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1.
《Geochimica et cosmochimica acta》1999,63(13-14):2043-2059
Effects of the organic acid (OA) anions, oxalate and citrate, on the solubility and dissolution kinetics of feldspars (labradorite, orthoclase, and albite) at 80°C and of quartz at 70°C were investigated at pH 6 in separate batch experiments and in media with different ionic strength (0.02–2.2 M NaCl). Although it has been shown that OAs can increase rates of feldspar dissolution, prior experiments have focused primarily on dilute, highly undersaturated and acidic conditions where feldspar dissolution kinetics are dominated by H+ adsorption and exchange reactions. Many natural waters, however, are only weakly acidic and have variable ionic strength and composition which would be expected to influence mineral surface properties and mechanisms of organic ligand-promoted reactions.Oxalate and citrate (2–20 mM) increased the rate of quartz dissolution by up to a factor of 2.5. Quartz solubility, however, was not increased appreciably by these OAs, suggesting that Si–OA complexation is not significant under these conditions. The lack of significant OA–SiO2 interaction is important to understanding the effects of OAs on the release of both Si and Al from feldspars. In contrast to quartz, both the rates of dissolution and amounts of Si and Al released from the three feldspars studied increased regularly with increasing OA concentration. Feldspar dissolution was congruent at all but the lowest OA concentrations. Total dissolved Al concentrations increased by 1–2 orders of magnitude in the presence of oxalate and citrate, and reached values as high as 43 mg/l (1.6 mM). Si concentrations reached values up to 65 mg/l (2.3 mM) in feldspar–OA experiments. Precipitation of authigenic clays was observed only in experiments without or at very low concentrations of OAs. The high concentrations of dissolved Si attained during dissolution of feldspars in OA solutions, relative to Si concentrations in quartz–OA experiments, is attributed to concomitant release of Si driven by strong Al–OA interactions.Modeling of the dependence of feldspar dissolution rates on OA concentration in natural diagenetic environments is complicated by the competing effects of overall solution chemistry and ionic strength on the dissolution mechanism. Results of experiments using labradorite (An70) indicate that in OA-free solutions, dissolution is progressively slower at increasing NaCl concentrations (up to 2.2 M), in agreement with prior experiments on the effects of alkali metals on feldspar dissolution. The combined effects of oxalate and NaCl on labradorite dissolution rates are such that the rate increase due to oxalate is suppressed by the addition of NaCl. Thus, feldspar dissolution kinetics should be most significantly affected by a given concentration of OAs in low ionic strength solutions. 相似文献
2.
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
3.
Yoshiharu Nakajima Nobuo Morimoto Masao Kitamura 《Physics and Chemistry of Minerals》1977,1(2):199-212
A modulation function representing the position and density of (Na, Ca) atoms in the superstructure of the e-plagioclase has been derived from the average structures of different plagioclase and a general modulation theory. Based on this function the superstructure of bytownite (An73) has been studied with the single crystal X-ray method. The cell dimensions by Megaw's axes are a=7.946(3)A, b=67.09(2)A, c=12.236(4)A, α=39.03(1)°, β=45.63(1)° and γ=59.63(1)°. Z=18(Na, Ca) Al(Al, Si)Si2O8. The initial phase factor of the modulation function for bytownite has been obtained from the intensity data of the satellite reflections. This modulation function indicates a coherent small-scale alternation of the Na-rich and Ca-rich bands in the superstructure. This superstructure has been refined by applying the albite and anorthite structures to the Na-rich and Ca-rich bands, respectively. The change of the superstructure of the e-plagioclase due to the compositional change has been described based on the movements of the satellites in reciprocal space. The direction of the coherent small-scale intergrowth of the anorthite-like and albite-like bands is perpendicular to the t vector. The thickness of the intergrowth is 1/|t|. Both direction and thickness change regularly from An75 to An25. 相似文献
4.
