Ultraviolet-blue ionic luminescence of alkali feldspars from bulk and interfaces

Laboratory driven ionic thermal exchange of alkali feldspars from K to Na produces samples which are strongly luminescent in the ultraviolet region near 320 nm. The sites providing this luminescence are suggested as being correlated with the motion of Na atoms along interface-interphases of the material (i.e. with Na-O bond fracture). The thermoluminescence peaks show multi-order kinetics. Thermal preheatings of low albite sensitize the feldspar lattice with respect to thermoluminescence generated by exposure to UV irradiation and heating produces a strong blue luminescence spread over the range 350 nm to 500 nm band in feldspars. The upper temperature for thermoluminescence in feldspars is ∼300 °C, which is also the point where ionic conductivity of albite (010) begins, but the 300 °C region is also the starting point of a large second glow peak in adularia. Whilst it seems appropriate to link the Na motion to the 350–500 nm emission, it is unclear whether these changes are the result of the large anisotropic thermal vibration of Na atoms or the massive Na jumps that occur when the lattice reaches 300 °C. A speculative model is considered in which the UV TL emissions of natural minerals are linked to different interface-interphases (grain boundaries, exsolution limits, twinning planes, antiphase domains). Increased interface coherency energies are related to the kinetic order and the spectral position of luminescence emission peaks. Received: 3 December 1998 / Revised, accepted: 17 April 1999     

High-temperature thermodynamic properties of alkali feldspars

Recent hydrofluoric acid solution calorimetric data are used to derive standard enthalpies and Gibbs free energies of formation of low-albite, high-albite, NaAlSi₃O₈ glass, microcline, sanidine, and KAlSi₃O₈ glass. The data are presented as high-temperature functions from 298.15 to 1400° K.     

Structure energies of the alkali feldspars

Structural energetics of the alkali feldspars have been studied using a “lattice” or structure energy model. Electrostatic energies, U _e,for 20 well-refined, non-intergrown alkali feldspars were calculated using Bertaut's (1952) summation procedure and average about ?13,400 kcal/mol; the repulsive energies of the alkali site in each structure (～15 kcal/mol) were calculated using repulsive parameters for K-O and Na-O interactions estimated from bulk modulus data for NaF and KF and the exponential form of the repulsive potential. Using a procedure in which the position of the alkali cation was varied while the oxygen cage was kept fixed, structure energy gradients for the alkali sites of high albite and a hypersolvus Ab₄₂Or₅₈ structure were computed. In both cases, a broad structure energy well, elongated approximately parallel to c and subparallel to the observed split Na positions, was found. In both structures there is a single energy minimum corresponding closely with the observed single alkali positions. Comparison of U _e values for the alkali feldspars with different K/Na ratios shows that intermediate compositions are predicted to be less “stable” than either endmember and that the potassic end-member is predicted to be less “stable” than the sodic one, assuming that all other factors contributiong to the free energies of each phase are approximately the same. Comparison of U _e values for the high albite and low sanidine structures with different Al/Si distributions and a fixed tetrahedral framework indicates that the ordered charge distributions are 63.0 and 54.8 kcal/mol, respectively, more “stable” than the disordered distributions. Smaller, more realistic energy differences were obtained by using U _evalues averaged from four separate calculations with a +3 charge on a different T site in each and with +4 charges on the other T sites. If, in addition, the charges on cations and oxygen are reduced to half their nominal formal charges, in agreement with Pauling's electroneutrality principle and the results of recent molecular orbital calculations on silicates, the predicted electrostatic energy differences are reduced to 3.6 and 1.6 kcal/mol, respectively. These calculations also indicate that the T₁O site in the high albite structure energetically favors Al and that the Al/Si distribution determines the Na position within the alkali site.     

