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1.
Mechanisms of iron oxide transformations in hydrothermal systems   总被引：2，自引：0，他引：2  
Coexistence of magnetite and hematite in hydrothermal systems has often been used to constrain the redox potential of fluids, assuming that the redox equilibrium is attained among all minerals and aqueous species. However, as temperature decreases, disequilibrium mineral assemblages may occur due to the slow kinetics of reaction involving the minerals and fluids. In this study, we conducted a series of experiments in which hematite or magnetite was reacted with an acidic solution under H2-rich hydrothermal conditions (T = 100-250 °C, ) to investigate the kinetics of redox and non-redox transformations between hematite and magnetite, and the mechanisms of iron oxide transformation under hydrothermal conditions. The formation of euhedral crystals of hematite in 150 and 200 °C experiments, in which magnetite was used as the starting material, indicates that non-redox transformation of magnetite to hematite occurred within 24 h. The chemical composition of the experimental solutions was controlled by the non-redox transformation between magnetite and hematite throughout the experiments. While solution compositions were controlled by the non-redox transformation in the first 3 days in a 250 °C experiment, reductive dissolution of magnetite became important after 5 days and affected the solution chemistry. At 100 °C, the presence of maghemite was indicated in the first 7 days. Based on these results, equilibrium constants of non-redox transformation between magnetite and hematite and those of non-redox transformation between magnetite and maghemite were calculated. Our results suggest that the redox transformation of hematite to magnetite occurs in the following steps: (1) reductive dissolution of hematite to and (2) non-redox transformation of hematite and to magnetite.  相似文献   

2.
Redox and nonredox reactions of magnetite and hematite in rocks   总被引：1，自引：0，他引：1  
Redox and nonredox reactions causing pseudomorphic replacement of hematite by magnetite and magnetite by hematite are compared.Pseudomorphic replacements resulting from redox reactions are known as martitization [replacement of magnetite by hematite due to oxidation; reaction (1)] and mushketovitization [replacement of hematite by magnetite due to reduction; reaction (2)]. These two replacements cause characteristic ore textures and volume changes (reaction (1): increase of 1.66%; reaction (2): decrease of 1.64%). These small volume changes are the reason that martitization and mushketovitization are widespread in many rocks under condition, however, that oxidizing or reducing fluids (solutions) are present.The same initial and end products may also be involved in nonredox reactions. Reaction (3) is the replacement of hematite by magnetite due to simple addition of Fe2+ atoms under basic conditions. This reaction causes an increase of the volume of 47.6%. Reaction (4), causing a volume decrease of 32.2%, is the replacement of magnetite by hematite due to leaching of Fe2+ atoms under acidic conditions. From these volume changes it is concluded that reaction (4) may occur in many rock types, whereas reaction (3) is restricted to unlithified sediments only. However, ore textures caused by nonredox reactions are unknown and therefore their occurrence in rocks is hypothetical.  相似文献   

3.
The Blue Dot gold deposit, located in the Archean Amalia greenstone belt of South Africa, is hosted in an oxide (± carbonate) facies banded iron formation (BIF). It consists of three stratabound orebodies; Goudplaats, Abelskop, and Bothmasrust. The orebodies are flanked by quartz‐chlorite‐ferroan dolomite‐albite schist in the hanging wall and mafic (volcanic) schists in the footwall. Alteration minerals associated with the main hydrothermal stage in the BIF are dominated by quartz, ankerite‐dolomite series, siderite, chlorite, muscovite, sericite, hematite, pyrite, and minor amounts of chalcopyrite and arsenopyrite. This study investigates the characteristics of gold mineralization in the Amalia BIF based on ore textures, mineral‐chemical data and sulfur isotope analysis. Gold mineralization of the Blue Dot deposit is associated with quartz‐carbonate veins that crosscut the BIF layering. In contrast to previous works, petrographic evidence suggests that the gold mineralization is not solely attributed to replacement reactions between ore fluid and the magnetite or hematite in the host BIF because coarse hydrothermal pyrite grains do not show mutual replacement textures of the oxide minerals. Rather, the parallel‐bedded and generally chert‐hosted pyrites are in sharp contact with re‐crystallized euhedral to subhedral magnetite ± hematite grains, and the nature of their coexistence suggests that pyrite (and gold) precipitation was contemporaneous with magnetite–hematite re‐crystallization. The Fe/(Fe+Mg) ratio of the dolomite–ankerite series and chlorite decreased from veins through mineralized BIF and non‐mineralized BIF, in contrast to most Archean BIF‐hosted gold deposits. This is interpreted to be due to the effect of a high sulfur activity and increase in fO2 in a H2S‐dominant fluid during progressive fluid‐rock interaction. High sulfur activity of the hydrothermal fluid fixed pyrite in the BIF by consuming Fe2+ released into the chert layers and leaving the co‐precipitating carbonates and chlorites with less available ferrous iron content. Alternatively, the occurrence of hematite in the alteration assemblage of the host BIF caused a structural limitation in the assignment of Fe3+ in chlorite which favored the incorporation of magnesium (rather than ferric iron) in chlorite under increasing fO2 conditions, and is consistent with deposits hosted in hematite‐bearing rocks. The combined effects of reduction in sulfur contents due to sulfide precipitation and increasing fO2 during progressive fluid‐rock interactions are likely to be the principal factors to have caused gold deposition. Arsenopyrite–pyrite geothermometry indicated a temperature range of 300–350°C for the associated gold mineralization. The estimated δ34SΣS (= +1.8 to +2.5‰) and low base metal contents of the sulfide ore mineralogy are consistent with sulfides that have been sourced from magma or derived by the dissolution of magmatic sulfides from volcanic rocks during fluid migration.  相似文献   