With previous two-dimensional (2D) simulations based on surface-specific feldspar dissolution succeeding in relating the macroscopic feldspar kinetics to the molecular-scale surface reactions of Si and Al atoms (
[Zhang and Lüttge, 2008] and [Zhang and Lüttge, 2009]), we extended our modeling effort to three-dimensional (3D) feldspar particle dissolution simulations. Bearing on the same theoretical basis, the 3D feldspar particle dissolution simulations have verified the anisotropic surface kinetics observed in the 2D surface-specific simulations. The combined effect of saturation state, pH, and temperature on the surface kinetics anisotropy has been subsequently evaluated, found offering diverse options for morphological evolution of dissolving feldspar nanoparticles with varying grain sizes and starting shapes. Among the three primary faces on the simulated feldspar surface, the (1 0 0) face has the biggest dissolution rate across an extensively wide saturation state range and thus acquires a higher percentage of the surface area upon dissolution. The slowest dissolution occurs to either (0 0 1) or (0 1 0) faces depending on the bond energies of Si-(O)-Si (ΦSi-O-Si/kT) and Al-(O)-Si (ΦAl-O-Si/kT). When the ratio of ΦSi-O-Si/kT to ΦAl-O-Si/kT changes from 6:3 to 7:5, the dissolution rates of three primary faces change from the trend of (1 0 0) > (0 1 0) > (0 0 1) to the trend of (1 0 0) > (0 0 1) > (0 1 0). The rate difference between faces becomes more distinct and accordingly edge rounding becomes more significant. Feldspar nanoparticles also experience an increasing degree of edge rounding from far-from-equilibrium to close-to-equilibrium. Furthermore, we assessed the connection between the continuous morphological modification and the variation in the bulk dissolution rate during the dissolution of a single feldspar particle. Different normalization treatments equivalent to the commonly used mass, cube assumption, sphere assumption, geometric surface area, and reactive surface area normalizations have been used to normalize the bulk dissolution rate. For each of the treatments, time consistence and grain size dependence of the normalized dissolution rate have been evaluated and the results revealed significant dependences on the magnitude of surface kinetic anisotropy under differing environmental conditions. In general, the normalized dissolution rates are strongly dependent on grain size. Time-consistent normalization treatment varies with the investigated condition. The modeling results suggest that the sphere-, cube-, and BET-normalized dissolution rates are appropriate under the far-from-equilibrium conditions at low pH where these normalizations are time-consistent and are slightly dependent on grain size. 相似文献
5.
Robert J. Stull 《Lithos》1978,11(3):243-249
Mantled feldspars that formed by resorption, development of skeletal plagioclase crystals, and filling with alkali feldspar are common in the Golden Horn batholith, Washington. Subhedral plagioclase mantles have weak normal zoning from An17 to An10. Plagioclase zoning and twinning are crosscut by resorption channels. Resorption cavities and channels are coated with albite (An10). Anhedral, perthitic orthoclase within the plagioclase is optically continuous with orthoclase in channels and on the mantle exterior.This texture resulted from resorption of calcic cores of plagioclase as pressure decreased when water-undersaturated granite magma intruded to a shallow crustal level. At shallow level, only alkali feldspar and quartz crystallized and were available to fill the skeletal plagioclase. 相似文献
6.
Taking account of the Cˉ1/Iˉ1 (Al/Si order/disorder) transformation at high temperatures in the albite-anorthite solid solution
leads to a simple model for the mixing properties of the high structural state plagioclase feldspars. The disordered (Cˉ1)
solid solution can be treated as ideal (constant activity coefficient) and, for anorthite-rich compositions, deviations from
ideality can be ascribed to cation ordering. Values of the activity coefficient for anorthite in the Cˉ1 solid solution (γ
An
Cˉ1
) are then controlled by the free energy difference between Cˉ1 and Iˉ1 anorthite at the temperature (T) of interest according
to the relation: ΔˉG
ord
Iˉ1
⇌Cˉ1 =RT ln γ
An
Cˉ1
. If the Iˉ1⇌Cˉ1 transformation in pure anorthite is treated, to a first approximation, as first order and the enthalpy and
entropy of ordering are taken as 3.7±0.6 kcal/mole (extrapolated from calorimetric data) and 1.4–2.2 cal/mole (using an equilibrium
order/disorder temperature for An100 of 2,000–2,250 K), a crude estimate of γ
An
Cˉ1
for all temperatures can be made. The activity coefficient of albite in the Cˉ1 solid solution (γ
Ab
Cˉ1
) can be taken as 1.0. The possible importance of this model lies in its identification of the principal constraints on the
mixing properties rather than in the actual values of γ
An
Cˉ1
and γ
Ab
Cˉ1
obtained. In particular it is recognised that γ
An
Cˉ1
depends critically on ordering in anorthite as well as, at lower temperatures, any ordering in the Cˉ1 solid solution.
