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1.
Mössbauer effect, (ME) and powder X-ray diffraction, (XRD) have been used to study the relationship between cationic size, tetrahedral layer rotation, octahedral layer flattening, stability, and Mössbauer quadrupole splitting, qs, of iron bearing trioctahedral micas. Tetrahedral layer rotation accounts for much of the lattice adjustment but biotites that require an angle of rotation higher than 21 degrees are not stable. Both experimental and computational data show that qs for Fe3+ (IV) increases with increasing degree of tetrahedral layer rotation. A systematic increase of qs for Fe2+ (VI) is also observed, but this could be due to factors other than tetrahedral layer rotation.  相似文献   

2.
The 29Si and 27Al nuclear magnetic resonance (NMR) analysis of synthetic trioctahedral phyllosilicates 2:1, with tetrahedral ratios Al T/(Si + Al T) ranging from 0 to 0.5, has shown that the ditrigonal distortion of tetrahedral rings (angle ) is the main factor controlling chemical shift values of tetrahedral components in both signals. The increase of ditrigonal rotation angle shifts these components towards more positive values. For each sample, the composition of tetrahedral and octahedral sheets determine the value of , and from this parameter, the mean tetrahedral Tot angle and the chemical shift values of components are deduced. For a given environment, variations on ditrigonal angle are responsibles for the observed evolution of chemical shift values with bulk composition. The comparative analysis of micas and saponite samples has demonstrated that the location of compensating charge (interlayer and octahedral sheet) does not affect chemical shift values.  相似文献   

3.
Chemical and mineralogical analyses of the clay fraction of eleven soils containing a large amount of vermiculite clay and representing a wide range of parent materials revealed that two types of vermiculite clays exist: (1) An aluminous type in which Al3+ substitutes for Si4+ in tetrahedral positions in the same order of magnitude as in the coarse grained vermiculites and micas, and with Al3+ as the dominant octahedral ion. (2) A silicious type in which only Si4+ occupies the tetrahedral positions, and with Fe3+ and Mg2+ as the dominant octahedral ions. The aluminous vermiculite clay was found to occur in soils derived from acid igneous rocks and is usally associated with mica, whereas the silicious type was found to occur in soils derived from basic igneous rocks which do not contain mica. Because of this close association of these two types to their parent material, it was concluded that the aluminous vermiculite is a product of alteration of mica whereas the silicious type is a product of synthesis from primary oxides of silica, alumina, iron, and magnesium. Both types of vermiculite clays tend to be dioctahedral in contrast to the trioctahedral nature of the coarse-grained vermiculite.  相似文献   

4.
Quantum mechanical calculations based on the density functional theory (DFT) are used to study the crystal structures of dioctahedral 2:1 phyllosilicates. The isomorphous cation substitution is investigated by exploring different substitutions of octahedral Al3+ by Mg2+ or Fe3+, tetrahedral substitution of Si4+ by Al3+, and different interlayer cations (IC) (Na+, K+, Ca2+, and Mg2+). Samples with different kinds of layer charges are studied: only tetrahedrally charged, only octahedrally charged, or mixed octahedral/tetrahedral charged. The effect of the relative arrangements of these substitutions on the lattice parameters and total energy is studied. The experimental observation of segregation tendency of Fe3+ and dispersion tendency of Mg2+ in the octahedral sheet is reproduced and explained with reference to the relative energies of the octahedral cation arrangements. These energies are higher than those due to the IC/tetrahedral and IC/octahedral relative arrangements. The tetrahedral and octahedral substitutions that generate charged layers also tend to be dispersed. The octahedral cation exchange potentials change with the IC-charge/ionic radius value.  相似文献   

