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1.
Kazuya Tanaka Yukinori Tani Masaharu Tanimizu Naofumi Kozai 《Geochimica et cosmochimica acta》2010,74(19):5463-5477
Sorption of rare earth elements (REEs) and Ce oxidation on natural and synthetic Mn oxides have been investigated by many researchers. Although Mn(II)-oxidizing microorganisms are thought to play an important role in the formation of Mn oxides in most natural environments, Ce oxidation by biogenic Mn oxide and the relevance of microorganisms to the Ce oxidation process have not been well understood. Therefore, in this study, we conducted sorption experiments of REEs on biogenic Mn oxide produced by Acremonium sp. strain KR21-2. The distribution coefficients, Kd(REE), between biogenic Mn oxide (plus hyphae) and 10 mmol/L NaCl solution showed a large positive Ce anomaly and convex tetrad effect variations at pH 3.8, which was consistent with previous works using synthetic Mn oxide. The positive Ce anomaly was caused by oxidation of Ce(III) to Ce(IV) by the biogenic Mn oxide, which was confirmed by analysis of the Ce LIII-edge XANES spectra. With increasing pH, the positive Ce anomaly and convex tetrad effects became less pronounced. Furthermore, negative Ce anomalies were observed at a pH of more than 6.5, suggesting that Ce(IV) was stabilized in the solution (<0.2 μm) phase, although Ce(III) oxidation to Ce(IV) on the biogenic Mn oxide was confirmed by XANES analysis. It was demonstrated that no Ce(III) oxidation occurred during sorption on the hyphae of strain KR21-2 by the Kd(REE) patterns and XANES analysis. The analysis of size exclusion HPLC-ICP-MS showed that some fractions of REEs in the filtrates (<0.2 μm) after sorption experiments were bound to organic molecules (40 and <670 kDa fractions), which were possibly released from hyphae. A line of our data indicates that the negative Ce anomalies under circumneutral pH conditions arose from Ce(III) oxidation on the biogenic Mn oxide and subsequent complexation of Ce(IV) with organic ligands. The suppression of tetrad effects is also explained by the complexation of REEs with organic ligands. The results of this study demonstrate that the coexistence of the biogenic Mn oxide and hyphae of strain KR21-2 produces a specific redox chemistry which cannot be explained by inorganic species. 相似文献
2.
A manganese-bearing mineral characterized by a black hair-like surface crystal growth, and somewhat unique to the Socorro County, New Mexico Area, has been referred to as psilomelane or pseudo-pyrolusite. X-ray diffraction measurements indicated the structure to be the tetragonal (a=4.42 Å, c=2.87Å) MnO2 (pyrolusite) structure; with α-Mn enrichment. Detailed examinations of the mineral specimens made in the scanning and transmission electron microscopes showed the fiber crystals to be pseudo-fluted as a result of an apparent stacking of long needles to form continuous single-crystral bundles oriented along the x-axis These crystals were shown by selected-area electron diffraction to be composed of extended superstructure cells, and these to be commposed of as many as 10 MnO2 unit cells stacked along the x-axis; interrupted by a stacking fault shear of the basic MnO2 lattice resulting in stacking faults. Individual whisker crystals were observed to be terminated by crystallographic facets which is indicative of solution growth expected on considering their geological and mineralogical environment. 相似文献
3.