4.
成矿作用过程中赤铁矿—磁铁矿之间非氧化还原转变   总被引：1，自引：0，他引：1  
自然界中铁氧化物的主要存在形式为赤铁矿和磁铁矿,两者之间的相互转变一直是人们关注和研究的热点。磁铁矿和赤铁矿之间的相互转变一直被认为是一个氧化还原反应的结果,反应的发生与一定的氧化剂或还原剂密切相关。然而,近年来一个铁氧化物之间的非氧化还原反应机制被提出,这种非氧化还原反应机制对于认识和了解复杂的成矿作用具有重要的意义。本文阐述了自然界中铁氧化物之间的相互交代结构,对BIF研究和实验学两方面的证据进行了综述,认为这种非氧化还原反应可能存在于很多不同类型的成矿作用过程之中。这种赤铁矿和磁铁矿之间的非氧化还原反应机制具有重要的理论和实际意义:一方面,仅靠地质作用过程中出现磁铁矿或赤铁矿现象不一定就能判别其形成流体的氧化还原状态;另一方面,它可以为勘探含后生赤铁矿的铁矿床提供新的找矿思路,进一步指导深埋在古风化面以下铁矿体的寻找。  相似文献   

5.
The rare garnet end member calderite, Mn 3 2+ Fe 2 3+ Si3O12, has been synthesized, under the oxygen fugacity of the hematite/magnetite buffer, at pressures not lower than 22 kbar. The synthetic crystals are generally zoned and may contain up to 3 mol% of the Fe2+-(=skiagite-) or 10 mol% of the Mn3+-(=blythite-) end members, but, under equilibrium conditions, the stable garnets have a restricted compositional range with about 1–4 mol% skiagite. Mn3+ represents only a residue of the Mn2O3 used in the starting material. At temperatures above 720° C (at 24 kbar) to 850° C (at 30 kbar) these garnets break down into coexisting pairs of magnetite-jacobsite and pyroxmangite-FeSiO3 solid solutions. No indication for divariancy of this breakdown reaction could be established so that the observed coexistence of garnet and breakdown products over a PT interval must be due to disequilibrium. Although extrapolations of the high-pressure stability data towards lower pressures are hazardous, it is clear that nearly pure calderite garnets can only form in metamorphic environments characterized by geothermal gradients not exceeding some 10°–15° C/km, that is in subduction zone metamorphism. A low-pressure end of the calderite stability is likely because, at temperatures below 250°–300° C, pyroxmangite probably becomes unstable and hydrous Mn2+-silicates appear among the low-temperature breakdown products of calderite. Since the upper temperature stability limits of the common garnet end members spessartine and andradite lie some 800° C above that for calderite, solid solutions with these components will drastically stabilize the garnet phase towards both higher temperatures and lower pressures. This explains why garnets containing around 70 mol% calderite can be formed in amphibolitefacies metamorphism.  相似文献   