Structural state of detrital alkali feldspars

The structural state of an alkali feldspar is determined by the nature of the distribution of Al and Si in the tetrahedral sites of the feldspar structure. This state is a function of a number of genetic controls including temperature, cooling rate, deformation, crystal size, and several chemical factors. Together these controls constitute a genetic regime. Identification of the structures of detrital feldspars may enable recognition of genetic regimes and be useful in provenance interpretation and mineral province definition. A 2-peak method of X-ray diffraction (XRD) determination as a variant of an earlier proposed 3-peak method of structural state determination is used in this study. Total analytical time for each determination is about 50–55 min per grain. Results of structural state identification of 126 detrital feldspars from Holocene stream sands derived from volcanic, plutonic and metamorphic rocks are presented in order to illustrate the application and potential of the technique. Detrital feldspars from the metamorphic rocks are all maximum microcline; those from the plutons range from orthoclase to microcline depending on the age of the pluton, whereas those from the volcanic rocks are sanidines.     

On the constitution of the alkali feldspars

Summary The crystalline variants of the alkali feldspars differ from each other in the pattern of Al/Si disorder. The interrelations of the several variants are graphically shown in Figs. 1, 2, and 3. In high albite thekind of disorder is different from that in any other alkali feldspar; therefore the transition high albitemonalbite is diffusive; but the transition monalbiteanalbite is displacive. See Fig. 10.The phase diagram of the system NaAlSi₃O₈–KAlSi₃O₈ is presented in Fig. 4. The volume relations of the mixed crystals (Figs. 5 and 8) indicate that albite exhibiting monoclinic symmetry at room temperature has a defect lattice (defect monalbite) with vacant Na sites. A vacant cation site behaves as if a large cation (for example K) were present; therefore the defect monalbite behaves like a mixed crystal with some K replacing Na.

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Zusammenfassung Die verschiedenen kristallinen Modifikationen der Alkalifeldspate unterscheiden sich bezüglich der Art und Weise ihrer Al/Si-Verteilung. Die Interrelationen sind in den Abb. 1, 2 und 3 dargestellt. Im Hochalbit ist die Al/Si-Verteilung andersartig als in irgendeinem anderen Alkalifeldspat. Die meisten Alkalifeldspate haben eine zwifache Unendlichkeit von Variationsmöglichkeiten der Al/Si-Verteilung (entsprechend der in Abb. 2 eingezeichneten Ebene), Hochalbit aber steht einzig da und weist eine dreifache Unendlichkeit von Möglichkeiten auf. Infolgedessen entspricht dem Übergang HochalbitMonalbit ein diffuser Umwandlungsmechanismus, dem Übergang MonalbitAnalbit aber ein displaciver (Abb. 10).Das Phasendiagramm des Systems NaAlSi₃O₈–KAlSi₃O₈ ist in Abb. 4 dargestellt. Die Volumverhältnisse der Mischkristalle (Abb. 5 und 8) deuten darauf hin, daß der bei gewöhnlicher Temperatur monokline Albit ein defektes Gitter hat (= defekter Monalbit mit teilweise unbesetzten Na-Punktlagen). Die Wirkung einer unbesetzten Kation-Punktlage im Gitter ist der Wirkung eines großen Kations (z. B. Kalium) gleich; hierdurch erklärt sich die Tatsache, daß der defekte Monalbit die Eigenschaften eines etwas K-haltigen Mischkristalls nachahmt.

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With 10 Figures

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Dedicated to ProfessorF. Machatschki on the occasion of his 70th birthday.     

