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1.
The distributions of Al 3+/Mg 2+ and Al 3+/ Fe 3+ were studied in the octahedral sheet of illites and smectites. Cation exchange interaction parameters J i, as first, second, third and fourth neighbours were calculated by means of empirical interatomic potentials. Several compositions with different interlayer cations and tetrahedral charge were studied in both Al/Mg and Al/Fe systems. The values of J i parameters were similar in all Al/Mg samples. From these J i values, a strong trend to form AlMg pairs was observed in the Al/Mg system. In the Al/Fe system, the values of J i are very small, indicating no preference for Al/Fe mixing. From these J i parameters, Monte Carlo simulations of octahedral cation ordering were performed. In the Al/Mg system, an order/disorder phase transition was observed obtaining a fully ordered distribution without presence of an MgMg pair, according to experimental data. Similar phase transitions were observed for the octahedral compositions Al/Mg 1/1 and 3/1. In the Al/Fe system an order/disorder phase transition was also detected but at very low temperature for illite and smectite. Complete Al/Fe mixing is observed in the most stable ordered distribution. This is consistent with experimental results for synthetic Fe/Al smectites.  相似文献   

2.
《地学前缘(英文版)》2020,11(4):1353-1367
Chronologically well-constrained loess-palaeosols(recorded glacial and inter-glacial climate) revealed pedogenesis induced ionic substitutions,caused end-member compositional deviations in illite and chlorite,linked to widespread climatic changes occurred during Late Pleistocene.Further,micro-level climatic resolution is yet to be resolved.Thus,layer-wise X-ray diffraction analyses of clay separates,followed by Rietveld refinement revealed varied cell parameters and interatomic distances.Obtained values for detrital and pedogenic illite and chlorite when plotted against stratigraphic succession show notable changes in the crystallographic axes.The illite lattices associated with inadequately pedogenized palaeosols have been altered into illite/smectite mixed layers,but,the chlorite lattices represent expansion of a-,b-and contraction of c-axes with much greater amount of distortions,suggestive of warm-humid and acidic environment.The detrital 48,44 and 83,74 bonded illite and chlorite with2 sub-types each,when pedogenized retained 48,44 and 34;and 83 and 74 bonds(in their neo-formed 3 and 2 sub-types),respectively.The Al-O bond shows expansion,but,unchanged Si-O and decreased Si-K and K-O bonds show loss of Al and retention of Si and K ions in the illite lattices.The illite with 32 atoms and 48 bonds represent contraction of K-O,Si-K,Al-O and Si-O bonds caused bond reinforcement;however,loss of Al~(3+)reflects all-out illite alteration.Owing to Al-O and K-O bond expansion,major K~+ and Al~(3+) ionic loss occurred during the LGM,however,further ionic loss depends upon the magnitude of the loess-palaeosol weathering that they have suffered.The clilate sensitive Fe,Mg and Al ionic losses for Fe-O,Mg-O and Al_(11)-O_9 bond length expansions were recognized in the chlorite lattices.Such ionic losses are common,but,complete distortion is attributed to Al,Si,Fe and Mg ionic losses,followed by weakening of Al-O,Si-O,Fe-O and Mg-O bonds.Though,Si-O_4 and Fe_1-O_4 bonds,and Si and Fe_(1 st) ions remain intact.Thus,three major glacial episodes of ～5 ka each occurred under alkaline environment,but,intervened by two successive cycles of 55 ka each,encompassing three alternate warm and cold climatic sub-cycles of 12-15 ka.But,the coldness increases with each warm-cold sub-cycle that attained the glacial maxima.Further,these events correlate well with the deep-sea records of the North Atlantic(MIS-1 to MIS-5 e) and CLP loess-palaeosols(～127 ka).  相似文献   