5.
Observation of major bands seen in infrared spectra of 26 phyllosilicates (23 of which were produced in the laboratory) are reported for wave numbers from 50 to 280 cm?1. Substitutions in the various structural sites (interlayer, tetrahedral and octahedral) permit one to identify the ions which contribute to the vibrations which give rise to bands in the infrared spectra. No attempt is made to assign vibrational modes or specific vibrational types. Using the following ion substitutions, OH-OD; Na-K-Sr-Mg-Ca; Si-Ge; Al-Ga; Mg-Co-Ni-Fe, it is apparent that in the 7 Å chlorite (amesite and chrysotile), kaolinite, pyrophyllite, aluminous dioctahedral mica, aluminous smectites and trioctahedral micas it is not possible to attribute any low frequency bands as being dominated by interlayer ion stretch vibrations (alkali ions). The cations which participate in the vibrators responsible for the dominant modes observed then seem to be Si and Al. This does not exclude the existence of interlayer ion stretch modes in these spectral regions, however they could not be identified. In the materials studied only a few bands can be attributed to hydroxyl-related vibrations and little influence is seen for octahedrally coordinated ions in dioctahedral minerals. It is important to note that the lowest frequency bands (80–140 cm?1) are apparently dominated by vibrations in the network and especially to the Si-O part of the structure. Low frequency bands are however most apparent in charged layer structures, i.e. micas and smectites.  相似文献   

6.
Zinc uptake in suspensions (?3.7 g L−1) of MX80 montmorillonite was investigated at pH 4.0 and 7.3, a total Zn concentration ([Zn]total) of 500 μM, and dissolved Si concentrations ([Si]aq) of ∼70 and ∼500 μM in 0.5 M NaCl, by kinetics experiments and polarized extended X-ray absorption fine structure (P-EXAFS) spectroscopy. Differential thermogravimetric analysis verified the cis-vacant character of the montmorillonite. No Zn uptake occurred at pH 4.0, confirming that cation exchange was hampered by the high ionic strength of the suspension. At pH 7.3 and low [Si]aq (∼70 μM), Zn uptake occurred rapidly during the first hour of reaction, and then leveled off to 50 μmol/g montmorillonite at 168 h. The uptake rate is consistent with Zn sorption on pH-dependent edge sites. At pH 7.3 and high [Si]aq (∼500 μM), the initial sorption rate was similar, but Zn sorption continued, reaching 130 μmol/g at 168 h, and was paralleled by Si uptake with a Si/Zn uptake ratio of 1.51(10), suggesting formation of a Zn (hydrous) silicate. P-EXAFS data indicated that the first oxygen coordination shell of sorbed Zn is split into two subshells at 1.97(2) and 2.08(3)-2.12(2) Å for all EXAFS samples. These two distances are assigned to a mixture of tetrahedral (IVZn) and octahedral (VIZn) Zn complexes. The proportion of IVZn was lower in the high [Si]aq samples and decreased with reaction time. Al low [Si]aq and 216 h of reaction, nearest cationic shells of 0.6(4) Al in the film plane and 0.5(4) Si out of the film plane were detected at 3.00(2) and 3.21(2) Å, respectively, and were interpreted as the formation of IVZn and VIZn mononuclear complexes at the edges of montmorillonite platelets, in structural continuity to the (Al, Mg) octahedral sheets. At high [Si]aq, in-plane Zn and Al and out-of-plane Si neighbors were detected at 4 h, indicating the formation of Zn phyllosilicate nuclei at the layer edges. At 313 h, Zn-Al pairs were no longer detected, and Zn atoms were surrounded on average by 3.4(5) in-plane Zn at 3.10(1) Å and 1.7(9) out-of-plane Si at 3.30(2) Å, supporting the precipitation of a Zn phyllosilicate. Thus, dioctahedral Al phyllosilicate may act as a nucleating surface for the heterogeneous formation of trioctahedral Zn phyllosilicate at [Si]aq relevant to natural systems.  相似文献   

