to the groundwater at a site near Bemidji, Minnesota. The degradation of hydrocarbons affects the concentrations of oxidized and reduced aqueous species in the anoxic part of the contaminant plume that developed downgradient from the oil body. The concentrations of Fe2+, Mn2+ and CH4, Eh measurements, and the δ13C ratios of the total inorganic C indicate that the plume became more reducing ver a 5-a period. However, the size of the contaminant plume remained stable during this time. Field data coupled with laboratory microcosm experiments indicate that benzene and the alkylbenzenes are degraded in an anoxic environment. In anaerobic microcosm experiments conducted under field conditions, almost complete degradation (98%) was observed for benzene in 125 d and for toluene in 45 d. Concentrations of aqueous Fe2+ and Mn2+ increased in these experiments, indicating that the primary reactions were hydrocarbon degradation coupled with Fe and Mn reduction.Mass transfer calculations on a 40-m flowpath in the anoxic zone, downgradient from the oil body, indicated that the primary reactions in the anoxic zone are oxidation of organic compounds, precipitation of siderite and a ferroan calcite, dissolution of iron oxide and outgassing of CH4 and CO2. The major difference in the two models presented is the ratio of CO2 and CH4 that outgasses. Both models indicate quantitatively that large amounts of Fe are dissolved and reprecipitated as ferrous iron in the anoxic zone of the contaminant plume.  相似文献   

8.
The stability relations of calcite and siderite in the system Ca2+-Fe2+-CO 3 2– Cl 2 2– -H2O have been determined between 150 and 400° C in the pressure range from 250 to 2000 bars.It was found that the composition of the fluid phase coexisting with calcite and siderite is very poor in Fe2+ and correspondingly very rich in Ca2+ (see Tab. 1 and Fig. 3). The mole proportion Ca2+/(Ca2++Fe2+) exceeds the value 0.98 at temperatures below 250° C when fluid pressure is 1000 bars. The stability field of calcite narrows with decreasing temperature, increasing pressure, and decreasing concentration of dissolved salts (CaCl2++FeCl2). In our experiments siderite becomes unstable at about 400° C (see p. 158).The experimental data indicate that siderite will be formed by reaction of calcite with FeCl2-bearing solutions that have very low concentrations of Fe2+ as well as high Ca2+/(Ca2++Fe2+)-ratios. Solutions coexisting with calcite must be very poor in Fe2+, otherwise siderite is formed.

Herrn Prof. Dr. H. G. F. Wikkleb danke ich sehr für sein förderndes Interesse an dieser Arbeit und für eine kritische Durchsicht des Manuskriptes. Der Deutschen Forschungsgemeinschaft gebiihrt Dank für die Arbeitsmöglichkeit mit den Apparaturen, die Herrn Prof. Dr. Winkler zür Verfugung gestellt wurden.  相似文献   

9.
In the Ospin–Kitoi ultramafic massif of the Eastern Sayan, accessory and ore Cr-spinel are mainly represented by alumochromite and chromite. Copper–nickel mineralization hosted in serpentinized ultramafic rocks occurs as separate grains of pentlandite and pyrrhotite, as well as assemblages of (i) hexagonal pyrrhotite + pentlandite + chalcopyrite and (ii) monoclinal pyrrhotite + pentlandite + chalcopyrite. Copper mineralization in rodingite is presented by bornite, chalcopyrite, and covellite. Talc–breunnerite–quartz and muscovite–breunnerite–quartz listvenite contains abundant sulfide and sulfoarsenide mineralization: pyrite, gersdorffite, sphalerite, Ag–Bi and Bi-galena, millerite, and kuestelite. Noble metal mineralization is represented by Ru–Ir–Os alloy, sulfides, and sulfoarsenides of these metals, Au–Cu–Ag alloys in chromitite, laurite intergrowth, an unnamed mineral with a composition of Cu3Pt, orcelite in carbonized serpentinite, and sperrylite and electrum in serpentinite. Sulfide mineralization formed at the late magmatic stage of the origination of intrusion and due to fluid–metamorphic and retrograde metasomatism of primary rocks.  相似文献   