3.
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   

4.
We examined aluminosilicate glasses containing a variety of network modifying to intermediate cations (Li, La, Sc, and Fe), quenched from melts at 1 atm to 8 GPa, to further investigate the role of cation field strength in Al coordination changes and densification. 27Al Nuclear Magnetic Resonance Spectroscopy (NMR) reveals that the mean Al coordination increases with increasing pressure in the Li-containing glasses, which can be explained by a linear dependence of fractional change in Al coordination number on cation field strengths in similar K-, Na-, and Ca-containing aluminosilicate glasses (K < Na < Li < Ca). Measured recovered densities follow a similar linear trend. In contrast, the La-containing glasses have significantly lower mean Al coordination numbers at given pressures than the cation field strength of La and glass density would predict. La L3 X-ray absorption fine structure (XAFS) spectroscopy results indicate a significant increase with pressure in average La-O bond distances, suggesting that La and Al may be “competing” for higher coordinated sites and hence that both play a significant role in the densification of these glasses, especially in the lower pressure range. However, in Na aluminosilicate glasses with small amounts of Sc, 45Sc NMR reveals only modest Sc coordination changes, which do not seem to significantly affect the mean Al coordination values. For a Li aluminosilicate glass, 17O MAS and multiple quantum magic angle spinning (3QMAS) NMR data are consistent with generation of more highly coordinated Al at the expense of non-bridging oxygen (NBO), whereas La aluminosilicate glasses have roughly constant O environments, even up to 8 GPa. Finally, we demonstrate that useful 23Na and 27Al MAS NMR spectra can be collected for Ca-Na aluminosilicate glasses containing up to 5 wt.% Fe oxide. We discuss the types of structural changes that may accompany density increases with pressure and how these structural changes are affected by the presence of different cations.  相似文献   

5.
Thermal transformations of kaolinite of different degree of crystallinity have been monitored by 27Al and 29Si high-resolution NMR with magic-angle spinning (MAS NMR), X-ray diffraction, Fourier transform infrared, atomic absorption spectrophotometry and thermogravimetric analysis. NMR shows differences in the dehydroxylation process of kaolinites with different degree of crystallinity and reveals the presence of short-range order in metakaolinite. 29Si NMR spectra acquired with a 30 s recycle delay of poorly and highly crystalline samples heated at 480 and 500° C, respectively, contain three distinct signals; we discuss their assignment in the light of experiments involving leaching of the samples with aqueous KOH. Ca. 40% of Si sites retain their original Q 3 symmetry just above the onset of dehydroxylation and the Q 4 environment is present showing that a small amount of amorphous silica has already segregated. The spectrum of samples treated at 1000° C contains a signal at -110ppm (from Q 4 silicons) and a faint resonance, from mullite, at ca. -87 ppm. 29Si NMR also shows that cristobalite germs are already present at 950–1000° C. The 27Al MAS NMR spectra of metakaolinite reveal the presence of 4-, 5-and 6-coordinated Al. Changes in the three Al populations as a function of temperature have been monitored quantitatively. Below 800° C, 4-and 5-coordinated Al appears at the expense of 6-coordinated Al, but above 800° C the amount of 6-coordinated Al increases again. We suggest a dehydroxylation scheme which accounts for the presence of 4-and 5 coordinated Al. Above 900–950° C the latter signal is no longer present in the 27Al NMR spectra and new 4-and 6-coordinated Al species (mullite and γ-alumina) appear. We propose new ideas for the structure of metakaolinite.  相似文献   

6.
Sedimentary biogenic silica from Redeyef in Gafsa basin (southern Tunisia) was analysed for its 29Si and 27Al magic angle spinning nuclear magnetic resonance (MAS NMR) spectra and complemented by X-ray diffraction and SEM observations. The 29Si MAS NMR spectrum is characterized by the abundance of hydroxylated silicon, displayed in resonance intensities and reflects a clear tendency towards dissolution of diatomaceous amorphous silica and the occurrence of the hydrated silica, which is the main component that ensures the diagenetic transition via the mechanism of dissolution–precipitation to other more crystalline silica phases, after the lost of its hydroxyls groups (water) by heating (burial). 27Al MAS NMR reveals two coordinations of Al; the octahedrally coordinated Al suggests the presence of clay relics trapped during crystal growth or a microcrystalline zeolite (clinoptilolite detected by SEM observations), while the tetrahedrally coordinated Al suggests the presence of minor quantities of minerals with tetrahedral Al, such as an Al-rich fluid and/or minerals such as feldspars.  相似文献   