6.
The Golyamo Kamenyane serpentinite is a portion of a metaophiolite, located in the Upper High-Grade Unit of the metamorphic basement of the Eastern Rhodope Metamorphic Complex, SE Bulgaria. It consists of metaharzburgite and metadunite hosting layers of metagabbro and some chromitite bodies. All these lithologies were affected by ultrahigh-pressure (UHP) metamorphism and subsequent retrograde evolution during exhumation. Chromite from chromitites can be classified into four textural groups: (1) partly altered chromite, (2) porous chromite, (3) homogeneous chromite and (4) zoned chromite. Partly altered chromite shows unaltered, Al-rich cores with unit cell size of 8.255 Å and Cr# [Cr/(Cr + Al) atomic ratio] = 0.52–0.60, Mg# [Mg/(Mg + Fe2+) atomic ratio] = 0.65–0.70 and Fe3+/(Fe3+ + Fe2+) = 0.20–0.30, surrounded by porous chromite, with a cell size of 8.325 Å, Fe3+/(Fe3+ + Fe2+) < 0.20 and values of Cr# and Mg# evolving from 0.60 to 0.91 and 0.65–0.44, respectively, from core to rim. The chemical composition of porous chromite varies within the following ranges: Cr# = 0.93–0.96, Mg# = 0.48–0.35 and Fe3+/(Fe3+ + Fe2+) = 0.22–0.53. Its unit cell size is very constant (8.350 Å). Most pores in porous and partly altered chromite are filled with chlorite, which also occurs between chromite grains. Homogeneous chromite has Fe3+/(Fe3+ + Fe2+) = 0.55–0.66, Cr# = 0.96–0.99, Mg# = 0.32–0.19 and a cell size of 8.385 Å. The cores of zoned chromite are similar to those of partially altered chromite, but the rims are identical to homogeneous chromite. Although chlorite predominates in the silicate matrix of homogeneous and zoned chromite, it coexists with some antigorite, talc and magnesiohornblende. Mineral data and thermodynamic modeling allow interpretation of the alteration patterns of chromite as the consequence of a two-stage process developed during retrograde metamorphic evolution coeval with fluid infiltration. During the first stage, chromite reacts in the presence of fluid with olivine to produce chlorite and Cr- and Fe2+-rich residual chromite (ferrous chromite) at ~700 to ~450 °C. This dissolution–precipitation reaction involves continuous chromite mass loss resulting in the development of a porous texture. This stage takes place progressively on cooling under water-saturated and reducing conditions. The second stage mainly consists of the formation of homogeneous chromite with ferrian chromite composition by the addition of magnetite to the porous ferrous chromite during a late oxidizing hydrothermal event.  相似文献   

7.
The Damoshan deposit is a small B-F-Sn Bi exoskarn deposit and contains a distinctive mineral assemblage comprising andradite,vesuvianite,calcite,diopside,magnetite,hematite,nordenskioldine,cassiterite,varlamoffite,schenfliesite,native bismuth,eulytite,bismite and bismuthite,in which the occurrence of eulytite is the first reported in China.Textures of the mineral paragenses show that andradite,vesuvianite and diopside were the earliest phases formed during metasomatism,i.e.,the skarn forming stage.Then nordenskioldine,magnetite and native bismuth,perhaps together with eulytite,were precipitated at the stage of retrograde alteration.The minerals varlamoffite,schoenfliesite,hematite ,bismite and bismuthite were probably the product of supergene alteration.The minerals were analyzed by means of electron microprobe.The data on the ,coexisting phases and their compositons show that during the metasomatism reduced F-and Sn-rich primary mineralizing solutions reacted with highly oxidized carbonated of the Gejie Formation,producing a high Fe^2 /Fe^3 skarn(vesuvianite-fluorite skarn)near the contact of granite,and a low Fe^2 /Fe^3 skarn(vesuvianite-fluorite skarn)near the contact of granite,and a low Fe^2 /Fe^3 skarn(andradite skarn)in the outer zone of the skarn body in which andradite is extremely tin-bearing up to 5.14 wt% SnO2),In the retrograde alteration stage ,B-rich,but F-and Si-deficient mineralizing solutions replaced the tin-bearing andradite,forming an association of nordenskioldine and magnetite,No sulphides were deposited at this stage because of the oxidization ambient conditions in the andradite skarn.In the spergene oxidation zone,the nordenskioldine was dissolved into varlmoffite and calcite,the native bismuth was transformed into bismite or bismuthite ,and the magnetite was altered into hematite under the action of the CO2-rich supergene solutions.  相似文献   