Turbid alkali feldspars from the Isle of Skye,northwest Scotland

Partially turbid alkali feldspars from hydrothermally altered Tertiary granites on the Isle of Skye (the Red Hills granites) were studied using light microscopy, scanning and transmission electron microscopies, and energy-dispersive X-ray spectroscopy. Limpid cores and turbid rims of individual crystals were compared to determine the causes of the turbidity. The limpid cores were cryptoperthitic, with lamellar widths of 0.1–0.3 μm. In contrast, the turbid rims contained K-rich and Narich areas coarsened to >0.5 μm. Turbid regions contained abundant inclusions, whereas limpid regions did not. Two generations of turbidity were recognized. Feldspars from the Beinn an Dubhaich granite, a granite with near-normal values for ¹⁸O/¹⁶O possessed limpid cores surrounded by turbid rims that cast a reddish-brown hue in transmitted light. When viewed in darkfield light microscopy, the regions with the reddish-brown turbidity were blue. This is consistent with the hypothesis that the cloudy appearance of these turbid regions arises from the scattering of light by micrometerto submicrometer-sized inhomogeneities in refractive index caused by fluid-filled cavities. Feldspars from the Loch Ainort granite, a granite with low values for ¹⁸O/¹⁶O possessed limpid and reddish-brown-turbid cores surrounded by turbid rims that cast a blackish hue in transmitted light. Ion thinning of the turbid areas produced an abundance of small holes (≤1–2 μm) apparently the remains of fluid inclusions. Transmission electron microscopy revealed that some holes from regions of reddish-brown turbidity contained non-feldspar material, including halite and metal-rich phases of various compositions. In contrast, blackish turbid regions contained cavities filled with alteration products, such as kaolinite. Hence, the feldspars from granites on the Isle of Skye apparently record interactions with at least two fluids: a saline fluid (possibly a late-stage magmatic fluid) and a meteoric fluid.     

Mantled feldspars in alkali rhyolite from Oki-Dogo island,Japan

Summary Feldspar phenocrysts in alkali rhyolite from Oki-Dogo island in the Sea of Japan show mantled textures with cores of anorthoclase and rims of sanidine. These feldspars were examined by electron microscopy, X-ray diffraction and X-ray microanalysis. Anorthoclase first crystallized, then was partially resorbed, and finally sanidine overgrew on the anorthoclase. Saw-tooth or comb-like interfaces between the cores and rims were likely formed at the magmatic stage of resorption and overgrowth. Optically perthitic intergrowths appear in thin sections cutting saw-tooth or comb-like interfaces of the mantled feldspars. The sanidine preserves primary cryptoperthitic textures of a periodicity smaller than 10 nm, which are considered to have been produced by subsolidus exsolution after the resorption event ended. The anorthoclase has no exsolution texture under an electron microscope.

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Feldspatkristalle in Alkali-Rhyolith von der Insel Oki-Dogo, Japan

Zusammenfassung Feldspatkristalle in Alkali-Rhyolith von der Oki-Dogo Insel im Japanischen Meer zeigen ummantelte Texturen mit Kernen von Anorthoklas und Rändern von Sanidin. Diese Feldspate wurden mit Elektronenmikroskopie, Röntgendiffraktion und Mikrosondenanalyse untersucht. Anorthoklas kristallisierte zuerst, wurde dann teilweise resorbiert und schließlich wuchs Sanidin über den Anorthoklas. Sägezahn- und Kamm-ähnliche Grenzen zwischen Kernen und Rändern wurden wahrscheinlich wahrend des magmatischen Stadiums von Resorption und Überwachsung gebildet. Unter dem Mikroskop erkennt man, daß perthitische Verwachsungen durch Sägezahn- oder Kamm-artige Grenzen der ummantelten Feldspäte hinwegsetzen. Der Sanidin erhellt primäre kryptoperthitische Texturen mit einer Periodizität von > 10 nm, die als Produkte einer Subsolidus-Entmischung nach der Resorption interpretiert werden. Anorthoklas läßt unter dem Elektronenmikroskop keine Entmischungstexturen erkennen.