A brief review of activity-composition data, from published experiments involving ranges of plagioclase compositions and from
the combined heats of mixing plus Al-avoidance entropy model (Newton et al. 1980), reveals some inconsistencies. The values
of γ
An
Cˉ1
calculated using the approach of Newton et al. (1980), although consistent with Orville's (1972) ion exchange data, are slightly
lower than values derived from experiments by Windom and Boettcher (1976) and Goldsmith (1982) or from ion-exchange experiments
of Kotel'nikov et al. (1981). Based on the Cˉ1/Iˉ1 transformation model, values of γ
An
Cˉ1
<1.0 are unlikely.
Discrepancies between the experimental data sets are attributed to incomplete (non-equilibrium) Al/Si order attained during
the experiments. It is suggested that the choice of activity coefficients remains somewhat subjective. The development of
accurate mixing models would be greatly assisted by better thermodynamic data for ordering in pure anorthite and by more thorough
characterisation of the state of order in plagioclase crystals used for phase equilibrium experiments. 相似文献
7.
Mechanical albite and pericline twins were induced in seven feldspars, (Na, Ca) (Al, Si)4O8, in triaxial compression tests at 800° C, 8 to 10 kb confining pressure. Two were initially in a high temperature structural state (disordered) (An1, An59). Three (An32, An39, and An53) were slightly disordered, and two (An76 and An95) had the transitional and primitive anorthite structure, respectively. No microscopic twinning was detected in comparable tests on ordered albite and oligoclase (An1, An20), feldspars in the peristerite range (An11 An14) or in a low structural state labradorite (An51). Other deformational features include lamellae 60 to 80° from the c axis and (010) slip in the opposite sense for (010) twinning.Work performed under the auspices of the U. S. Atomic Energy Commission. 相似文献
8.
Stable silicon isotopes of groundwater, feldspars, and clay coatings in the Navajo Sandstone aquifer, Black Mesa, Arizona, USA 总被引：2，自引：0，他引：2
We present some of the first analyses of the stable isotopic composition of dissolved silicon (Si) in groundwater. The groundwater samples were from the Navajo Sandstone aquifer at Black Mesa, Arizona, USA, and the Si isotope composition of detrital feldspars and secondary clay coatings in the aquifer were also analyzed. Silicon isotope compositions were measured using high-resolution multi-collector inductively coupled mass spectrometry (HR-MC-ICP-MS) (Nu1700 & NuPlasma HR). The quartz dominated bulk rock and feldspar separates have similar δ30Si of −0.09 ± 0.04‰ and −0.15 ± 0.04‰ (±95% SEM), respectively, and clay separates are isotopically lighter by up to 0.4‰ compared to the feldspars. From isotopic mass-balance considerations, co-existing aqueous fluids should have δ30Si values heavier than the primary silicates. Positive δ30Si values were only found in the shallow aquifer, where Si isotopes are most likely fractionated during the dissolution of feldspars and subsequent formation of clay minerals. However, δ30Si decreases along the flow path from 0.56‰ to −1.42‰, representing the most negative dissolved Si isotope composition so far found for natural waters. We speculate that the enrichment in 28Si is due to dissolution of partly secondary clay minerals and low-temperature silcretes in the Navajo Sandstone. The discovery of the large range and systematic shifts of δ30Si values along a groundwater flow path illustrates the potential utility of stable Si isotopes for deciphering the Si cycling in sedimentary basins, tracing fluid flow, and evaluating global Si cycle. 相似文献
9.