7.
A dravite from Yemen of near end-member composition was treated in air and hydrogen atmospheres at 600–900 °C to reveal changes in Mg and Al order over the octahedrally coordinated Y and Z sites, and to explore related changes in the characteristic vibrational bands in the principal (OH)-stretching frequency. Relevant information was obtained using electron microprobe analysis (EMPA), structural refinement (SREF) and polarized infrared (IR) single-crystal spectroscopy. Overall, the EMPA, SREF and IR data show that only minor changes occur during thermal treatment up to at least 800 °C, including variations in structural parameters, Mg–Al order–disorder and (OH)-stretching bands, indicating limited hydrogen loss. Untreated and treated dravite samples have very similar long-range and short-range atomic structures, which may be related to the occurrence of stable Al–Mg extended clusters around the O1 (=W) and O3 (=V) sites: W(F)–Y(MgMgMg)–V(OH)3–Z[AlAlAlAlAl(Al,Mg)]; W(OH)–Y(MgMgAl)–V(OH)3–Z[AlAlAlAlAl(Al,Mg)]; W(O2–)–Y(AlAlAl)–V(OH)3–Z[AlAlAlAlAl(Al,Mg)]. These extended clusters remain stable to temperatures close to the observed start of decomposition (~900 °C).  相似文献   

8.
 Ni-saturated montmorillonite from Camp-Bertaux heated at different temperatures has been studied by X-ray powder diffraction, X-ray absorption (EXAFS) and vibration IR spectroscopy. Analysis of the experimental data has shown that heating of samples at temperatures higher than 150° C was accompanied by migration of Ni cations into vacant cis-octahedra of 2:1 layers. In the octahedral sheet the Ni cation has two “heavy” (Fe) and four “light” (Al and Mg) nearest octahedral cations. A model for the octahedral cation distribution in Camp-Bertaux montmorillonite was proposed in which Fe and Mg octahedral cations are segregated in small clusters. Received July 7, 1996 / Revised, accepted August 23, 1996  相似文献   

9.
(Mg,Fe)(Si,Al)O3 perovskite samples with varying Fe and Al concentration were synthesised at high pressure and temperature at varying conditions of oxygen fugacity using a multianvil press, and were characterised using ex?situ X-ray diffraction, electron microprobe, Mössbauer spectroscopy and analytical transmission electron microscopy. The Fe3+/ΣFe ratio was determined from Mössbauer spectra recorded at 293 and 80?K, and shows a nearly linear dependence of Fe3+/ΣFe with Al composition of (Mg,Fe)(Si,Al)O3 perovskite. The Fe3+/ΣFe values were obtained for selected samples of (Mg,Fe)(Si,Al)O3 perovskite using electron energy-loss near-edge structure (ELNES) spectroscopy, and are in excellent agreement with Mössbauer data, demonstrating that Fe3+/ΣFe can be determined with a spatial resolution on the order of nm. Oxygen concentrations were determined by combining bulk chemical data with Fe3+/ΣFe data determined by Mössbauer spectroscopy, and show a significant concentration of oxygen vacancies in (Mg,Fe)(Si,Al)O3 perovskite.  相似文献   