7.
In its only natural occurrence known thus far sodium phlogopite is found in a dolomite containing large porphyroblasts of albite, three other magnesium phyllosilicates, dravite-uvite tourmaline, quartz, rutile, and pyrite. Sodium phlogopites are close to the ideal formula NaMg3[AlSi3O10](OH)2, although they may possibly contain additional Li. They are invariably coated by thin rims of potassium phlogopite with octahedral and tetrahedral occupancies different from those of sodium phlogopite. These rims may have prevented the retrograde hydration of sodium phlogopite which seems to be the main reason for its general absence in natural rocks. For the low-grade metamorphic conditions undergone by the dolomite a solvus relationship is indicated between sodium and potassium phlogopite.Sodium phlogopite also coexists, at least prior to the appearance of K phlogopite, with a talc phase containing Na and Al[4] substituting for Si. This type of substitution leading from pure talc to sodium phlogopite was found to extend as far as 36 mole percent. However, the nature of this phase as a genuine solid solution or as a disordered mixed-layer between talc and sodium phlogopite could not be identified as yet. The final phyllosilicate appearing in millimeter-size porphyroblasts is an ordered 11 mixed layer between clinochlore and sodian aluminian talc representing a new mineral.Metamorphic temperatures at the supposedly low water and CO2 fugacities are estimated to have been below 400 °C.  相似文献   

8.
The dependence on the composition of the thermodynamic stability of an illite can be treated in terms of a regular solution site-mixing model. Four end-member micas (muscovite, pyrophyllite, phlogopite, and annite) were mixed to simulate an illite in this study. In the model, random mixing of cations was assumed over each given class of cation sites. Mixing over cation sites between different classes of cation sites was not allowed. The resulting free energy and chemical potential equations contain four site interaction parameters: three for octahedral site interactions and one for interlayer and tetrahedral site interactions. These parameters cannot presently be evaluated because of a lack of experimental data on Fe3+-free illites. The model does imply that the octahedral site interaction parameters must be significantly more positive than the interlayer and tetrahedral site interaction parameter to account for the dominant dioctahedral nature of most natural illites. This constraint is necessary to balance out the increase in stability due to the configurational entropy of an illite having a major trioctahedral component.The model can be extended to cover a wider range of illite compositions by the inclusion of an end-member mica containing Fe3+ ions in the octahedral sites. At present the thermodynamic properties of such an end-member are unknown.  相似文献   

9.
The maintenance of waterways generates large amounts of dredged sediments, which are deposited on adjacent land surfaces. These sediments are often rich in metal contaminants and present a risk to the local environment. Understanding how the metals are immobilized at the molecular level is critical for formulating effective metal containment strategies such as phytoremediation. In the present work, the mineralogical transformations of Zn-containing phases induced by two graminaceous plants (Agrostis tenuis and Festuca rubra) in a contaminated sediment ([Zn] = 4700 mg kg−1, [P2O5] = 7000 mg kg−1, pH = 7.8), untreated or amended with hydroxylapatite (AP) or Thomas basic slag (TS), were investigated after two yr of pot experiment by scanning electron microscopy coupled with energy-dispersive spectrometry (SEM-EDS), synchrotron-based X-ray microfluorescence (μ-SXRF), and powder and laterally resolved extended X-ray absorption fine structure (μ-EXAFS) spectroscopy. The number and nature of Zn species were evaluated by principal component (PCA) and least-squares fitting (LSF) analysis of the entire set of μ-EXAFS spectra, which included up to 32 individual spectra from regions of interest varying in chemical composition. Seven Zn species were identified at the micrometer scale: sphalerite, gahnite, franklinite, Zn-containing ferrihydrite and phosphate, (Zn-Al)-hydrotalcite, and Zn-substituted kerolite-like trioctahedral phyllosilicate. Bulk fractions of each species were quantified by LSF of the powder EXAFS spectra to linear combinations of the identified Zn species spectra.In the untreated and unvegetated sediment, Zn was distributed as ∼50% (mole ratio of total Zn) sphalerite, ∼40% Zn-ferrihydrite, and ∼10 to 20% (Zn-Al)-hydrotalcite plus Zn-phyllosilicate. In unvegetated but amended sediments (AP and TS), ZnS and Zn-ferrihydrite each decreased by 10 to 20% and were replaced by Zn-phosphate (∼30∼40%). In the presence of plants, ZnS was almost completely dissolved, and the released Zn bound to phosphate (∼40-60%) and to Zn phyllosilicate plus (Zn,Al)-hydrotalcite (∼20-40%). Neither the plant species nor the coaddition of mineral amendment affected the Zn speciation in the vegetated sediment. The sediment pore waters were supersaturated with respect to Zn-containing trioctahedral phyllosilicate, near saturation with respect to Zn-phosphate, and strongly undersaturated with respect to (Zn,Al)-hydrotalcite. Therefore, the formation of (Zn,Al)-hydrotalcite in slightly alkaline conditions ought to result from heterogeneous precipitation on mineral surface.  相似文献   