10.
A new mineral, droninoite, was found in a fragment of a weathered Dronino iron meteorite (which fell near the village of Dronino, Kasimov district, Ryazan oblast, Russia) as dark green to brown fine-grained (the size of single grains is not larger than 1 μm) segregations up to 0.15 × 1 × 1 mm in size associated with taenite, violarite, troilite, chromite, goethite, lepidocrocite, nickelbischofite, and amorphous Fe3+ hydroxides. The mineral was named after its type locality. Aggregates of droninoite are earthy and soft; the Mohs hardness is 1–1.5. The calculated density is 2.857 g/cm3. Under a microscope, droninoite is dark gray-green and nonpleochroic. The mean (cooperative for fine-grained aggregate) refractive index is 1.72(1). The IR spectrum indicates the absence of S O 4 2? and C O 3 2? anions. Chemical composition (electron microprobe, partition of total iron into Fe2+ and Fe3+ made on the basis of the ratio (Ni + Fe2+): Fe3+ = 3: 1; water is calculated from the difference) is as follows, wt %: 36.45 NiO, 12.15 FeO, 17.55 Fe2O3, 23.78 H2O, 13.01 Cl, ?O=Cl2 ?2.94, total is 100.00. The empirical formula (Z = 6) is Ni2.16Fe 0.75 2+ Fe 0.97 3+ Cl1.62(OH)7.10 · 2.28H2O. The simplified formula is Ni3Fe3+Cl(OH)8 · 2H2O. Droninoite is trigonal, space group R \(\bar 3\) m, R3m, or R32; a = 6.206(2), c = 46.184(18) Å; V = 1540.4(8) Å3. The strong reflections in the X-ray powder diffraction pattern [d, Å (I, %) (hkl)] are 7.76(100)(006), 3.88(40)(0.0.12), 2.64(25)(202, 024), 2.32(20)(0.2.10), 1.965(0.2.16). The holotype specimen is deposited at the Fersman Mineralogical Museum, Russian Academy of Sciences, Moscow, registration number 3676/1.  相似文献   

11.
Samples of the eosphorite-childrenite [(Mn2+, Fe2+)AlPO4(OH)2H2O] series from Divino das Laranjeiras and Araçuaí (Minas Gerais State) and Parelhas (Rio Grande do Norte State) pegmatites have been investigated by X-ray diffraction, microprobe analysis and Mössbauer spectroscopy at 295 and 77 K. The Mössbauer spectra of ernstite [(Mn2+, Fe3+)AlPO4(OH)2-xOx] showed the existence of ferric ions in both A and B sites, whereas ferrous ions seem to be located exclusively in the A site. Nonoxidised samples show ferrous ions located in both sites, and no Fe3+ could be detected. The interpretation of the Mössbauer spectra of both, oxidised and nonoxidised samples, is difficult because the hyperfine parameters of these minerals are rather similar, rendering it difficult to make proper site assignments.  相似文献   

12.
X-ray absorption spectroscopy, including extended X-ray absorption fine structure (EXAFS) and X-ray absorption near-edge structure (XANES) techniques, have been used to determine the structure and speciation of complexes for Fe2+ and Fe3+ chloride solutions at a variety of pH's, ionic strengths, and chloride/iron ratios.Low intensity K-edge transition features and analysis of modified pair correlation functions, derived from Fourier transformation of EXAFS spectra, show a regular octahedral coordination of Fe(II) by water molecules with a first-shell Fe2+-O bond distance, closely matching octahedral Fe2+-O bonds obtained from solid oxide model compounds. Solution Fe2+-O bond distances decrease with chloride/iron ratio, pH, and total FeCl2 concentration. A slight intensification of the 1s → 3d transition with increasing FeCl2 concentration suggests that chloride may begin to mix with water as a nearest-neighbor octahedral ligand. Fe3+ solutions show a pronounced increase in the 1s → 3d transition intensities between 1.0 M FeCl3/7.8 M Cl? to 1.0 M FeCl3/ 15 M Cl?, indicating a coordination change from octahedral to tetrahedral complexes. EXAFS analyses of these solutions show an increase in first-shell Fe3+-ligand distances despite this apparent reduction in coordination number. This can be best explained by a change from regular octahedral complexes of ferric iron (either Fe(H2O)63+ or trans-Fe(H2O)4Cl2 or both; Fe3+-O bond distances of 2.10 Å) to tetra-chloro complexes [Fe3+-Cl bond distances of 2.25 Å].  相似文献   