The removal of Mn(II) from coal mine drainage (CMD) by chemical addition/active treatment can significantly increase treatment costs. Passive treatment for Mn removal involves promotion of biological oxidative precipitation of manganese oxides (MnOx). Manganese(II) removal was studied in three passive treatment systems in western Pennsylvania that differed based on their influent Mn(II) concentrations (20–150 mg/L), system construction (±inoculation with patented Mn(II)-oxidizing bacteria), and bed materials (limestone vs. sandstone). Manganese(II) removal occurred at pH values as low as 5.0 and temperatures as low as 2 °C, but was enhanced at circumneutral pH and warmer temperatures. Trace metals such as Zn, Ni and Co were removed effectively, in most cases preferentially, into the MnOx precipitates. Based on synchrotron radiation X-ray diffraction and Mn K-edge extended X-ray absorption fine structure spectroscopy, the predominant Mn oxides at all sites were poorly crystalline hexagonal birnessite, triclinic birnessite and todorokite. The surface morphology of the MnOx precipitates from all sites was coarse and “sponge-like” composed of nm-sized lathes and thin sheets. Based on scanning electron microscopy (SEM), MnOx precipitates were found in close proximity to both prokaryotic and eukaryotic organisms. The greatest removal efficiency of Mn(II) occurred at the one site with a higher pH in the bed and a higher influent total organic C (TOC) concentration (provided by an upstream wetland). Biological oxidation of Mn(II) driven by heterotrophic activity was most likely the predominant Mn removal mechanism in these systems. Influent water chemistry and Mn(II) oxidation kinetics affected the relative distribution of MnOx mineral assemblages in CMD treatment systems. 相似文献
4.
The oxidation of Mn(II) by O2 to Mn(III) or Mn(IV) is thermodynamically favored under the pH and pO2 conditions present in most near surface waters, but the kinetics of this reaction are extremely slow. This work investigated whether reactive oxygen species, produced through illumination of humic substances, could oxidize Mn at an environmentally relavent rate. The simulated sunlight illumination of a solution containing 200 μM Mn(II) and 5 mg/L Aldrich humic acid buffered at pH 8.1 produced ∼19 μM of oxidized Mn (MnOx where x is between one and two) after 45 minutes. The major oxidants reponsible for this reaction appear to be photoproduced superoxide radical anion, O2−, and singlet molecular oxygen, 1O2. The dependencies of MnOx formation on Mn(II), humic acid, and H+ concentration were characterized. A kinetic model based largely on published rate constants was established and fit to the experimental data. As expected, analysis of the model indicates that the key reaction rate controlling MnOx production is the rate of decomposition of a MnO2+ complex formed from the reaction of Mn(II) with O2−. This rate is strongly dependent on the Mn(II) complexing ligands in solution. The MnOx production in the seawater sample taken from Bodega Bay, USA and spiked with 200 μM Mn(II) was well reproduced by the model. Extrapolations from the model imply that Mn photo-oxidation should be a significant reaction in typical surface seawaters. Calculated rates, 5.8 to 55 pM h−1, are comparable to reported rates of biological Mn oxidation, 0.07 to 89 pM h−1. Four fresh water samples that were spiked with 200 μM Mn(II) also showed significant MnOx production. Based on these results, it appears that Mn photo-oxidation could constitute a significant, and apparently unrecognized geochemical pathway in natural waters. 相似文献
5.
J. Karuppiah E. Linga Reddy P. Manoj Kumar Reddy B. Ramaraju Ch. Subrahmanyam 《International Journal of Environmental Science and Technology》2014,11(2):311-318
Oxidative decomposition of dilute benzene in air was carried out in a dielectric barrier discharge reactor with inner metal fiber electrode that was later modified with transition metal oxides. Typical results indicated the best performance of the designed reactor for the removal of dilute benzene, where conventional techniques may not be efficient. The introduction of transition metal oxides in the discharge zone increased the conversion of benzene and shifted the product distribution to total oxidation. The performance of the reactor was further improved on humidification of air stream. The better performance of MnOx/SMF over CoOx and SMF may be due to in situ decomposition of ozone that may lead to the formation of strong oxidant atomic oxygen, whereas the best performance with TiO2/MnOx/SMF may be assigned due to the synergy between ozone decomposition on MnOx surface and photocatalytic action on TiO2. 相似文献
6.