10.
This paper reports on the new application of polarized extended X-ray absorption fine structure (P-EXAFS) spectroscopy to fine-grained layer silicates taking the Garfield nontronite as a case study. Up to now application of P-EXAFS to structural studies of layer silicates has been restricted to single phyllosilicate crystals (Manceau et al. 1988; Manceau et al. 1990), but we show here that P-EXAFS can rigorously be applied to self-supporting clay films without loss of spatial resolution. The quantitative analysis of P-EXAFS requires however the preparation of highly oriented clay films, the orientation distribution of which can be assessed by texture goniometry. The Fe K-edge linear dichroism measurements were simulated by ab initio EXAFS modeling performed on a nontronite cluster whose structure was refined by distance-valence least-squares calculations. It is shown that ab initio modeling quantitatively accounts for the angular dependence of experimental EXAFS spectra. These calculations allowed for the identification of the fundamental character of single- and multiple-scattering paths of the photoelectron, and the structural interpretation of all spectral features observed up to 6.5?Å for the in-plane and out-of-plane radial structure functions of nontronite. In practice, P-EXAFS measurements allow the determination of the flattening angle of Fe(O,OH)6 octahedra, cations distribution in the octahedral sheet with an enhanced sensitivity, and differentiation between dioctahedral and trioctahedral structures.  相似文献   

11.
 As part of a wider study of the nature and origins of cation order–disorder in micas, a variety of computational techniques have been used to investigate the nature of tetrahedral and octahedral ordering in phengite, K2 [6](Al3Mg)[4](Si7Al)O20(OH)4. Values of the atomic exchange interaction parameters J n used to model the energies of order–disorder were calculated. Both tetrahedral Al–Si and octahedral Al–Mg ordering were studied and hence three types of interaction parameter were necessary: for T–T, O–O and T–O interactions (where T denotes tetrahedral sites and O denotes octahedral sites). Values for the T–T and O–O interactions were taken from results on other systems, whilst we calculated new values for the T–O interactions. We have demonstrated that modelling the octahedral and tetrahedral sheets alone and independently produces different results from modelling a whole T–O–T layer, hence justifying the inclusion of the T–O interactions. Simulations of a whole T–O–T layer of phengite indicated the presence of short-range order, but no long-range order was observed. Received: 8 August 2002 / Accepted: 14 February 2003 Acknowledgements The authors are grateful to EPSRC (EJP) and the Royal Society (CIS) for financial support. Monte Carlo simulations were performed on the Mineral Physics Group's Beowulf cluster and the University of Cambridge's High Performance Computing Facility.  相似文献   