13.
A first experimental study was conducted to determine the equilibrium iron isotope fractionation between pyrrhotite and silicate melt at magmatic conditions. Experiments were performed in an internally heated gas pressure vessel at 500 MPa and temperatures between 840 and 1000 °C for 120-168 h. Three different types of experiments were conducted and after phase separation the iron isotope composition of the run products was measured by MC-ICP-MS. (i) Kinetic experiments using 57Fe-enriched glass and natural pyrrhotite revealed that a close approach to equilibrium is attained already after 48 h. (ii) Isotope exchange experiments—using mixtures of hydrous peralkaline rhyolitic glass powder (∼4 wt% H2O) and natural pyrrhotites (Fe1 − xS) as starting materials— and (iii) crystallisation experiments, in which pyrrhotite was formed by reaction between elemental sulphur and rhyolitic melt, consistently showed that pyrrhotite preferentially incorporates light iron. No temperature dependence of the fractionation factor was found between 840 and 1000 °C, within experimental and analytical precision. An average fractionation factor of Δ 56Fe/54Fepyrrhotite-melt = −0. 35 ± 0.04‰ (2SE, n = 13) was determined for this temperature range. Predictions of Fe isotope fractionation between FeS and ferric iron-dominated silicate minerals are consistent with our experimental results, indicating that the marked contrast in both ligand and redox state of iron control the isotope fractionation between pyrrhotite and silicate melt. Consequently, the fractionation factor determined in this study is representative for the specific Fe2+/ΣFe ratio of our peralkaline rhyolitic melt of 0.38 ± 0.02. At higher Fe2+/ΣFe ratios a smaller fractionation factor is expected. Further investigation on Fe isotope fractionation between other mineral phases and silicate melts is needed, but the presented experimental results already suggest that even at high temperatures resolvable variations in the Fe isotope composition can be generated by equilibrium isotope fractionation in natural magmatic systems.  相似文献   

14.
The Garson Ni–Cu–platinum group element deposit is a deformed, overturned, low Ni tenor contact-type deposit along the contact between the Sudbury Igneous Complex (SIC) and stratigraphically underlying rocks of the Huronian Supergroup in the South Range of the 1.85-Ga Sudbury structure. The ore bodies are coincident with steeply south-dipping, north-over-south D1 shear zones, which imbricated the SIC, its ore zones, and underlying Huronian rocks during mid-amphibolite facies metamorphism. The shear zones were reactivated as south-over-north, reverse shear zones during D2 at mid-greenschist facies metamorphism. Syn-D2 metamorphic titanite yields an age of 1,849?±?6 Ma, suggesting that D1 and D2 occurred immediately after crystallization of the SIC during the Penokean Orogeny. The ore bodies plunge steeply to the south parallel to colinear L1 and L2 mineral lineations, indicating that the geometry of the ore bodies are strongly controlled by D1 and D2. Sulfide mineralization consists of breccia ores, with minor disseminated sulfides hosted in norite, and syn-D2 quartz–calcite–sulfide veins. Mobilization by ductile plastic flow was the dominant mechanism of sulfide/metal mobilization during D1 and D2, with additional minor hydrothermal mobilization of Cu, Fe, and Ni by hydrothermal fluids during D2. Metamorphic pentlandite overgrows a S1 ferrotschermakite foliation in D1 deformed ore zones. Pentlandite was exsolved from recrystallized polygonal pyrrhotite grains after cessation of D1, which resulted in randomly distributed large pentlandite grains and randomly oriented pentlandite loops along the grain boundaries of polygonal pyrrhotite within the breccia ore. It also overgrows a S2 chlorite foliation in D2 shear zones. Pyrrhotite recrystallized and was flattened during D2 deformation of breccia ore along narrow shear zones. Exsolution of pentlandite loops along the grain boundaries of these flattened grains produced a pyrrhotite–pentlandite layering that is not observed in D1 deformed ore zones. The overprinting of the two foliations by pentlandite and exsolution of pentlandite along the grain boundaries of flattened pyrrhotite grains suggest that the Garson ores reverted to a metamorphic monosulfide solid solution at temperatures ranging between 550 and 600 °C during D1 and continued to deform as a monosulfide solid solution during D2.  相似文献   