8.
The thermal stability of sideronatrite, ideally Na2Fe3+(SO4)2(OH)·3(H2O), and its decomposition products were investigated by combining thermogravimetric and differential thermal analysis, in situ high-temperature X-ray powder diffraction (HT-XRPD) and Fourier transform infrared spectroscopy (HT-FTIR). The data show that for increasing temperature there are four main dehydration/transformation steps in sideronatrite: (a) between 30 and 40 °C sideronatrite transforms into metasideronatrite after the loss of two water molecules; both XRD and FTIR suggest that this transformation occurs via minor adjustments in the building block. (b) between 120 and 300 °C metasideronatrite transforms into metasideronatrite II, a still poorly characterized phase with possible orthorhombic symmetry, consequently to the loss of an additional water molecule; X-ray diffraction data suggest that metasideronatrite disappears from the assemblage above 175 °C. (c) between 315 and 415 °C metasideronatrite II transforms into the anhydrous Na3Fe(SO4)3 compound. This step occurs via the loss of hydroxyl groups that involves the breakdown of the [Fe3+(SO4)2(OH)] ∞ 2? chains and the formation of an intermediate transient amorphous phase precursor of Na3Fe(SO4)3. (d) for T > 500 °C, the Na3Fe(SO4)3 compound is replaced by the Na-sulfate thenardite, Na2SO4, plus Fe-oxides, according to the Na3Fe3+(SO4)3 → 3/2 Na2(SO4) + 1/2 Fe2O3 + SOx reaction products. The Na–Fe sulfate disappears around 540 °C. For higher temperatures, the Na-sulfates decomposes and only hematite survives in the final product. The understanding of the thermal behavior of minerals such as sideronatrite and related sulfates is important both from an environmental point of view, due to the presence of these phases in evaporitic deposits, soils and sediments including extraterrestrial occurrences, and from the technological point of view, due to the use of these materials in many industrial applications.  相似文献   

9.
We have investigated grain boundary diffusion rates in enstatite by heating single crystals of quartz packed in powdered San Carlos olivine (Mg0.90Fe0.10)2SiO4 at controlled oxygen fugacities in the range 10?5.7 to 10?8.7?atm and temperatures from 1350° to 1450?°C for times from 5 to 100?h at 1?atm total pressure. Following the experiments, the thickness of the coherent polycrystalline reaction rim of pyroxene that had formed between the quartz and olivine was measured using backscatter scanning imaging in the electron microprobe. Quantitative microprobe analysis indicated that the composition of this reaction phase is (Mg0.92Fe0.08)2Si2O6. The rate of growth of the pyroxene increases with increasing temperature, is independent of the oxygen fugacity, and is consistent with a parabolic rate law, indicating that the growth rate is controlled by ionic diffusion through the pyroxene rim. Microstructural observations and platinum marker experiments suggest that the reaction phase is formed at the olivine-pyroxene interface, and is therefore controlled by the diffusion of silicon and oxygen. The parabolic rate constants determined from the experiments were analyzed in terms of the oxide activity gradient across the rim to yield mean effective diffusivities for the rate-limiting ionic species, assuming bulk transport through the pyroxene layer. These effective diffusivities are faster than the lattice diffusivities for the slowest species (silicon) calculated from creep experiments, but slower than measured lattice diffusivities for oxygen in enstatite. Thus, silicon grain boundary diffusion is most likely to be the rate-limiting process in the growth of the pyroxene rims. Also, as oxygen transport through the pyroxene rims must be faster than silicon transport, diffusion of oxygen along the grain boundaries must be faster than through the lattice. The grain boundary diffusivity for silicon in orthopyroxenite is then given by D¯gbSiδ=(3.3±3.0)×10?9f0.0O2e?400±65/RT?m3s?1, where the activation energy for diffusion is in kJ/mol, and δ is the grain boundary width in m. Calculated growth rates for enstatite under these conditions are significantly slower than predicted by an extrapolation from similar experiments performed at 1000?°C under high pressure (hydrous) conditions by Yund and Tullis (1992), perhaps due to water-enhancement of diffusion in their experiments.  相似文献   

10.
Spinels, Fe–Ti oxide minerals, apatites, and carbonates hosted in ophiolitic serpentinites and metagabbros of Gabal Garf (southern ED) and Wadi Hammariya (central ED) of Egypt are discussed. Microscopic and electron probe studies on these minerals are made to evaluate their textural and compositional variations. Alteration of chromites led to form ferritchromite and magnetite; rutile–magnetite intergrowths and martite are common in serpentinites. Fine trillis exsolution of ilmenite–magnetite and ilmenite–hematite and intergrowth of rutile–magnetite and ilmenite–sphene are recorded. Composite intergrowth grains of titanomagnetite–ilmenite trellis lamellae are common in metagabbros. The formation of ilmenite trellis and lamellae in magnetite and titanomagnetite indicate an oxidation process due to excess of oxygen contained in titanomagnetite; trapped and external oxidizing agents. This indicates the high P H2O and oxygen fugacity of the parental magma. The sulfides minerals include pyrrhotite, pyrite and chalcopyrite. Based on the chemical characteristics, the Fe–Ti oxide from the ophiolitic metagabbros in both areas corresponds to ilmenite. The patites from the metagabbros are identified as fluor-apatite. Carbonates are represented by dolomites in serpentinites and calcite in metagabbros. Spinel crystals in serpentinites are homogenous or zoned with unaltered cores of Al-spinel to ferritchromit and Cr-magnetite toward the altered rims. Compared to cores, the metamorphic rims are enriched in Cr# (0.87–1.00 vs. 0.83–0.86 for rims and cores, respectively) and impoverished in Mg# (0.26–0.48 vs. 0.56–0.67) due to Mg–Fe and Al (Cr)–Fe3+ exchange with the surrounding silicates during regional metamorphism rather than serpentinization process. The Fe–Ti oxides have been formed under temperature of ~800 °C for ilmenite. Al-spinels equilibrated below 500–550 °C, while the altered spinel rims correspond to metamorphism around 500–600 °C. Geochemical evidence of the podiform Al-spinels suggest a greenschist up to lower amphibolite facies metamorphism (at 500–600 °C), which is isofacial with the host rocks. Al-spinel cores do not appear to have re-equilibrated completely with the metamorphic spinel rims and surrounding silicates, suggesting relic magmatic composition unaffected by metamorphism. The composition of Al-spinel grains suggest an ophiolitic origin and derivation by crystallization of boninitic magma that belonging to a supra-subduction setting could form either in forearcs during an incipient stage of subduction initiation or in back-arc basins.  相似文献   