12.
Ti-spessartite, Ti-andradite and its indium homolog, Ca3In2(Si, Ti)3O12, have been synthesized and investigated by infrared (ir) spectroscopy. The use of isotopic species (46Ti-50Ti) gives the unequivocal proof that some of the additional bands observed in the 800–600 cm?1 region are due to TiO4 tetrahedra. For Si-Ti replacements up to 10 mol%, the localization of Ti on the available tetrahedral sites depends on the nature of the cations. For the In garnet all (or nearly all) Ti is located on tetrahedral sites; in Ti-andradite Ti is distributed over tetrahedral and octahedral sites, tetrahedral sites being thus occupied, in part by Ti (ir band near 700 cm?1) and in part by Fe (ir band near 650 cm?1); and Ti-spessartite the presence of Ti on tetrahedral sites is doubtful, these sites being essentially occupied by Al.  相似文献   

13.
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   

14.
层状硅酸盐矿物晶体结构的多体性组装模式与构筑原理   总被引：2，自引：0，他引：2  
将层状硅酸盐矿物晶体结构中属性不同的二维结构单元体看成是不同的结晶学模块,研究了一般层状硅酸盐矿物和间层矿物的多体性组装模式和构筑原理。结果表明,不同二维结构单元体(包括硅氧四面体片、八面体片、层间域(物))的构筑基本符合球体紧密堆积原理,紧密堆积层平行{0001};四面体片与八面体片构筑TO和TOT结构层时采取多种机制消除二者在二维尺寸上的差异;两种模式的结构层与不同类型的层间物(域)组装形成六种组装模式的晶层;并通过二维结构单元体的组合规律的分析,计算出可能存在的28种TOT型间层结构,它们分属于6种间层结构多体性组装模式;间层结构中,结构层对于八面体片是不对称的,并在属性上表现出极性特征;间层矿物的晶层类型可用6种多体性组装模式加以表达。层状硅酸盐矿物结构的多体性分析与组装模式的研究,对于矿物晶体化学研究是非常重要的。  相似文献   

15.
Transmission and scanning electron microscopy were utilized to investigate the nature and mechanisms of alteration of abundant detrital biotite of volcanic origin and progressive modification of phyllosilicate aggregates in a prograde sequence of pelitic rocks (illite crystallinity index = 0.19–0.58λ2θ) from the Gaspé Peninsula in Quebec.
Detrital biotite has been diagenetically altered to form corrensite and chlorite through two mechanisms; (1) layer-by-layer replacement gave rise to interstratification of packets of layers and complex mixed layering via several kinds of layer transitions between biotite and chlorite, corrensite or smectite; (2) dissolution-transport-precipitation resulted in the formation of relatively coarse-grained aggregates of randomly orientated, corrensite-rich flakes and fine-grained corrensite intergrown with chlorite and illite in the matrix.
The data show that stacks consisting of alternating packets of trioctahedral and dioctahedral phyllosilicates originated during early diagenesis when lenticular fissures in strained altering biotite were filled by dioctahedral clays. Subsequent prograde evolution of dioctahedral clays occurred through deformation, dissolution and crystallization, and overgrowth. Illite evolved to muscovite, with K in part provided through biotite alteration, and corrensite/chlorite to homogeneous chlorite. The alteration of detrital biotite is closely related to the formation of titanite and magnetite in diagenetic rocks, and pyrite, calcite and anatase or rutile in the higher grade rocks.
The observations demonstrate that detrital biotite of volcanic origin may be the principal precursor of chlorite in chlorite-rich metapelites originating in marginal basins. The mineral parageneses suggest that the transitions from corrensite to chlorite and illite to muscovite may be a function of local chemistry and time.  相似文献   