15.
The exceptional ability of dendrimers to coordinate metal ions yields the potential for many applications including wastewater remediation, which is the focus of this study. Here, the comparison of metal ion removal rate from simulated wastewater by generation 4 dendrimers with external hydroxyl functional groups (G4-OH) is evaluated for Ni2+, Fe2+, and Fe3+ ions. Ni2+ to amine complexation occurred more rapidly than Fe3+, which was more rapid than Fe2+ complexation. These results indicate that both charge density and d-electron configuration are important toward the chelation rate. The impact of both factors is discussed in light of existing models in which precursor aquation rates have been proposed as a key intermediate step. Additionally, the application of the dendrimers as chelation agents is further advanced by immobilizing the dendrimer to titania and re-evaluating its chelation ability for Ni2+ removal. The dendrimer immobilization decreased the pseudo-first-order rate coefficient for Ni2+—amine complexation at a pH of 7 by a factor of 7.5. This result is significant as it suggests that mass transfer becomes important following immobilization of the dendrimer to titania.  相似文献   

16.
Fifteen samples of (Mg,Fe)SiO3 majorite with varying Fe/Mg composition and one sample of (Mg,Fe)(Si,Al)O3 majorite were synthesized at high pressure and temperature under different conditions of oxygen fugacity using a multianvil press, and examined ex situ using X-ray diffraction and Mössbauer and optical absorption spectroscopy. The relative concentration of Fe3+ increases both with total iron content and increasing oxygen fugacity, but not with Al concentration. Optical absorption spectra indicate the presence of Fe2+–Fe3+ charge transfer, where band intensity increases with increasing Fe3+ concentration. Mössbauer data were used in conjunction with electron microprobe analyses to determine the site distribution of all cations. Both Al and Fe3+ substitute on the octahedral site, and charge balance occurs through the removal of Si. The degree of Mg/Si ordering on the octahedral sites in (Mg,Fe)SiO3 majorite, which affects both the c/a ratio and the unit cell volume, is influenced by the thermal history of the sample. The Fe3+ concentration of (Mg,Fe)(Si,Al)O3 majorite in the mantle will reflect prevailing redox conditions, which are believed to be relatively reducing in the transition zone. Exchange of material across the transition boundary to (Mg,Fe) (Si,Al)O3 perovskite would then require a mechanism to oxidize sufficient iron to satisfy crystal-chemical requirements of the lower-mantle perovskite phase.  相似文献   