Oxic limestone beds are commonly used for the passive removal of Mn(II) from coal mine drainage (CMD). Aqueous Mn(II) is removed via oxidative precipitation of Mn(III/IV) oxides catalyzed by Mn(II)-oxidizing microbes and Mn oxide (MnOx) surfaces. The relative importance of these two processes for Mn removal was examined in laboratory experiments conducted with sediments and CMD collected from eight Mn(II)-removal beds in Pennsylvania and Tennessee, USA. Sterile and non-sterile sediments were incubated in the presence/absence of air and presence/absence of fungicides to operationally define the relative contributions of Mn removal processes. Relatively fast rates of Mn removal were measured in four of the eight sediments where 63–99% of Mn removal was due to biological oxidation. In contrast, in the four sediments with slow rates of Mn(II) removal, 25–63% was due to biological oxidation. Laboratory rates of Mn(II) removal were correlated (R2 = 0.62) to bacterial biomass concentration (measured by phospholipid fatty acids (PLFA)). Furthermore, laboratory rates of Mn(II) removal were correlated (R2 = 0.87) to field-scale performance of the Mn(II)-removal beds. A practical recommendation from this study is to include MnOx-coated limestone (and associated biomass) from an operating bed as “seed” material when constructing new Mn(II)-removal beds. 相似文献
7.
The surface binding site characteristics and Ni sorptive capacities of synthesized hydrous Mn oxyhydroxides experimentally conditioned to represent three hydrological conditions—MnOXW, freshly precipitated; MnOXD, dried at 37°C for 8 d; and MnOXC, cyclically hydrated and dehydrated (at 37°C) over a 24-h cycle for 7 d—were examined through particle size analysis, surface acid-base titrations and subsequent modelling of the pKa spectrum, and batch Ni sorption experiments at two pH values (2 and 5). Mineralogical bulk analyses by XRD indicate that all three treatments resulted in amorphous Mn oxyhydroxides; i.e., no substantial bulk crystalline phases were produced through drying. However, drying and repeated wetting and drying resulted in a non-reversible decrease in particle size. In contrast, total proton binding capacities determined by acid-base titrations were reversibly altered with drying and cyclically re-wetting and drying from 82 ± 5 μmol/m2 for the MnOXW to 21 ± 1 μmol/m2 for the MnOXD and 37 ± 5 μmol/m2 for the MnOXC. Total proton binding sites measured decreased by ≈75% with drying from the MnOXW and then increased to ≈50% of the MnOXW value in the MnOXC. Thus, despite a trend of higher surface area for the MnOXD, a lower total number of sites was observed, suggesting a coordinational change in the hydroxyl sites. Surface site characterization identified that changes also occurred in the types and densities of surface sites for each hydrologically conditioned Mn oxyhydroxide treatment (pH titration range of 2-10). Drying decreased the total number of sites as well as shifted the remaining sites to more acidic pKa values. Experimentally determined apparent pHzpc values decreased with drying, from 6.82 ± 0.06 for the MnOXW to 3.2 ± 0.3 for the MnOXD and increased again with rewetting to 5.05 ± 0.05 for the MnOXC. Higher Ni sorption was observed at pH 5 for all three Mn oxyhydroxide treatments compared to pH 2. However, changes in relative sorptive capacities among the three treatments were observed for pH 2 that are not explainable simply as a function of total binding site density or apparent pHzpc values. These results are the first to our knowledge, to quantitatively link the changes induced by hydrologic variability for surface acid base characteristics and metal sorption patterns. Further, these results likely extend to other amorphous minerals, such as Fe oxyhydroxides, which are commonly important geochemical solids for metal scavenging in natural environments. 相似文献
8.