The diffraction, n.q.r. and optical data on plagioclase feldspars are used to derive kinetic interpretations of structural changes induced by laboratory heat treatment and by geological processes. For anorthite, the Si, Al configuration is essentially ordered except for unusual transient processes. Cooperation between Ca atoms, and random nucleation, produces a domain texture in the primitive structure which is highly sensitive to temperature. The rapid inversion from the primitive to the body-centered structure is explained by increasingly rapid “rattling” of the Ca ions in the interstices of the semi-flexible alumino-silicate framework. The weakening of “b” reflections at higher temperatures is ascribed to incipient Si, Al disorder associated with irregular vibration of the alumino-silicate framework and the Ca atoms. Quenching phenomena are explained by variation of the domain boundary texture inherited from disorder at high temperature. For albite, the Si, Al configuration changes sluggishly from an ordered to a disordered pattern, and vice versa. Kinetic data are reinterpreted using a model in which the cell dimensions depend on local rather than distant order: the major change in distant order is deduced to occur at 450–600° C. Sodic plagioclase grown at high temperature shows distant disorder of the atoms, but cell dimensions suggest development of strong local order for calcic compositions. Low-entropy plagioclases of intermediate composition show complex intergrowths and domain structures because of kinetic barriers to atomic diffusion. X-ray diffraction data for slowly-cooled specimens are consistent with nucleation of albite- and anorthite-like regions from a high-temperature disordered phase. Electrostatic energy calculations show that Na and Ca atoms, although they face smaller energy barriers for diffusion, cannot form domains until the Si and Al atoms have moved jointly. The Si, Al ordering patterns of low albite and anorthite are topologically incompatible in a continuous framework if oxygen is not to be bonded to two Al. Therefore domains of low-albite and anorthite must be separated by disordered boundaries. For intermediate compositions, An15-An75, domains remain small. The anorthite-like domains probably form at higher temperatures than the albite-like domains. The latter tend to be about the same size for all bulk compositions. The atomic positions are influenced by neighboring atoms. Upon heating rapidly, Si and Al atoms remain in position and provide a memory for reformation of an identical structure upon cooling. The framework changes shape, and some Na, Ca atoms inter-diffuse to yield a quasi-homogeneous structure with a diffraction pattern which qualitatively approaches that of high albite. Upon prolonged heating at high temperature, Si, Al atoms inter-diffuse producing nonquenchable changes to the high-albite structure. At Na-rich bulk compositions, some domains of low albite grow into large lamellae while others remain small in contact with anorthite domains producing alternate lamellae of intermediate structure type; hence the peristerite intergrowth. A similar but opposite process could cause an intergrowth of lamellae of anorthite structure interposed with an intermediate type structure. A unique low plagioclase series is not expected. Plagioclases of intermediate composition trend towards slightly different endproducts depending on the details of the cooling history. Breaks and bends in plots of physical properties, and intergrowths for certain specimens, depend on special compositional, growth and annealing factors. The intergrowth responsible for iridescence of intermediate plagioclase is ascribed to Na, K segregation prior to development of the complex domain structure. Prolonged annealing at high temperature in a dry environment is suggested. It is futile to attempt to describe low entropy plagioclases in terms of classical thermodynamics: only a kinetic interpretation based on atomic and sub-microscopic textural factors can be viable. 相似文献
10.
Art F. White Marjorie S. Schulz Alex E. Blum Suzanne P. Anderson 《Geochimica et cosmochimica acta》2008,72(1):36-68
The spatial and temporal changes in element and mineral concentrations in regolith profiles in a chronosequence developed on marine terraces along coastal California are interpreted in terms of chemical weathering rates and processes. In regoliths up to 15 m deep and 226 kyrs old, quartz-normalized mass transfer coefficients indicate non-stoichiometric preferential release of Sr > Ca > Na from plagioclase along with lesser amounts of K, Rb and Ba derived from K-feldspar. Smectite weathering results in the loss of Mg and concurrent incorporation of Al and Fe into secondary kaolinite and Fe-oxides in shallow argillic horizons. Elemental losses from weathering of the Santa Cruz terraces fall within the range of those for other marine terraces along the Pacific Coast of North America.Residual amounts of plagioclase and K-feldspar decrease with terrace depth and increasing age. The gradient of the weathering profile bs is defined by the ratio of the weathering rate, R to the velocity at which the profile penetrates into the protolith. A spreadsheet calculator further refines profile geometries, demonstrating that the non-linear regions at low residual feldspar concentrations at shallow depth are dominated by exponential changes in mineral surface-to-volume ratios and at high residual feldspar concentrations, at greater depth, by the approach to thermodynamic saturation. These parameters are of secondary importance to the fluid flux qh, which in thermodynamically saturated pore water, controls the weathering velocity and mineral losses from the profiles. Long-term fluid fluxes required to reproduce the feldspar weathering profiles are in agreement with contemporary values based on solute Cl balances (qh = 0.025-0.17 m yr−1).During saturation-controlled and solute-limited weathering, the greater loss of plagioclase relative to K-feldspar is dependent on the large difference in their respective solubilities instead of the small difference between their respective reaction kinetics. The steady-state weathering rate under such conditions is defined as
11.