10.
Reduction of octahedral Fe in the crystalline structure of smectites influences, possibly controls, surface-sensitive physical and chemical properties. The purpose of this study was to investigate if reduction of structural Fe by Na-dithionite or bacteria affects the chemical environment of constituent cations in montmorillonite, employing solid state multinuclear (29Si and 27Al) magic angle spinning nuclear magnetic resonance (MAS NMR) spectroscopy. Reduction of structural Fe resulted in a positive (down field) chemical shift of the main Si Q3 (Q3(0Al)) site which was strongly correlated with Fe(II) content and inferred that distortions in Si-OT (T=Si, Al) bond angles and Si-O bond lengths occur with increasing layer charge. The line width (W) of the 29Si Q3 signal also increased with increasing levels of reduction. No change occurred in the position of the peak maximum for the octahedral Al (27AlVI) signal; however, an increased W was observed for this peak with increasing Fe(II) content. These results are attributed to decreases in Si-O-T bond angles and Si-O bond distances, corresponding to a better fit between the tetrahedral and octahedral sheets brought about by the presence of Fe(II) in the clay structure. The increased 27AlVI signal width (W) may also be due to a lessening of the paramagnetic influence of Fe(III) nuclei and enhancement of 27AlVI signals with different quadrupole coupling constants (QCC). Multinuclear MAS NMR analyses of dithioniteand microbially-reduced montmorillonite indicate that reduction of structural Fe caused reversible changes in the smectite structure, at least as far as this method could discern.  相似文献   

11.
羟基铁铝柱撑蒙脱石Keggin结构的稳定性   总被引：12，自引：1，他引：11  
本文利用Ｋｅｇｇｉｎ结构可以发生类质同象置的性质,制备了含过渡金属离子Ｆｅ的羟基铁铝撑蒙脱石。  相似文献   

12.
A multinuclear solid-state NMR investigation of the structure of the amorphous alteration products (so called gels) that form during the aqueous alteration of silicate glasses is reported. The studied glass compositions are of increasing complexity, with addition of aluminum, calcium, and zirconium to a sodium borosilicate glass. Two series of gels were obtained, in acidic and in basic solutions, and were analyzed using 1H, 29Si, and 27Al MAS NMR spectroscopy. Advanced NMR techniques have been employed such as 1H-29Si and 1H-27Al cross-polarization (CP) MAS NMR, 1H double quantum (DQ) MAS NMR and 27Al multiple quantum (MQ) MAS NMR. Under acidic conditions, 29Si CP MAS NMR data show that the repolymerized silicate networks have similar configuration. Zirconium as a second nearest neighbor increases the 29Si isotropic chemical shift. The gel porosity is influenced by the pristine glass composition, modifying the silicon-proton interactions. From 1H DQ and 1H-29Si CP MAS NMR experiments, it was possible to discriminate between silanol groups (isolated or not) and physisorbed molecular water near Si (Q2), Si (Q3), and Si (Q4) sites, as well as to gain insight into the hydrogen-bonding interaction and the mobility of the proton species. These experiments were also carried out on heated samples (180 °C) to evidence hydrogen bonds between hydroxyl groups on molecular water. Alteration in basic media resulted in a gel structure that is more dependent on the initial glass composition. 27Al MQMAS NMR data revealed an exchange of charge compensating cations of the [AlO4]− groups during glass alteration. 1H-27Al CP MAS NMR data provide information about the proximities of these two nuclei and two aluminum environments have been distinguished. The availability of these new structural data should provide a better understanding of the impact of glass composition on the gel structure depending on the nature of the alteration solution.  相似文献   

13.
We have taken a systematic approach utilizing advanced solid-state NMR techniques to gain new insights into the controversial issue concerning the dissolution mechanisms of water in aluminosilicate melts (glasses). A series of quenched anhydrous and hydrous (∼2 wt% H2O) glass samples along the diopside (Di, CaMgSi2O6)—anorthite (An, CaAl2Si2O8) join with varying An components (0, 20, 38, 60, 80, and 100 mol %) have been studied. A variety of NMR techniques, including one-dimensional (1D) 1H and 27Al MAS NMR, and 27Al → 1H cross-polarization (CP) MAS NMR, as well as two-dimensional (2D) 1H double-quantum (DQ) MAS NMR, 27Al triple-quantum (3Q) MAS NMR, and 27Al → 1H heteronuclear correlation NMR (HETCOR) and 3QMAS/HETCOR NMR, have been applied. These data revealed the presence of SiOH, free OH ((Ca,Mg)OH) and AlOH species in the hydrous glasses, with the last mostly interconnected with Si and residing in the more polymerized parts of the structure. Thus, there are no fundamental differences in water dissolution mechanisms for Al-free and Al-bearing silicate melts (glasses), both involving two competing processes: the formation of SiOH/AlOH that is accompanied by the depolymerization of the network structure, and the formation of free OH that has an opposite effect. The latter is more important for depolymerized compositions corresponding to mafic and ultramafic magmas.Aluminum is dominantly present in four coordination (AlIV), but a small amount of five-coordinate Al (AlV) is also observed in all the anhydrous and hydrous glasses. Furthermore, six-coordinate Al (AlVI) is also present in most of the hydrous glasses. As Al of higher coordinations are favored by high pressure, AlVIOH and AlVOH may become major water species at higher pressures corresponding to those of the Earth’s mantle.  相似文献   