Olaf Dellwig Thomas Leipe Michael Glockzin Bernhard Schnetger Michael E. Böttcher 《Geochimica et cosmochimica acta》2010,74(24):7100-7115
Pelagic redoxclines of anoxic basins and deeps form the suboxic transition between oxygenated surface and anoxic or even sulfidic bottom waters. Intense element cycling, favoured by elevated microbial activity, causes steep gradients of physico-chemical parameters, nutrients and redox-sensitive trace metals. This study presents a conceptual model for authigenic particle formation at pelagic redoxclines, which is based on the tight coupling of Mn, Fe, and P cycles. Besides the well-known occurrence of Mn-oxides, textural (SEM-EDX) and geochemical (ICP-OES, ICP-MS) analyses of particles from the redoxclines of the Black Sea and the Baltic Sea (Gotland Basin, Landsort Deep) evidence the existence of earlier postulated Fe-oxyhydroxo-phosphates and emphasize mixed phases consisting of Mn-oxides and Fe-oxyhydroxo-phosphates as a new solid species. Most of the analyzed particles are star-shaped, of about 5 μm in size, and occur as single particles or aggregates without any morphological differences between Mn-oxides, Fe-oxyhydroxo-phosphates, and mixed phases. Throughout the redoxcline, these minerals show a general succession with maximum abundance of Mn-oxides above the redoxcline followed by mixed phases and almost pure Fe-phosphates within and below the redoxcline, respectively. Molar Fe/P ratios of single particles argue against the formation of known pure Fe-phosphates like vivianite or strengite at the lower end of the redox transition zone, but are consistent with recent experimental findings for colloidal P-bearing hydrous ferric oxides. Moreover, morphological similarities suggest the formation of irregular Fe-oxyhydroxo coatings due to oxidation of upward diffusing Fe2+ by oxygen and stepwise replacement of Mn(IV) by Fe(III) on sinking MnOx particles followed by immediate adsorption or even co-precipitation of phosphate. Batch-type experiments using biogenic MnOx particles demonstrate the efficient potential of Fe2+ oxidation by sinking MnOx particles. When entering sulfidic waters MnOx particles are progressively reduced leading to an increasing relative abundance of Fe- and P-rich particles. In deeper parts of the water column these particles are also reductively dissolved, thereby releasing Fe2+ and phosphate to the water column. This Mn-Fe-P-shuttle likely affects phosphate transport throughout the water column and thus impacts primary production at least over longer time scales. Furthermore, the particulate Mn-Fe-P-shuttle must have played an important role for the cycling of P and certain trace metals in ancient ocean basins, e.g., during certain periods of Cretaceous black shale formation and should be considered in future mass balances and modeling approaches dealing with oxic/anoxic interfaces of aquatic ecosystems. 相似文献
9.
The sorption of silver by poorly crystallized manganese oxides was studied using synthesized samples of three members of the manganous manganite (birnessite) group, of different chemical composition and crystallinity, and a poorly organized γ-MnO2. All four oxides sorbed significant quantities of silver. The manganous manganites showed the greatest sorption (up to 0.5 moles silver/mole MnOx at pH 7) while the γ-MnO2 showed the least (0.3 moles silver/ mole MnOx at pH 7). Sorption of silver was adequately described by the Langmuir equation over a considerable concentration range. The relationship failed at low pH values and high equilibrium silver concentrations. The sorption capacity showed a direct relationship with pH. However, the rate of increase of sorption capacity decreased at the higher pH values.Silver sorption maxima. were not directly related to surface area but appeared to vary with the amount of occluded sodium and potassium present in the manganese oxide. The important processes involved in the uptake of silver by the four poorly crystallized manganese oxides ara considered to be surface exchange for manganese, potassium and sodium as well as exchange for structural manganese, potassium and sodium. 相似文献
10.