11.
The Madoonga iron ore body hosted by banded iron formation (BIF) in the Weld Range greenstone belt of Western Australia is a blend of four genetically and compositionally distinct types of high-grade (>55 wt% Fe) iron ore that includes: (1) hypogene magnetite–talc veins, (2) hypogene specular hematite–quartz veins, (3) supergene goethite–hematite, and (4) supergene-modified, goethite–hematite-rich detrital ores. The spatial coincidence of these different ore types is a major factor controlling the overall size of the Madoonga ore body, but results in a compositionally heterogeneous ore deposit. Hypogene magnetite–talc veins that are up to 3 m thick and 50 m long formed within mylonite and shear zones located along the limbs of isoclinal, recumbent F1 folds. Relative to least-altered BIF, the magnetite–talc veins are enriched in Fe2O3(total), P2O5, MgO, Sc, Ga, Al2O3, Cl, and Zr; and depleted in SiO2 and MnO2. Mafic igneous countryrocks located within 10 m of the northern contact of the mineralised BIF display the replacement of primary igneous amphibole and plagioclase, and metamorphic chlorite by hypogene ferroan chlorite, talc, and magnetite. Later-forming, hypogene specular hematite–quartz veins and their associated alteration halos partly replace magnetite–talc veins in BIF and formed during, to shortly after, the F2-folding and tilting of the Weld Range tectono-stratigraphy. Supergene goethite–hematite ore zones that are up to 150 m wide, 400 m long, and extend to depths of 300 m replace least-altered BIF and existing hypogene alteration zones. The supergene ore zones formed as a result of the circulation of surface oxidised fluids through late NNW- to NNE-trending, subvertical brittle faults. Flat-lying, supergene goethite–hematite-altered, detrital sediments are concentrated in a paleo-topographic depression along the southern side of the main ENE-trending ridge at Madoonga. Iron ore deposits of the Weld Range greenstone belt record remarkably similar deformation histories, overprinting hypogene alteration events, and high-grade Fe ore types to other Fe ore deposits in the wider Yilgarn Craton (e.g. Koolyanobbing and Windarling deposits) despite these Fe camps being presently located more than 400 km apart and in different tectono-stratigraphic domains. Rather than the existence of a synchronous, Yilgarn-wide, Fe mineralisation event affecting BIF throughout the Yilgarn, it is more likely that these geographically isolated Fe ore districts experienced similar tectonic histories, whereby hypogene fluids were sourced from commonly available fluid reservoirs (e.g. metamorphic, magmatic, or both) and channelled along evolving structures during progressive deformation, resulting in several generations of Fe ore.  相似文献   

12.
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   

13.
In the present work, we investigate the iron oxides and oxyhydroxides behavior and evolution, related to the geochemical behavior of some metals, which could be retained as solid phases in the sediments from an urban water reservoir lake, placed in Taiaçupeba, Great São Paulo, Brazil. These tasks were performed by the establishment of a proceduring setting for environmental monitoring analysis through Mössbauer spectroscopy measurements associated to hysteresis loops measurements and chemical analysis [X-ray fluorescence (XRF)]. We inferred the possibility of goethite occurrence in broad particle size distribution (5–50 nm), and related to ferrihydrite, and small grain-size hematite (about 8 nm). The magnetometry results pointed to the paramagnetic/superparamagnetic behavior of the magnetic phases present in the samples and also suggested the occurrence of small grain-size magnetite. We also verified the presence of clay minerals related to Fe, as well as the occurrence of Fe3+ and/or Fe2+ in short-range structural order. Through a straight correlation among Mössbauer spectra data gained at T = 77 K and Al-metal, metal-Fe molar ratios, provided through XRF data, we found remarkable indications of interference on meta-stable phases evolution to its final products. Such results can be pointing for evidences about the possible isomorphic replacing and/or adsorption of Al and other metals in goethite and hematite.  相似文献   