14.
A 29Si and 27Al magic angle spinning nuclear magnetic resonance study is reported for differently synthesized mullites. The 29Si MAS NMR spectra of all samples are essentially identical. They consist of a main resonance at -86.8 ppm, a shoulder around -90 ppm and a second resonance at -94.2 ppm. The main resonance is interpreted as being due to a sillimanite-type geometry around Si and the second one is tentatively assigned to a Si environment typical for mullite. The 27Al MAS NMR spectra of sinter- and fused-mullite measured at different Larmor frequencies revealed clearly the presence of three distinct Al sites in mullite, i.e. of octahedral (M1), tetrahedral (M2) and distorted tetrahedral (Al*) sites.  相似文献   

15.
A simple theory is developed which relates cation ordering in the olivine structure to compositional trends in the vibrational spectra of olivines. Quantitative results for (Mg, Mn) and (Fe, Mn) olivines indicate that Mn2+ favors the M2 site relative to both Mg2+ and Fe2+.  相似文献   

16.
The paper presents results of lithological-mineralogical, Mossbauer, and isotope-geochronological study of globular phyllosilicates (glauconite and illite) from the Lower Cambrian Virbalis Formation in western Lithuania. K-Ar dates of these minerals (382 and 374 Ma) do not correspond to stratigraphic positions of the studied samples and indicate the loss of radiogenic 40Ar, probably, in Middle Devonian. Simulation of cation distribution in the mineral structure and comparison of the obtained data with Mossbauer spectral characteristics suggest that loss of 40Ar was caused by the structural rearrangement of globular phyllosilicates during the postdiagenetic substitution of Fe2+, Mg2+, and Fe3+ by Al3+, with the subsequent ordering of cation distribution in octahedral layers. These processes were presumably related to the same Caledonian tectonic events that were responsible for metasomatic dolomitization of Lower Paleozoic rocks in adjacent areas of the Baltic region at the terminal Silurian-Devonian. Diffraction analysis showed that globules consist of two micaceous phases with different Fe contents (illite and glauconite). Two alternative models are considered to explain the formation of two-phase globules: (1) disequilibrium conditions of diagenetic mineral formation; (2) transformation of glauconite into illite. Although the available data are insufficient to make an unambiguous choice between these models, the second mechanism seems to be more preferable.__________Translated from Litologiya i Poleznye Iskopaemye, No. 4, 2005, pp. 403–415.Original Russian Text Copyright © 2005 by Zaitseva, Gorokhov, Ivanovskaya, Zvyagina, Mel’nikov, Yakovleva.  相似文献   