Dorothy L. Parker Takami Morita Rebecca Verity James K. McCarthy 《Geochimica et cosmochimica acta》2007,71(23):5672-5683
To examine the pathways that form Mn(III) and Mn(IV) in the Mn(II)-oxidizing bacterial strains Pseudomonas putida GB-1 and MnB1, and to test whether the siderophore pyoverdine (PVD) inhibits Mn(IV)O2 formation, cultures were subjected to various protocols at known concentrations of iron and PVD. Depending on growth conditions, P. putida produced one of two oxidized Mn species - either soluble PVD-Mn(III) complex or insoluble Mn(IV)O2 minerals - but not both simultaneously. PVD-Mn(III) was present, and MnO2 precipitation was inhibited, both in iron-limited cultures that had synthesized 26-50 μM PVD and in iron-replete (non-PVD-producing) cultures that were supplemented with 10-550 μM purified PVD. PVD-Mn(III) arose by predominantly ligand-mediated air oxidation of Mn(II) in the presence of PVD, based on the following evidence: (a) yields and rates of this reaction were similar in sterile media and in cultures, and (b) GB-1 mutants deficient in enzymatic Mn oxidation produced PVD-Mn(III) as efficiently as wild type. Only wild type, however, could degrade PVD-Mn(III), a process linked to the production of both MnO2 and an altered PVD with absorbance and fluorescence spectra markedly different from those of either PVD or PVD-Mn(III). Two conditions, the presence of bioavailable iron and the absence of PVD at concentrations exceeding those of Mn, both had to be satisfied for MnO2 to appear. These results suggest that P. putida cultures produce soluble Mn(III) or MnO2 by different and mutually inhibitory pathways: enzymatic catalysis yielding MnO2 under iron sufficiency or PVD-promoted oxidation yielding PVD-Mn(III) under iron limitation. Since PVD-producing Pseudomonas species are environmentally prevalent Mn oxidizers, these data predict influences of iron (via PVD-Mn(III) versus MnO2) on the global oxidation/reduction cycling of various pollutants, recalcitrant organic matter, and elements such as C, S, N, Cr, U, and Mn. 相似文献
11.
Alexandra Navrotsky Gilles Peraudeau Paul McMillan Jean-Pierre Coutures 《Geochimica et cosmochimica acta》1982,46(11):2039-2047
Enthalpies of solution in molten 2PbO · B2O3 at 985 K are reported for series of glasses xCa0.5AlO2-(1?x)SiO2 (O ≤ x ≤ 0.99) and xNaAlO2-(1?x)SiO2 (0 ≤ x ≤ 0.56). The data are compared to values for the corresponding crystalline aluminosilicates and to preliminary data for systems containing KAlO2 and Mg0.5AlO2. The enthalpies of mixing of glasses become more exothermic with increasing basicity of the mono- or divalent oxide. The tendency toward immiscibility on the silica-rich side, indicated by the shape of the heat of mixing curve between x = 0 and x = 0.4, is pronounced in the calcium aluminate system, but not in the sodium aluminate system. The shape of the heat of mixing curve, which is roughly symmetrical about x = 0.5, can be rationalized in terms of glass structure by considering essentially random substitution of Si and Al on a continuous three dimensional tetrahedral framework, with stabilization arising from electrostatic interactions between aluminum and the nonframework cation balancing the destabilizing effects arising from perturbation of the aluminosilicate framework by the nonframework cation. These trends are consistent with the variation of physical properties of aluminosilicate melts. 相似文献
12.
Mélanie Davranche Olivier Pourret Gérard Gruau Aline Dia Dan Jin Dominique Gaertner 《Chemical Geology》2008,247(1-2):154-170
The competitive binding of rare earth elements (REE) to purified humic acid (HA) and MnO2 was studied experimentally using various HA/MnO2 ratios over a range of pH (3 to 8). MnO2, humic acid and REE solutions were simultaneously mixed to investigate the kinetics of the competitive reactions. Aqueous REE–HA complex is the dominant species whatever the experiment time, pH and HA/MnO2 ratio. The value of the distribution coefficients between MnO2 and solution (log KdRee/Mno2) increases with the HA/MnO2 ratio, indicating that part of the REE–HA complexes are adsorbed onto MnO2. The development of a Ce anomaly appears strongly limited in comparison with inorganic experimental conditions. Throughout the experimental run time, for HA/MnO2 ratios of less than 0.4, MnO2 acts as a competitor leading to a partial dissociation of the REE–HA complex. The majority of the dissociated REE is readsorbed onto the MnO2 surface. The readsorption of REE is expressed by an increased Ce anomaly on the log KdRee/Mno2 pattern as well as a change in shape of the coefficient distribution of REE between soluble HA and solution pattern (log KdRee/HA decrease for the heavy rare earth elements — HREE). Thus, REE are not only bound to MnO2 as a REE–HA complex, but also as REE(III). Moreover, the competition between HA and MnO2 for REE binding is shown to be higher at low pH (< 6) and low DOC/Mn ratio. This study partially confirms previous work that demonstrated the control of REE adsorption by organic matter, while shedding more light on the impact of pH as well as complexation reaction competition on long-term REE partitioning between solid surface and organic solutions. The latter point is important as regards to REE speciation under conditions typical of rock and/or mineral alteration. 相似文献
13.