14.
Oxidation of magnetite pellet concentrates (from LKAB, Sweden) during drying and storage was studied using thermogravimetric analysis (TGA). The Fe2+content of a standard LKAB pellet feed decreased by 0.2% during heat treatment at 105 °C for 2 days. The results indicate that magnetite concentrates of pelletizing fineness already start to oxidize to γ-hematite during drying at 105 °C, although 105 °C is recommended by ISO 7764 and ISO 3087 and given as the maximum allowable drying temperature in ISO 3082. The importance of drying time for the amount of magnetite oxidized should also be recognized, but is not mentioned in the ISO standards. The sensitivity of magnetite particles for oxidation during drying could not be predicted by measuring the BET surface area. A simple isothermal TGA run gives exact experimental data and is recommended as a standard procedure before choosing the drying temperature for magnetite concentrate samples.Oxidation during storage at room temperature was observed as well. The Fe2+content in a standard Luossavaara-Kiirunavaara (LKAB) pellet feed decreased by 0.3% Fe2+during 4 years of storage at room temperature. Oxidation during storage was completely hindered when the samples were stored in a freezer at −50 °C. Therefore, freezer storage is recommended for all magnetite reference materials. These materials are used over several years and are especially susceptible to oxidation because they are usually finely ground and high in Fe2+content. The results also show that if the magnetite sample has partly oxidized to γ-hematite, the oxidation curve obtained by TGA will overestimate the Fe2+content of the sample, if background correction is necessary.  相似文献   

15.
Twin formation in hematite during dehydration was investigated using X-ray diffraction, electron diffraction, and high-resolution transmission electron microscopy (TEM). When synthetic goethite was heated at different temperatures between 100 and 800 °C, a phase transformation occurred at temperatures above 250 °C. The electron diffraction patterns showed that the single-crystalline goethite with a growth direction of [001]G was transformed into hematite with a growth direction of [100]H. Two non-equivalent structures emerged in hematite after dehydration, with twin boundaries at the interface between the two variants. As the temperature was increased, crystal growth occurred. At 800 °C, the majority of the twin boundaries disappeared; however, some hematite particles remained in the twinned variant. The electron diffraction patterns and high-resolution TEM observations indicated that the twin boundaries consisted of crystallographically equivalent prismatic (100) (010), and (1\(\bar{1}\)0) planes. According to the total energy calculations based on spin-polarized density functional theory, the twin boundary of prismatic (100) screw had small interfacial energy (0.24 J/m2). Owing to this low interfacial energy, the prismatic (100) screw interface remained after higher-temperature treatment at 800 °C.  相似文献   

16.
Chitosan was cross-linked using glutaraldehyde in the presence of magnetite. The resin obtained was chemically modified through the reaction with tetraethylenepentamine ligand. The obtained resin was loaded with Mo(VI) and investigated. The adsorption characteristics of the obtained resin toward As(V) at different experimental conditions were investigated by means of batch and column methods. The resin showed high affinity and fast kinetics for the adsorption of As(V) where an uptake value of 1.30 mmol g?1 was reported in 6 min at 25 °C. Various parameters such as pH, agitation time, As(V) concentration and temperature had been studied. The kinetics and thermodynamic behavior of the adsorption reaction were defined. These data indicated an endothermic and spontaneous adsorption process and kinetically followed pseudo-second-order model, Fickian diffusion low and Elovich equation. Breakthrough curves for the removal of As(V) were studied at different flow rates and bed heights. The critical bed height for the studied resin column was found to be 0.656 cm at flow rate of 4 mL min?1. The mechanism of interaction between As(V) and resin’s active sites was discussed. Regeneration and durability of the loaded resin toward the successive cycles were also clarified.  相似文献   