17.
Optical absorption spectra (OAS) of synthetic single crystals of the solid solution spinel sensu stricto (s.s.)–magnesioferrite, Mg(Fe3+Al1???y)2O4 (0?y?≤ 0.3), have been measured between 12 500 and 28 500?cm?1. Chemical composition and Fe3+ site distribution have been measured by electron microprobe and Mössbauer spectroscopy, respectively. Ferric iron is ordered to the tetrahedral site for samples with small magnesioferrite component, and this ordering is shown to increase with magnesioferrite component. The optical absorption spectra show a strong increase in band intensities with Fe3+→Al substitution. Prominent and relatively sharp absorption bands are observed at 25 300 and 21 300?cm?1, while less intense bands occur at 22 350, 18 900, 17 900 and 15 100?cm?1. On the basis of band energies, band intensities and the compositional effect on band intensity, as well as structural considerations, we assign the observed bands to electronic transitions in IVFe3+–VIFe3+clusters. A linear relationship (R 2= 0.99) between the αnet value of the absorption band at 21 300?cm?1 and [IVFe3+]?·?[VIFe3+] concentration product has been defined: αnet=2.2?+?15.8 [IVFe3+]?·?[VIFe3+]. Some of the samples have been heat-treated between 700 and 1000?°C to investigate the relation between Fe3+ ordering and absorption spectra. Increase of cation disorder with temperature is observed, which corresponds to a 4% reduction in the number of active clusters. Due to the high spatial resolution (??～?10?μm), the OAS technique may be used as a microprobe for determination of Fe3+ concentration or site partitioning. Potential applications of the technique include analysis of small crystals and of samples showing zonation with respect to total Fe3+ and/or ordering.  相似文献   

18.
Solid solution in vesuvianite is elucidated by examining chemical trends and cation abundances in 22 microprobe analyses of samples from the Big Maria Mountains, southeastern California. Two recent structure refinements indicate 50 filled cation sites per formula, providing the basis for data normalization. Previous optical absorption and Mössbauer studies help clarify site occupancies. Stoichiometric abundances of Si and Ca + Na indicate 18 and 19 per formula, filling all 4- and 8-fold sites respectively. The four 6-fold A-sites are filled with Al. The solid solution occurs mainly within the eight 6-fold AlFe-sites (Al, Mg, Fe2+, Fe3+, Ti) and one 5-fold B-site (Mg, Fe2+, Fe3+). Chemical trends and crystal chemical constraints delineate eight independent substitutions.An extensive solid solution in the elements Mg, Fe, Al, and Ti suggests considerable potential as a petrogenetic indicator. In order to treat equilibria involving vesuvianite thermodynamically, a reference composition must be chosen and activity-composition relations modeled. For a reference composition, Mg-vesuvianite (Fe, Ti, Na-free) was chosen because of its chemical simplicity, but problems in ascertaining its stoichiometry have led previous workers to propose at least six different formulas. In this study, its formula is determined from the microprobe analyses by applying exchange vectors to substitute components of pure Mg-vesuvianite for Fe and Ti. This yields Ca19Mg2Al11-Si18 O69(OH)9, with AlFe-sites=MgAl7, and B-sites=Mg. Subdivision of the AlFe-sites into at least two distinct sites is suggested by observed chemical trends which are explanable only when different substitutions are considered to operate within different AlFe-sites.A thermodynamic mole fraction is formulated for Mg-vesuvianite based on an ideal mixing-on-sites solution model. A method is provided for estimating the distribution of Fe between the AlFe- and B-sites. Thermodynamic mole fractions calculated using Fe site distributions estimated from microprobe data yield results similar to those calulated using Fe site distributions determined from Mössbauer analysis.  相似文献   