Chemical and mineralogical analyses of a well-controlled suite of ferromanganese encrustations from the Line Islands Archipelago (Central Pacific) suggest that they represent purely hydrogenous deposits—i.e. they have formed through the slow accumulation of trace metal-enriched oxides directly from the water-column. Mineralogically they consist predominantly of δMnO2 and amorphous FeOOHxH2O. Compositionally, they are similar to δMnO2 nodules from adjoining basinal areas but are enriched in both Mn (mean = 20.4%, max = 29.3%) and Co (mean = 0.55%, max = 1.57%). δMnO2 is the most important trace metal bearing phase; strong associations are noted between it and Co, Mo, Ni, Zn, and Cd, whilst only Be is associated specifically with FeOOH. V, Sr and Pb are partitioned between the authigenic oxide phases, whilst Ti most probably occurs as TiO2xH2O. Cu is contained in both aluminosilicate contaminant phases and Fe oxide phases. These relations are considered to reflect the differing scavenging behaviour of Mn and Fe oxides in the water column.Crusts from ~1–2 km are enriched in Mn and the Mn-related elements and exhibit higher ratios than deeper crusts, which are compositionally constant. The higher ratios may result from a supply of Mn from continental borderland sediments at these depths, which is transported horizontally by advective-diffusive processes. Since manganophile elements are enriched relative to Mn in the 1–2 km crusts, it is considered that the supply of Mn is scavenged by existing oxides, is oxidised and effectively occludes them. A higher proportion of oxide particles thus exhibit Mn oxide scavenging properties in the 1–2 km depth zone. The increased vertical flux of Mn resulting from the supply at ~1–2 km is not reflected by higher ratios in deeper crusts, so that the vertical flux of oxides is not simply related to the standing crop. The ratios of the crusts thus reflect the composition of suspended oxides at similar depths. 相似文献
14.
B. Ghazi-Bayat M. Behruzi F. J. Litterst W. Lottermoser G. Amthauer 《Physics and Chemistry of Minerals》1992,18(8):491-496
The dependence of the electronic and the crystallographic structure on temperature of synthetic Mnbearing ilvaites CaFe2+ 2-xMn2+ xFe3+ [Si2O7/O/OH] with 0≤x≤0.19 has been investigated. The change of the electronic structure was studied by 57Fe Mössbauer spectroscopy. The spectra show an increasing valence fluctuation rate between Fe2+ and Fe3+ in the double chain of edge-sharing octahedra with increasing temperature resulting in a mixed valent state of iron. The valence fluctuation rate is distinctly increased by the Mnsubstitution. The temperature of the crystallographic phase transition T x as studied by a high temperature Guinier method is distinctly lowered by the Mn-substitution (x = 0.0, T x=390K; x = 0.12, T x =370K; x = 0.19, T x=295K). The reasons for this behaviour are discussed in terms of Fe2 +, Fe3 + cation order-disorder, electronic relaxation rate, and relaxation of the lattice. In the monoclinic phase there is electron hopping between Fe2 +, Fe3 + pairs whereas in the orthorhombic phase there is extended electron delocalization via a narrow, d-band mechanism. 相似文献
15.