Liquidus phase equilibria have been determined in the system CaAl2Si2O8-NaAlSi3O8-KAlSi3O8-NaAlSiO4-KAlSiO4 (An-Ab-Or-Ne-Ks) at a pressure of water of 5 kb, for low anorthite contents. The main effects of increasing anorthite content on phase relationships in the system Ab-Or-Ne-Ks include the expansion of the plagioclase stability field towards the potassium-rich part of the system, and an accompanying contraction of the alkali feldspar, leucite, nepheline and kalsilite stability fields; and an increase in liquidus temperatures throughout most of the compositional range. Two quaternary invariant points have been identified in the system, one a reaction point between the fields of alkali feldspar, plagioclase, nepheline and kalsilite at approximately An4, and the other probably a quaternary eutectic between the fields of alkali feldspar, plagioclase, leucite and kalsilite at approximately An6. A shallow minimum trough in liquidus temperatures occurs on the two-feldspar surface, and this would be expected to control the paths of liquids cooling under equilibrium conditions. Phase relationships in this quaternary system have been applied to the interpretation of the histories of the potassium-rich rocks of the Roman Volcanic Region, Italy. Differentiation of the phonolitic series in this region may have occurred by two-feldspar fractionation. 相似文献
12.
Origin of mantle (rapakivi) feldspars: experimental evidence of a dissolution- and diffusion-controlled mechanism 总被引：1，自引：0，他引：1
Experiments designed to simulate the dissolution of alkali feldspar during magma mixing produced plagioclase mantles that are texturally and compositionally similar to those in some hybrid volcanic rocks. In hydrous dacite melt (69% SiO2) at 0.8 GPa, 850°C, orthoclase (Or93) and sanidine (Or30) partially dissolved and were mantled by sodic plagioclase (An25–30). Although plagioclase nucleated epitaxially as a thin shell on the alkali feldspar surface near the time of initial resorption, plagioclase subsequently grew inward —mostly in the form of parallel blades — toaard the receding dissolution surface. Orthoclase dissolved at a rate approximately proportional to the square root of run duration, indicating diffusional control. Plagioclase grew inward within a static boundary zone of melt that formed between the original crystal-dacite interface and the dissolution surface. During orthoclase dissolution, this boundary zone rapidly and simultancously gained Na (by diffusion from dacite) and lost K (by diffusion into dacite); Ca diffused more slowly into this zone, from which non-feldspar species were mostly excluded. Plagioclase was stable where sufficient Ca had diffused in that the boundary zone melt intersected the plagioclase-saturation liquidus. Plagioclase subsequently grew toward the receding dissolution surface as the Ca compositional gradient (and hence the site of plagioclase saturation) stepped inward. Crystallization of plagioclase in the form of parallel blades allowed continued diffusive exchange of melt components between the dissolution surface and the host melt. Bladed growth also served to maintain (at blade tips) proximity of plagioclase to the dissolution surface, thereby apparently preserving (locally) a thin zone of low-variance melt. In natural systems, mantling of alkali feldspar by plagioclase will occur in a similar manner when (a) P, T, or X are changed to induce alkali feldspar dissolution, (b) sufficient Ca is available in the host melt to drive (by diffusion) boundary zone melt compositions to plagioclase saturation, and (c) temperatures are low enough to stabilize sodic plagioclase and to maintain a coherent boundary zone. These reqjirements are satisfied in volcanic systems when alkali feldspar is juxtaposed during mixing with hybrid melts of dacitic composition. Mantled feldspars in some intrusive systems (i.e., rapakivi granites) may form by a similar dissolution- and diffusion-controlled mechanism. Textural evidence of a similar origin may be obscurred in intrusive rocks, however, by products of late-stage magmatic and subsolidus processes. 相似文献
13.