19.
Hydrothermal alteration, involving chiefly chlorite and illite, is extensively distributed within host rocks of the Pleistocene Hishikari Lower Andesites (HLA) and the Cretaceous Shimanto Supergroup (SSG) in the underground mining area of the Hishikari epithermal gold deposit, Kagoshima, Japan. Approximately 60% of the mineable auriferous quartz‐adularia veins in the Honko vein system occur in sedimentary rocks of the SSG, whereas all the veins of the Yamada vein system occur in volcanic rocks of the HLA. Variations in the abundance and chemical composition of hydrothermal minerals and magnetic susceptibility of the hydrothermally altered rocks of the HLA and SSG were analyzed. In volcanic rocks of the HLA, hydrothermal minerals such as quartz, chlorite, adularia, illite, and pyrite replaced primary minerals. The amount of hydrothermal minerals in the volcanic rocks including chlorite, adularia, illite, and pyrite as well as the altered and/or replaced pyroxenes and plagioclase phenocrysts increases toward the veins in the Honko vein system. The vein‐centered variation in mineral assemblage is pronounced within up to 25 m from the veins in the peripheral area of the Honko vein system, whereas it is not as apparent in the Yamada vein system. The hydrothermal minerals in sandstone of the SSG occur mainly as seams less than a few millimeters thick and are sporadically observed in halos along the veins and/or the seams. The alteration halos in sandstone of the SSG are restricted to within 1 m of the veins. In the peripheral area of the Honko vein system, chlorite in volcanic rocks is characterized by increasing in Al in its tetrahedral layer and the Fe/Fe + Mg ratio toward the veins, while illite in volcanic rocks has relatively low K and a restricted range of Fe/Fe + Mg ratios. Temperature estimates derived from chlorite geothermometry rise toward the veins within the volcanic rocks. The magnetic susceptibility of tuff breccia of the HLA varies from 21 to less than 0.01 × 10?3 SI within a span of 40 m from the veins and has significant variation relative to that of andesite (27–0.06 × 10?3 SI). The variation peripheral to the Honko vein system correlates with an increase in the abundance of hematite pseudomorphs after magnetite, the percentage of adularia and chlorite with high Fe/Fe + Mg ratios, and the degree of plagioclase alteration with decreasing distance to the veins. In contrast, sedimentary rocks of the SSG maintain a consistent magnetic susceptibility across the alteration zone, within a narrow range from 0.3 to 0.2 × 10?3 SI. Magnetic susceptibility of volcanic rocks of the HLA, especially tuff breccia, could serve as an effective exploration tool for identifying altered volcanic rocks.  相似文献   

20.
The dissolution rate of illite, a common clay mineral in Australian soils, was studied in saline-acidic solutions under far from equilibrium conditions. The clay fraction of Na-saturated Silver Hill illite (K1.38Na0.05)(Al2.87Mg0.46Fe3+0.39Fe2+0.28Ti0.07)[Si7.02Al0.98]O20(OH)4 was used for this study. The dissolution rates were measured using flow-through reactors at 25 ± 1 °C, solution pH range of 1.0-4.25 (H2SO4) and at two ionic strengths (0.01 and 0.25 M) maintained using NaCl solution. Illite dissolution rates were calculated from the steady state release rates of Al and Si. The dissolution stoichiometry was determined from Al/Si, K/Si, Mg/Si and Fe/Si ratios. The release rates of cations were highly incongruent during the initial stage of experiments, with a preferential release of Al and K over Si in majority of the experiments. An Al/Si ratio >1 was observed at pH 2 and 3 while a ratio close to the stoichiometric composition was observed at pH 1 and 4 at the higher ionic strength. A relatively higher K+ release rate was observed at I = 0.25 in 2-4 pH range than at I = 0.01, possibly due to ion exchange reaction between Na+ from the solution and K+ from interlayer sites of illite. The steady state release rates of K, Fe and Mg were higher than Si over the entire pH range investigated in the study. From the point of view of the dominant structural cations (Si and Al), stoichiometric dissolution of illite occurred at pH 1-4 in the higher ionic strength experiments and at pH ?3 for the lower ionic strength experiments. The experiment at pH 4.25 and at the lower ionic strength exhibited lower RAl (dissolution rate calculated from steady state Al release) than RSi (dissolution rate calculated from steady state Si release), possibly due to the adsorption of dissolved Al as the output solutions were undersaturated with respect to gibbsite. The dissolution of illite appears to proceed with the removal of interlayer K followed by the dissolution of octahedral cations (Fe, Mg and Al), the dissolution of Si is the limiting step in the illite dissolution process. A dissolution rate law showing the dependence of illite dissolution rate on proton concentration in the acid-sulfate solutions was derived from the steady state dissolution rates and can be used in predicting the impact of illite dissolution in saline acid-sulfate environments. The fractional reaction orders of 0.32 (I = 0.25) and 0.36 (I = 0.01) obtained in the study for illite dissolution are similar to the values reported for smectite. The dissolution rate of illite is mainly controlled by solution pH and no effect of ionic strength was observed on the dissolution rates.  相似文献   

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