17.
This study focused on typical injection layers of deep saline aquifers in the Shiqianfeng Formation used in the Carbon Capture and Sequestration Demonstration Projects in the Ordos Basin, Northwest China. The study employed experiments and numerical simulations to investigate the mechanism of CO2 mineral sequestration in these deep saline aquifers. The experimental results showed that the dissolved minerals are plagioclase, hematite, illite–smectite mixed layer clay and illite, whereas the precipitated minerals are quartz (at 55, and 70 °C) and kaolinite (at 70 °C). There are rare carbonate mineral precipitations at the experimental time scale, while the precipitation of quartz as a product of the dissolution of silicate minerals and some intermediate minerals rich in K and Mg that transform to clay minerals, reveals the possibility of carbonate precipitation at the longer time scale. These results are consistent with some results previously reported in the literature. We calibrated the kinetic parameters of mineral dissolution and precipitation by these experimental results and then simulated the CO2 mineral sequestration under deep saline aquifer conditions. The simulation results showed that the dissolved minerals are albite, anorthite and minor hematite, whereas the precipitated minerals are calcite, kaolinite and smectite at 55 and 70 °C. The geochemical reaction of illite is more complex. At 55 °C, illite is dissolved at the relatively lag time and transformed to dawsonite; at 70 °C, illite is precipitated in the early reaction period and then transformed to kaolinite. Based on this research, sequestrated CO2 minerals, which are mainly related to the temperature of deep saline aquifers in Shiqianfeng Fm., are calcite and dawsonite at lower temperature, and calcite at higher temperature. The simulation results also establish that calcite could precipitate over a time scale of thousands of years, and the higher the temperature the sooner such a process would occur due to increased reaction rates. These characteristics are conducive, not only to the earlier occurrence of mineral sequestration, but also increase the sequestration capacity of the same mineral components. For a sequestration period of 10,000 years, we determined that the mineral sequestration capacity is 0.786 kg/m3 at 55 °C, and 2.180 kg/m3 at 70 °C. Furthermore, the occurrence of mineral sequestration indirectly increases the solubility of CO2 in the early reaction period, but this decreases with the increase in temperature.  相似文献   

18.
Textural and mineral–chemical characteristics in the Bangriposi wehrlites (Eastern India) provide insight into metamorphic processes that morphologically and chemically modified magmatic spinel during serpentinization of wehrlite. Aluminous chromite included in unaltered magmatic olivine is chemically homogenous. In sub-cm to 10s-of-micron-wide veins, magnetite associated with antigorite and clinochlore comprising the serpentine matrix is near-stoichiometric. But Al–Cr–Fe3+ spinels in the chlorite–magnetite veins are invariably zoned, e.g., chemically homogenous Al-rich chromite interior successively mantled by ferritchromite/Cr-rich magnetite zone and magnetite continuous with vein magnetite in the serpentine matrix. In aluminous chromite, ferritchromite/Cr-rich magnetite zones are symmetrically disposed adjacent to fracture-controlled magnetite veins that are physically continuous with magnetite rim. The morphology of ferritchromite–Cr-rich magnetite mimics the morphology of aluminous chromite interior but is incongruous with the exterior margin of magnetite mantle. Micropores are abundant in magnetite veins, but are fewer in and do not appear to be integral to the adjacent ferritchromite–Cr-rich magnetite zones. Sandwiched between chemically homogenous aluminous chromite interior and magnetite mantle, ferritchromite–Cr-rich magnetite zones show rim-ward decrease in Cr2O3, Al2O3 and MgO and complementary increase in Fe2O3 at constant FeO. In diffusion profiles, Fe2O3–Cr2O3 crossover coincides with Al2O3 decrease to values <0.5 wt% in ferritchromite zone, with Cr2O3 continuing to decrease within magnetite mantle. Following fluid-mediated (hydrous) dissolution of magmatic olivine and olivine + Al–chromite aggregates, antigorite + magnetite and chlorite + magnetite were transported in 10s-of-microns to sub-cm-wide veins and precipitated along porosity networks during serpentinization (T: 550–600 °C, f(O2): ?19 to ?22 log units). These veins acted as conduits for precipitation of magnetite as mantles and veins apophytic in chemically/morphologically modified magmatic Al-rich chromite. Inter-crystalline diffusion induced by chemical gradient at interfaces separating aluminous chromite interiors and magnetite mantles/veins led to the growth of ferritchromite/Cr-rich magnetite zones, mimicking the morphology of chemically modified Al–Cr–Fe–Mg spinel interiors. Inter-crystalline diffusion outlasted fluid-mediated aluminous chromite dissolution, mass transfer and magnetite precipitation.  相似文献   