Coexisting feldspars from across 2,000 km2 of the granulite facies Oaxacan Complex, southern Mexico exhibit variable amounts of solid solution from nearly binary (Ab-An and Ab-Or) to substantially ternary (Ab-An-Or). Reintegrated analyses of 21 coarsely exsolved perthite (AF)-plagioclase (PL) pairs yield AF=Or30–63 Ab30–56An2–15 and PL=Or1–2Ab70–84An11–28. These data have been used to test existing two feldspar geothermometers for this extended composition range.For all compositions, temperature estimates show relatively little spread in value (660° to 795° C, 7 kbar) using the Haselton et al. (1983) calibration (HHHR). These temperatures are in fair agreement with estimates of 750±40° C for feldspar pairs with nearly binary compositions using the Stormer (1975) thermometer (STO). However, STO temperatures increase significantly (to 990° C) with increasing ternary solid solution in AF, suggesting that thermometers derived for binary systems are inaccurate for ternary compositions. Isotherms drawn from HHHR which take into account variable anorthite solution in alkali feldspar show that estimated temperature decreased by 50–100° C for each 5 mole percent anorthite in alkali feldspar.Experimentally determined solvus relations (Seck 1971) require feldspars with significant ternary solid solution to have crystallized or to have equilibrated at higher temperature than feldspars with more binary compositions. However, petrographic and field relations of ternary and binary feldspars in the Oaxacan Complex suggest they were all equilibrated at similar metamorphic pressures and temperatures and do not support a model where ternary feldspars have preserved higher premetamorphic temperatures. The composition of coexisting feldspars from other Precambrian granulite-facies terranes are also inconsistent with Seck's (1971) results. Hence, thermometers which fit Seck's solvus relations may not yield accurate temperatures in high grade metamorphic terranes. Parallel tie-lines for ternary and binary feldspars in the Oaxacan Complex and the consistency of inferred temperatures (HHHR) for many granulite terranes suggest that estimation of temperature using tie-line slopes rather than solvus width may yield more accurate results for these samples.Peak metamorphic conditions in the Oaxacan Complex are inferred to have been 730±50° C, 7±1 kbar. Pressure estimates from four garnet-plagioclase barometers show good agreement. Results of feldspar thermometry are consistent with diopside-forsterite equilibria in marbles which restrict T=720–765° C at P=7 kbar. 相似文献
14.
Nicolas C.M. Marty Jordi Cama Daisuke Chino Angelina Razafitianamaharavo Jocelyne Brendlé Josep M. Soler Christophe Tournassat 《Geochimica et cosmochimica acta》2011,75(20):5849-5864
The effect of pH and Gibbs energy on the dissolution rate of a synthetic Na-montmorillonite was investigated by means of flow-through experiments at 25 and 80 °C at pH of 7 and 9. The dissolution reaction took place stoichiometrically at 80 °C, whereas at 25 °C preferential release of Mg over Si and Al was observed. The TEM-EDX analyses (transmission electronic microscopy with quantitative chemical analysis) of the dissolved synthetic phase at 25 °C showed the presence of newly formed Si-rich phases, which accounts for the Si deficit. At low temperature, depletion of Si concentration was attributed to incongruent clay dissolution with the formation of detached Si tetrahedral sheets (i.e., alteration product) whereas the Al behaviour remains uncertain (e.g., possible incorporation into Al-rich phases). Hence, steady-state rates were based on the release of Mg. Ex situ AFM measurements were used to investigate the variations in reactive surface area. Accordingly, steady-state rates were normalized to the initial edge surface area (11.2 m2 g−1) and used to propose the dissolution rate law for the dissolution reactions as a function of ΔGr at 25 °C and pH∼9:
15.
16.
The Storm King granite at Bear Mountain, New York contains coarse alkali feldspar mesoperthite. The microstructure of these perthites grades continuously from lamellae to isolated blebs. The K rich phase in all samples has a nerely constant composition (Õr97Ab3), but the Na-rich phase ranges from An3.8 (lamellae) to An21 (blebs). It is suggested that the more calcium-rich feldspars exsolved at a higher temperature and thus experienced a longer time at higher temperature, during which the microstructure became more bleby or spherical in response to minimization of the interfacial energy. Lack of perfect correlation of the microstructure with bulk composition, as well as variation in the Al/Si ordering, may be due to additional factors, of which water activity or concentration is the most likely. 相似文献
17.