R. H. Mitchell A. R. Chakhmouradian P. M. Woodward 《Physics and Chemistry of Minerals》2000,27(8):583-589
Perovskite-type compounds in the series tausonite-loparite, (Sr1?2 x Na x La x )TiO3, were synthesized by solid-state reaction (final heating at 1200–1300?°C), and studied using “conventional” and synchrotron X-ray powder diffractometry. The structures of intermediate compositions were determined using the Rietveld profile refinement method. In the compositional range 0?≤x?≤ 0.1, the series comprises perovskites characterized by an undistorted cubic structure (space group Pm3¯m, a?≈ 3.905–3.902?Å, Z?=?1). Intermediate compounds in the range 0.15?≤?x?≤?0.35 crystallize with tetragonal symmetry (I4/mcm, a?≈? , c?≈? , Z?=?4) derived from the cubic aristotype by antiphase rotation of the TiO6 octahedra about a fourfold axis. The angle of rotation estimated from the positional parameters of oxygen atoms ranges from 2.5(7)° to 5.5(4)°. The cubic-to-tetragonal transition arises from substitution of Sr2+ by the comparatively smaller Na1+ and La3+ cations. A further transition from the tetragonal to rhombohedral symmetry (R3¯c, a?≈? , c?≈?2 , Z?=?6) occurs between x?=?0.35 and 0.40, and apparently does not involve formation of perovskite with an intermediate two-tilt structure (Imma). The rhombohedral structure is characterized by a multicomponent octahedral tilt about a threefold axis ranging in magnitude from 6.5(2)° to 7.7(2)°. In the series (Sr1?2 x Na x La x )TiO3, the unit-cell dimensions decrease, and the degree of structural distortion increases with x. 相似文献
16.
Superstructures in synthetic mullite, Al4+2x Si2?2x O10?x , prepared using the zone melting technique, are studied by high resolution electron microscopy (HREM), electron diffraction, and in situ energy dispersive X-ray spectroscopy. For x=0.40 composition HREM images indicate only short-range order. Near x=0.5 composition mullite has an antiphase domain structure with antiphase boundaries (APB's) oriented parallel to (100). For higher Al-content the APB's run in non-rational orientations which are slightly inclined against the {601}-planes. We propose models for the superstructures in which oxygen vacancies are arranged in channels parallel to the crystal b-axis. The models are supported by a one-to-one match between observed and computer-simulated images. An Al-rich limit of x=2/3 for mullite is deduced on the basis of stereochemical considerations. Different ordering schemes for the tetrahedral cations are believed to result in the orientation change of the APB's near x=0.5 composition. 相似文献
17.
《地学前缘(英文版)》2022,13(4):101380
Melting experiments on ultramafic rocks rich in the hydrous minerals phlogopite or phlogopite + K-richterite, some including 5% of accessory phases, have been conducted at 15 and 50 kbar. The assemblages represent probable source components that contribute to melts in cratonic regions, but whose melt compositions are poorly known. A main series of starting compositions based on MARID xenoliths consisted of a third each of clinopyroxene (CPX), phlogopite (PHL) and K-richterite (KR) with or without 5% ilmenite, rutile or apatite. Additional experiments were run without KR and with higher proportions of accessory phases. Melt traps were used at near-solidus temperatures to facilitate accurate analysis of well-quenched melts, for which reversal experiments demonstrate equilibrium.Results show that KR melts rapidly and completely within 50 °C of the solidus, so that melts reflect the composition of the amphibole and its melting reaction. Melts have high SiO2 and especially K2O but low CaO and Al2O3 relative to basaltic melts produced from peridotites at similar pressures. They have no counterparts amongst natural rocks, but most closely resemble leucite lamproites at 15 kbar. KR and PHL melt incongruently to form olivine (OL) and CPX at 15 kbar, promoting SiO2 contents of the melt, whereas orthopyroxene OPX is increasingly stable at lower lithosphere pressures, leading to an increase in MgO and decrease in SiO2 in melts, which resemble olivine lamproites. Melts of mica pyroxenites without KR are richer in CaO and Al2O3 and do not resemble lamproites. These experiments show that low CaO and Al2O3 in igneous rocks is not necessarily a sign of a depleted peridotite source. Accessory phases produce melts exceptionally rich in P2O5 or TiO2 depending on the phases present and are unlike any melts seen at the Earth’s surface, but may be important agents of metasomatism seen in xenoliths. The addition of the 5% accessory phases ilmenite, rutile or apatite result in melting temperatures a few ten of degrees lower; at least two of these appear essential to explain the compositions of many alkaline igneous rocks on cratons.Melting temperatures for CPX + PHL + KR mixtures are close to cratonic geotherms at depths > 130 km: minor perturbations of the stable geotherm at >150 km will rapidly lead to 20% melting. Melts of hydrous pyroxenites with a variety of accessory phases will be common initial melts at depth, but will change if reaction with wall-rocks occurs, leading to volcanism that contains chemical components of peridotite even though the temperature in the source region remains well below the melting point of peridotite. At higher temperatures, extensive melting of peridotite will dilute the initial alkaline melts: this is recognizable as alkaline components in basalts and, in extreme cases, alkali picrites. Hydrous pyroxenites are, therefore, components of most mantle-derived igneous rocks: basaltic rocks should not be oversimplified as being purely melts of peridotite or of mixtures of peridotite and dry pyroxenite without hydrous phases. 相似文献
18.