19.
The Mianeh iron skarn deposit lies in the Arasbaran region within the Qaradagh metallogenic district, NW Iran. This high-grade massive magnetite skarn originated by the interaction of Upper Cretaceous limestone with metasomatic ore-bearing fluids associated with hypabyssal Oligo-Miocene quartz diorite. Mineral chemistry of the primary clinopyroxenes demonstrates the sub-alkaline, volcanic arc setting of magmatism. Two general stages of skarnification are recognized: (1) silicate skarn (stage I) is composed essentially of grossular and low-Fe diopside formed before the main mineralization and (2) magnetite-garnet skarn (stage II) composed of strongly anisotropic coarse-grained garnets with a narrow compositional zoning radially formed by addictive infiltrating of silica and iron-rich metasomatic fluids which overprint and/or crosscut the early stage silicate skarn. Anhydrous prograde calc-silicate assemblages were replaced by a series of hydrous calc-silicates (epidote, tremolite-actinolite) and/or quartz, calcite, magnetite, hematite, and pyrite. Magnetite (±hematite) is the dominant hypogene ore mineral that initially precipitated coincident with the late prograde to the early retrograde metasomatic stages. Mineralogical studies suggest that silicate skarn formation commenced at temperatures about 560 °C, X(CO2)fluid ≤ 0.15, αSiO2～?1.0, and fluid pressure 1.0 kbar. The magnetite-garnet skarn formed from H2O-rich fluids [X(CO2)fluid < 0.1] at a temperature of 525 to 450 °C and maximum log ?O2 between ?20.2 and ?23. During the late stages of prograde skarn development, the stability field of andradite shifted to low ?O2 and ?S2 conditions resulting in main iron ore deposition (as magnetite). The andradite replacement temperature and presence of pyrite (instead of pyrrhotite) suggest that log?S2 remained constant at about ?6 to ?7 during cooling of the system.  相似文献   

20.
The Shevaroy Hills of northern Tamil Nadu, southern India, expose the highest-grade granulites of a prograde amphibolite facies to granulite facies deep-crustal section of Late Archaean age. These highly oxidized quartzofeldspathic garnet charnockites generally show minor high-TiO2 biotite and amphibole as the only hydrous minerals and are greatly depleted in the incompatible elements Rb and Th. Peak metamorphic temperatures (garnet–orthopyroxene) and pressures (garnet–orthopyroxene–plagioclase–quartz) are near 750 °C and 8 kbar, respectively. Pervasive veinlets of K-feldspar exist throughout dominant plagioclase in each sample and show clean contact with orthopyroxene. They are suggested to have been produced by a low H2O activity, migrating fluid phase under granulite facies conditions, most likely a concentrated chloride/carbonate brine with high alkali mobility accompanied by an immiscible CO2-rich fluid. Silicate, oxide and sulphide mineral assemblages record high oxygen fugacity. Pyroxenes in the felsic rocks have high Mg/(Mg+Fe) (0.5–0.7). The major oxide mineral is ilmenite with up to 60 mole per cent exsolved hematite. Utilizing three independent oxygen barometers (ferrosilite–magnetite–quartz, ferrosilite–hematite–quartz and magnetite–hematite) in conjunction with garnet–orthopyroxene exchange temperatures, samples with XIlmHm>0.1 yield a consistent oxygen fugacity about two log units above fayalite stability. Less oxidized samples (XIlmHm<0.1) show some scatter with indications of having equilibrated under more reducing conditions. Temperature-f (O2 ) arrays result in self consistent conditions ranging from 660 °C and 10?16 bar to 820 °C and 10?11.5 bar. These trends are confirmed by calculations based on the assemblage clinopyroxene–orthopyroxene–magnetite–ilmenite using the QUIlF program. In the most oxidized granulite samples (XIlmHm>0.4) pyrite is the dominant sulphide and pyrrhotite is absent. Pyrite grains in these samples have marginal alteration to magnetite along the rims, signifying a high-temperature oxidation event. Moderately oxidized samples (0.1no coexisting magnetite. Chalcopyrite is a common accessory mineral of pyrite and pyrrhotite in all the samples. Textures in some samples suggest that it formed as an exsolution product from pyrrhotite. Extensive vein networks of magnetite and pyrite, associated principally with the pyroxene and amphibole, give evidence for a pervasive, highly oxidizing fluid phase. Thermodynamic analysis of the assemblage pyrrhotite, pyrite and magnetite yields consistent high oxidation states at 700–800 °C and 8 kbar. The oxygen fugacity in our most oxidized pyrrhotite-bearing sample is 10?12.65 bar at 770 °C. There are strong indications that the Shevaroy Hills granulites recrystallized in the presence of an alkali-rich, low H2O-activity fluid, probably a concentrated brine. It cannot be demonstrated at present whether the high oxidation states were set by initially oxidized protoliths or effected by the postulated fluids. The high correspondence of maximally Rb-depleted samples with the highest recorded oxidation states suggests that the Rb depletion event coincided with the oxidation event, probably during breakdown of biotite to orthopyroxene+K-feldspar. We speculate that these alterations were effected by exhalations from deep-seated alkali basalts, which provided both heat and high oxygen fugacity, low aH2O fluids. It will be of interest to determine whether greatly Rb-depleted granulites in other Precambrian terranes show similar highly-oxidizing signatures.  相似文献   

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