17.
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   

18.
The discovery of nickel-, copper-, and zinc-bearing iron sulfides from comet 81P/Wild 2 (Wild 2) represents the strongest evidence, in the Stardust collection, of grains that formed in an aqueous environment. We investigated three microtomed TEM sections which contain crystalline sulfide assemblages from Wild 2 and twelve thin sections of the hydrothermally altered CI chondrite Orgueil. Detailed structural and compositional characterizations of the sulfide grains from both collections reveal striking similarities. The Stardust samples include a cubanite (CuFe2S3) grain, a pyrrhotite [(Fe,Ni)1−xS]/pentlandite [(Fe,Ni)9S8] assemblage, and a pyrrhotite/sphalerite [(Fe,Zn)S] assemblage. Similarly, the CI-chondrite sulfides include individual cubanite and pyrrhotite grains, cubanite/pyrrhotite assemblages, pyrrhotite/pentlandite assemblages, as well as possible sphalerite inclusions within pyrrhotite grains. The cubanite is the low temperature orthorhombic form, which constrains temperature to a maximum of 210 °C. The Stardust and Orgueil pyrrhotites are the 4C monoclinic polytype, which is not stable above ∼250 °C. The combinations of cubanite and pyrrhotite, as well as pyrrhotite and pentlandite signify even lower temperatures. The crystal structures, compositions, and petrographic relationships of these sulfides constrain formation and alteration conditions. Taken together, these constraints attest to low-temperature hydrothermal processing.Our analyses of these minerals provide constraints on large scale issues such as: heat sources in the comet-forming region; aqueous activity on cometary bodies; and the extent and mechanisms of radial mixing of material in the early nebula. The sulfides in the Wild 2 collection are most likely the products of low-temperature aqueous alteration. They provide evidence of radial mixing of material (e.g. cubanite, troilite) from the inner solar system to the comet-forming region and possible secondary aqueous processing on the cometary body.  相似文献   

19.
The instability of transition metal dolomites [CaR2+(CO3)2 where R2+ is Fe, Co, Ni, Cu, or Zn] and the limited substitution of transition metal cations for Mg in the dolomite structure can be accounted for by the effect of octahedral distortion. For example, trigonal elongation of the Fe octahedron, due to the Jahn-Teller effect, observed in siderite and ankerite, results in elongation of the Ca octahedron which is sensitive to distortion because the radius of Ca2+ is close to the upper limit for octahedral coordination. Co, Ni, Cu, Zn octahedra are also thought to be deformed, relative to Mg octahedra, in carbonates.The free energy of formation (ΔGof) of R2+CO3 becomes more positive with increasing octahedral distortion. Estimated ΔGof(dolomite) as well as stabilities and solubility limits of R2+ in natural and synthetic dolomites suggest a series in order of decreasing stability: Mg >Mn >Zn >Fe >Co >Ni >Cu.ΔGof(est.) for the terminal Fe-dolomite solid solution [72 mol% CaFe(CO3)2] in the system CaCO3-MgCO3-FeCO3 may represent an empirical threshold value for dolomite stability which lies between ΔGof for Mn- and Zn-dolomites. While Zn-dolomite is probably not a stable phase, very extensive solid solution toward CaZn(CO3)2 is to be expected in the system CaCO3-MgCO3-ZnCO3. The tendency for transition metal dolomites to contain excess CaCO3 can also be accounted for in terms of octahedral distortion and AGof.  相似文献   

20.
Susceptibility, magnetisation and Mössbauer measurements are reported for a representative selection of 2:1 layer phyllosilicates. Eight samples from the mica, vermiculite and smectite groups include examples diluted in iron which are paramagnetic at all temperatures, as well as iron-rich silicates which order magnetically below 10 K. Anisotropic susceptibility of crystals of muscovite, biotite and vermiculite is quantitatively explained with a model where the Fe2+ ions lie in sites of effective trigonal symmetry, the trigonal axis lying normal to the sheets. The ferrous ground state is an orbital singlet. Ferric iron gives an isotropic contribution to the susceptibility. Fe2+-Fe2+ exchange interactions are ferromagnetic with y ～ 2 K, whereas Fe3+-Fe3+ coupling is antiferromagnetic in the purely ferric minerals. A positive paramagnetic Curie temperature for glauconite may be attributable to Fe2+ → Fe3+ charge transfer. Magnetic order was found to set in inhomogeneously for glauconite at 1–7 K. One biotite sample showed an antiferromagnetic transition at T N =7 K marked by a well-defined susceptibility maximum. Its magnetic structure, consisting of ferromagnetic sheets with moments in their planes coupled antiferromagnetically by other, weak interactions, resembles that found earlier for the 1:1 mineral greenalite.  相似文献   

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