Fe57 Mössbauer spectra were measured on compositions of the series Fe1?x/3Ta1+x/3O4, 0≤x≤1. The spectra are characterized by mixed valencies of Fe2+ and Fe3+ ions for 0<x<1. Starting from x=0 with rutile structure, a trirutile structure forms towards x=1. Quadrupole splitting QS of Fe3+ is QS(Fe3+)≈0.55 mm/s and isomer shift IS is IS(Fe3+)≈0.40 mm/s (referred to Fe); both quantities exhibit minor variations along the series. The Fe2+ subspectra for x>0.5 were fitted using one symmetrical doublet; however, for x<0.5 two symmetrical doublets were necessary to describe these patterns. QS(Fe2+)=2.0–3.2 mm/s and IS(Fe2+)=0.90–1.15 mm/s for all compositions. In the case x<0.5, marked temperature dependent QS values appear to exist. This feature may be related to short range order effects and possibly also in part to intervalence electron transfer betwee Fe2+ and Fe3+ ions. 相似文献
19.
Martine Mullet Frédéric Demoisson Laurent J. Michot 《Geochimica et cosmochimica acta》2007,71(13):3257-3271
Optical microscopy, confocal Raman micro-spectrometry, X-ray photoelectron micro-spectroscopy (XPS) and synchrotron based micro-X-ray fluorescence (XRF), micro-X-ray absorption near edge spectroscopy (XANES) and micro-extended X-ray absorption fine structure (EXAFS) were used to investigate the reduction of aqueous Cr(VI) by pyrite. Special emphasis was placed on the characterisation of the solid phase formed during the reaction process. Cr(III) and Fe(III) species were identified by XPS analyses in addition to non-oxidised pyrite. Optical microscopy images and the corresponding Raman spectra reveal a strong heterogeneity of the samples with three different types of zones. (i) Reflective areas with Eg and Ag Raman wavenumbers relative to non-oxidised pyrite are the most frequently observed. (ii) Orange areas that display a drift of the Eg and Ag pyrite vibration modes of −3 and −6 cm−1, respectively. Such areas are only observed in the presence of Cr(VI) but are not specifically due to this oxidant. (iii) Bluish areas with vibration modes relative to a corundum-like structure that can be assigned to a solid solution Fe2−xCrxO3, x varying between 0.2 and 1.5. The heterogeneity in the spatial distribution of chromium observed by optical microscopy and associated Raman microspectroscopy is confirmed by μ-XRF. In agreement with both solution and XPS analyses, these spectroscopies clearly confirm that chromium is in the trivalent state. XANES spectra in the iron K-edge pre-edge region obtained in rich chromium areas reveal the presence of ferric ion thus revealing a systematic association between Cr(III) and Fe(III). In agreement with Raman analyses, Cr K-edge EXAFS can be interpreted as corresponding to Cr atoms involved in a substituted-type hematite structure Fe2−xCrxO3. 相似文献