16.
《Geochimica et cosmochimica acta》1999,63(19-20):3193-3203
Formation of secondary Ni precipitates is an important mechanism of Ni retention in neutral and alkaline clay/water systems. However, the structure and composition of these secondary phases, and their stability is still disputable. Using existing structure refinement data and new ab-initio FEFF 7 calculations we show that Ni-edge X-ray absorption fine structure spectroscopy alone may not be able to unequivocally discriminate four possible candidate compounds: α-Ni(OH)2, the isostructural but Al-substituted layered double hydroxide (Ni-Al LDH), and 1:1 and 2:1 Ni-containing phyllosilicates. Hence, we investigated the potential of diffuse reflectance spectroscopy (DRS) in determining in situ the Ni phase forming in the presence of four sorbents, pyrophyllite, talc, gibbsite, and amorphous silica. The 3A2g → 3T1g(F) band (ν2) of octahedrally coordinated Ni2+ could be reliably extracted from the reflectance spectra of wet pastes. In the presence of the Al-free talc and amorphous silica, the ν2 band was at ≈14,900 cm−1, but shifted to 15,300 cm−1 in the presence of Al-containing pyrophyllite and gibbsite. This shift suggests that Al is dissolved from the sorbent and substitutes for Ni in brucite-like hydroxide layers of the newly forming precipitate phase, causing a decrease of the Ni-O distances and, in turn, an increase of the crystal-field splitting energy. Comparison with Ni model compounds showed that the band at 14,900 cm−1 is a unique fingerprint of α-Ni(OH)2, and the band at 15,300 cm−1 of Ni-Al LDH. Although the complete transformation of α-Ni(OH)2 into a Ni phyllosilicate causes a significant contraction of the Ni hydroxide sheet as indicated by band positions intermediate to those of α-Ni(OH)2 and Ni-Al LDH, incipient states of silication do not influence Ni-O distances and cannot be detected by DRS. The first evidence for the formation of a precipitate was obtained after 5 min (pyrophyllite), 7 hr (talc), 24 hr (gibbsite), and 3 days (amorphous silica). For both pyrophyllite and talc, where sufficiently long time series were available, the ν2 energy slightly increased as long as the Ni uptake from solution continued (3 days for pyrophyllite, 30 days for talc). This may be explained by a relative decrease of relaxed surface sites due to the growth of crystallites. Our study shows that the formation of both α-Ni(OH)2 and Ni-Al LDH may effectively decrease aqueous Ni concentrations in soils and sediments. However, Ni-Al LDH seems to be thermodynamically favored when Al is available.  相似文献   

17.
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   

18.
Glass-iron-clay setups were reacted at 90 °C for 6-18 months to investigate the coupled interactions between glass alteration, Fe corrosion and clay transformation. The reacted interfaces were probed at the microscopic level using complementary characterization methods (scanning electron microscopy coupled with energy-dispersive X-ray analysis, micro-Raman spectroscopy, micro X-ray diffraction, micro X-ray fluorescence spectroscopy, and micro X-ray absorption near-edge structure spectroscopy). The 10-μm thick Fe foil was fully corroded within 10 months, exposing glass to the pore solution. Iron corrosion led to the formation of a layer containing mostly magnetite, siderite and Fe-rich phyllosilicates with one tetrahedral and one octahedral sheet (TO) or two tetrahedral and one octahedral (TOT) sheet per layer. The clay in contact with this corrosion layer was enriched in siderite (FeCO3). Glass alteration resulted in the formation of a gel layer whose thickness increased with reaction time (from 20 μm after 6 months to 80 μm after 18 months) and a thin layer of secondary precipitates that concentrated lanthanides, P, and Mo. Assuming conservative behavior of Zr, the Si molar concentration in the gel is about 57% that in the glass. Glass dissolution remained at a rate close to the initial dissolution rate r0. The data are consistent with glass dissolution sustained by the uptake of dissolved Si and charge-compensating cations on secondary (corrosion) products, thus maintaining the gel porosity open and facilitating the leaching of easily soluble elements.  相似文献   