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With 6 Figures     

The petrological significance of misorientations between grains

Misorientation analysis quantifies microstructural features in tectonites, metamorphic and igneous rocks, and allows hypotheses on their formation to be tested. The misorientation between two lattices can be expressed by a rotation axis and rotation angle. For lattices with symmetry, it is conventional to take the minimum angle that enables one lattice to be rotated into the other. For a group of lattice measurements two types of misorientation distribution can be calculated. Selecting random pairs of grains gives the random-pair misorientation distribution. Selecting neighbouring pairs gives the neighbour-pair misorientation distribution. The forms of both distributions are visualised using histograms or cumulative frequency diagrams. They are strongly influenced by any overall crystallographic preferred orientation and by intrinsic crystal symmetry. In many rocks, the random-pair misorientation distribution and neighbour-pair misorientation distribution are statistically significantly different (quantified using the Kolmogorov-Smirnov test). Differences between the random-pair misorientation distribution and neighbour-pair misorientation distribution imply that adjacent grains have physically interacted or are inherited from a precursor microstructure. Interactions include (1) reduction in surface energy by lattice alignment. We show this may have occurred in garnet clusters in schist, and olivine in a cumulate. It is well-known in metals and may be a common geological process. (2) Nucleation, where those nuclei have influenced the orientation of adjacent nuclei. (3) Mechanical rotations of facetted grains in compacting crystal mushes, so that faces become parallel. (4) Growth twinning. Inheritance includes (1) subgrain rotation recrystallisation in tectonites deforming by crystal plastic processes. (2) Mechanical and transformation-related twinning. (3) Domainal microstructures, e.g. where grains have formed from a few large original grains, may give rise to spurious correlations when the orientation data cover more than one domain. With this proviso, misorientation analysis can be used to investigate many important microstructural processes.     

The composition and crystallinity of the near-surface regions of weathered alkali feldspars

Our ability to identify thin non-stoichiometric and amorphous layers beneath mineral surfaces has been tested by undertaking X-ray photoelectron spectroscopy (XPS) and transmission electron microscopy (TEM) work on alkali feldspars from pH 1 dissolution experiments. The outcomes of this work were used to help interpret XPS and TEM results from alkali feldspars weathered for <10,000 years in soils overlying the Shap Granite (north-west England). The chemistry of effluent solutions indicates that silica-rich layers a few nanometers in thickness formed during the pH 1 experiments. These layers can be successfully identified by XPS and have lower Al/Si, Na/Si, K/Si and Ca/Si values than the outermost ∼9 nm of unweathered controls. Development of Al-Si non-stoichiometry is coupled with loss of crystal structure to produce amorphous layers that are identifiable by TEM where >∼2.5 nm thick, whereas the crystallinity of albite is retained despite leaching of Na to depths of tens to hundreds on nanometers. Integration of XPS data over the outermost 6-9 nm of naturally weathered Shap feldspars shows that they have stoichiometric Al/Si and K/Si ratios, which is consistent with findings of previous TEM work on the same material that they lack amorphous layers. There is some XPS evidence for loss of K from the outermost couple of nanometers of Shap orthoclase, and the possibility of leaching of Na from albite to greater depths cannot be excluded using the XPS or TEM results. This study demonstrates that the leached layer model, as formulated from laboratory experiments, is inapplicable to the weathering of alkali feldspars within acidic soils, which is an essentially stoichiometric reaction.     

The microstructures of perthitic alkali feldspars revealed by hydrofluoric acid etching

Etching of alkali feldspar cleavage fragments with hydrofluoric acid vapor, followed by study of the surfaces by scanning electron microscopy (SEM), is a simple and rapid technique for characterizing the microtextures of crypto- and microperthites. This technique has a number of advantages over conventional transmission electron microscopy (TEM) including ease of sample preparation and the large areas of crystals which can be imaged. Alkali feldspars studied by the method can yield important information on the cooling history of igneous and metamorphic rocks, fluid-feldspar interactions and the morphology and microstructures of albite exsolution lamellae. Some of these applications are illustrated by examples of etched crypto- and micro-perthites from the Klokken layered syenite, south Greenland and the Shap granite, north-west England.     

Ion microprobe study of intragrain micropermeability in alkali feldspars

Alkali feldspar cleavage fragments from the Klokken layered syenite, South Greenland, were heated to 700°C at 0.1 GPa in 99% H₂ ¹⁸O for 75 h. These samples were then polished and imaged by ion microprobe for ¹⁸O. The feldspars were known to contain areas of pristine, braid micro-perthite which were not turbid and areas of deuteric patch perthite which were turbid. Turbidity is related to the presence of micropores in the feldspars. On imaging the grain, it was found that the ¹⁸O had penetrated into the parts of the grain which were microporous and not into the pristine areas. Micropores are therefore responsible for rendering the feldspars permeable as well as porous. The implications of micropermeable feldspars in several areas of geology are discussed.     