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
18.
Mineral weathering in soils is an important source of many nutrients to forest ecosystems. Apatite, a Ca phosphate mineral, occurs in trace amounts in virtually all igneous and metamorphic rocks and is often found as small mineral inclusions in more weathering-resistant silicate minerals. To better understand the distribution of apatite in soils and its exposure to soil solutions, a sequential extraction method was developed to selectively dissolve minerals from soils so that the amount of apatite in contact with soil solutions versus that armored by silicate minerals could be quantified. The use of three molarities of HNO3 (0.01, 0.1 and 1 M) at three temperatures (0, 10, or 20 °C) was explored and it was found that apatite congruently dissolved in 1 M HNO3 at all three temperatures, but did not completely dissolve in weaker HNO3 solutions. Soil horizons, glacial till (i.e., soil parent material), and individual minerals separated from till collected from the Hubbard Brook Experimental Forest (HBEF), NH, were subjected to a 4-step sequential extraction. Chemical analyses of the extracts indicate that 1 M NH4Cl (pH 7; 20 °C) removes exchangeable ions, 1 M HNO3 at 20 °C primarily dissolves apatite in contact with solutions, 1 M HNO3 at 200 °C primarily dissolves biotite and chlorite (and apatite armored by them), and a mixture of concentrated HNO3, HCl, and HF at 200 °C dissolves the more refractory minerals including muscovite, alkali feldspar, plagioclase feldspar and quartz (and apatite armored by these minerals). This extraction method was applied to soil profiles from HBEF to demonstrate that it could be used to interpret the abundance of apatite and other minerals as a function of depth. Approximately 70% of the apatite in the HBEF soil parent material is exposed to soil solutions; the remaining 30% is armored in more weathering-resistant micas and feldspars. In the upper soil horizons, the only apatite that has not been weathered from the soil occurs as inclusions in micas and feldspars and thus the rate of dissolution of apatite in weathered soil horizons is controlled by silicate mineral dissolution. 相似文献
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20.
The textural relationships and geochemistry of feldspars from least-altered to sericite-hematite altered and mineralised ~ 1.595 Ga Roxby Downs Granite (RDG) at Olympic Dam, South Australia, were examined. The sample suite is representative of RDG both distal (> 5 km) and proximal (< 1 km) to the hydrothermal breccias of the Olympic Dam Breccia Complex (ODBC), which host Fe-oxide Cu-Au-(U) mineralisation at Olympic Dam. Microscopic observations and quantitative analyses indicate that a range of feldspar reactions have taken place within the RDG hosting the Olympic Dam deposit. An early phase of igneous plagioclase (~ An27–34) is recognised, along with a more abundant, less-calcic plagioclase (~ An12–20) both displaying rapakivi and anti-rapakivi textures with alkali feldspar. Alkali feldspars (~ Or55Ab43An2) record post-magmatic evolution from cryptoperthite to patch perthite. Subsequent patch perthite is overprinted by highly porous, near end-member albite and K-feldspar, while plagioclase undergoes replacement by albite + sericite ± Ba-rich K-feldspar. In sericite-hematite altered and mineralised RDG along the margin of the ODBC, sericite replaces all plagioclase, whereas red-stained, Fe-rich K-feldspar persists. Sulphide-uranium-rare earth element mineralisation is observed in association with hydrothermal feldspars, and increases in abundance with proximity to the orebody. Petrographic observations and whole-rock geochemistry illustrate the transformation of plagioclase and alkali feldspar from igneous to hydrothermal processes, and indicate that hydrothermal albite and K-feldspar formed within the RDG without the need for an external source of alkalis. Feldspar geothermometry indicates a minimum crystallisation temperature of 765 °C at 2.2 kbar for alkali feldspar (pressure estimate obtained using plagioclase-amphibole geobarometry) followed by a range of lower temperature transformations. Late-stage magma mixing/contamination is postulated from supportive temperature and pressure estimates along with feldspar and mafic mineral relationships. 相似文献