19.
Although widely investigated in relation to acid mine drainage systems at pH > 1.0, we know little about the impact of sulfuric acid (H2SO4) on the geochemistry and mineralogy of clays at pH < 1.0 (including negative pH values). Thus, laboratory batch experiments were conducted on three mixed clay samples with different mass ratios of phyllosilicates (smectite, illite, and kaolinite) to investigate the impact of H2SO4 from pH 1.0 to −3.0 for exposure periods of 14, 90, 180, and 365 days. Si and Al K- and L2,3-edge X-ray absorption near edge structure (XANES) spectroscopy were employed on these samples to determine the chemical and structural changes that occur during acidic dissolution of phyllosilicates that cannot be distinguished using X-ray diffraction analyses. A series of silicate, phyllosilicate, and Al-bearing standard compounds were also studied to provide an explanation for the observed changes in the clay samples. The Si XANES results indicated the preferential dissolution of the phyllosilicates (pH ? 1.0, t ? 14 d), the persistence of quartz even at pH ? −3.0 and t ? 365 d, and the formation of an amorphous silica-like phase that was confined to the surface layer of the altered clay samples at pH ? 0.0 and t ? 90 d). Al XANES results demonstrated dissolution of Al-octahedral layers (pH ? 1.0, t ? 14 d), the persistence of four-fold relative to six-fold coordinated Al, and the precipitation of an Al-SO4-rich phase (pH ? −1.0, t ? 90 d). An existing conceptual model of phyllosilicate dissolution under extremely acidic conditions was modified to include the results of this study.  相似文献   

20.
Phyllosilicates occurring as replacements of olivine, clinopyroxene and interstitial materials and as veins or fracture-fillings in hydrothermally altered basalts from DSDP Hole 504B, Leg 83 have been studied using transmission and analytical electron microscopy. The parageneses of phyllosilicates generally change systematically with depth and with the degree of alteration, which in turn is related to permeability of basalts. Saponite and some mixed-layer chlorite/smectite are the dominant phyllosilicates at the top of the transition zone. Chlorite, corrensite, and mixed-layer chlorite/corrensite occur mainly in the lower transition zone and upper levels of the sheeted dike zone. Chlorite, talc, and mixed-layer talc/chlorite are the major phyllosilicates in the sheeted dike zone, although replacement of talc or ohvine by saponite is observed. The phyllosilicates consist of parallel or subparallel discrete packets of coherent layers with packet thicknesses generally ranging from< 100 Å to a few hundred Å. The packets of saponite layers are much smaller or less well defined than those of chlorite, corrensite and talc, indicating poorer crystal-linity of saponite. by contrast, chlorite and talc from the lower transition zone and the sheeted dike zone occur in packets up to thousands of Å thick. The Si/(Si+Al) ratio of these trioctahedral phyllosilicates increases and Fe/(Fe+Mg) decreases in the order chlorite, corrensite, saponite, and talc. These relations reflect optimal solid solution consistent with minimum misfit of articulated octahedral and tetrahedral sheets. Variations in composition of hydrothermal fluids and precursor minerals, especially in Si/(Si+Al) and Fe/(Fe+Mg) ratios, are thus important factors in controlling the parageneses of phyllosilicates. The phyllosilicates are generally well crystallized discrete phases, rather than mixed-layered phases, where they have been affected by relatively high fluid/rock ratios as in high-permeability basalts, in veins, or areas adjacent to veins. Intense alteration in basalts with high permeability (indicating high fluid/rock ratios) is characterized by pervasive albitization and zeolitization. Minimal alteration in the basalts without significant albitization and zeolitization is characterized by the occurrence of saponite±mixed-layer chlorite/smectite in the low-temperature alteration zone, and mixed-layer chlorite/corrensite or mixed-layer talc/chlorite in the high-temperature alteration zone. Textural non-equilibrium for phyllosilicates is represented by mixed layering and poorly defined packets of partially incoherent layers. The approach to textural equilibrium was controlled largely by the availability of fluid or permeability.Contribution No. 488 from the Mineralogical Laboratory, Department of Geological Sciences, The University of Michigan  相似文献   

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