Low-temperature coherent exsolution in alkali feldspars from high-grade metamorphic rocks of Sri Lanka

In the alkali feldspars of the amphibolite- and granulite-facies rocks of Sri Lanka, a late-stage, final exsolution event is observed which produced film lamellae and fine-scale spindles. These were investigated by optical, microprobe, single-crystal, transmission electron microscopy and atomic resolution microscopy techniques. The lamellae and spindles exsolved below the coherent solvus at temperatures as low as 300 to 350° C. Precession photographs and ARM micrographs show that the intergrowth is perfectly coherent. In sections (010) the rhombic section of the Pericline twins corresponds to analbite or high albite. The albite lamellae and spindles nucleated and grew at low temperatures in a metastable disordered structural state within a tweed-orthoclase matrix and became periodically twinned analbite or high albite, which subsequently developed only a slight increase in Al, Si order. The relationship between twin periodicity and lamellar width, predicted for coherent intergrowths by Willaime and Gandais (1972), is obeyed. In Or-rich grains, in which coherent exsolution is the only exsolution event, the film lamellae tend to be restricted to the rim, the fine-scale spindles to the centre of the grains. The films nucleated heterogeneously at grain boundaries and grew towards the grain centres. Fine-scale spindles probably nucleated homogeneously in the interior part of grains. Heterogeneous nucleation and coherent growth are not mutually exclusive.     

The contribution of authigenic feldspars to the geochemical balance of alkali metals

About 5 per cent of all feldspars in sediments are authigenic. This amounts to 0·94 per cent of the total sedimentary mass. At least 2.1 × 10¹⁸ kg Na and 3.4 × 10¹⁸kg K have been removed from sea water by reconstitution of authigenic feldspars in the total mass of surviving sediments. Consequently, 9.3 × 10¹⁹ moles CO₂ have been released by the formation of authigenic albite and 8.8 × 10¹⁹ moles CO₂ by the formation of authigenic K-feldspar.     

Nucleation on perthite-perthite boundaries and exsolution mechanisms in alkali feldspars

A transmission electron microscope study of intracrystalline boundaries between two perthites of markedly different composition in composite crystals, one a tenary mesoperthite (Or₂₆Ab₅₂An₂₂, initially a homogeneous potassian monalbite) the other a more potassic cryptoperthite (Or₆₁Ab₃₃An₆, initially a homogeneous sodian sanidine), shows that the two perthites are in nearly parallel intergrowth. Most boundaries examined were of (hkO) type; (010) boundaries are straight, whereas other (hkO) boundaries are curved or stepped. Exsolution occurred first in the potassian monalbite (mesoperthite) and was unaffected by the boundary. Subsequent exsolution in the sodian sanidine (cryptoperthite) was affected by the boundary, but for up to only a few micrometers. Exsolution occurred by heterogeneous nucleation and growth of oligoclase on and from the intracrystalline boundary. At almost the same time the rest of the volume of sanidine exsolved by spinodal decomposition. 1–2 μm from the boundary in the intervening K-rich matrix of the sodian sanidine, further exsolution occurred by homogeneous nucleation. Time — temperature — transition curves for continuous cooling have been devised to account for the unusual complexity of the exsolution texture. Except in such exceptional circumstances as the example studied, the initial exsolution in high-temperature alkali feldspars of intermediate composition, unlike other minerals, probably does not occur by nucleation, but only by spinodal decomposition.     

The mechanism of cation and oxygen isotope exchange in alkali feldspars under hydrothermal conditions

The mechanism of re-equilibration of albite in a hydrothermal fluid has been investigated experimentally using natural albite crystals in an aqueous KCl solution enriched in ¹⁸O at 600°C and 2 kbars pressure. The reaction is pseudomorphic and produces a rim of K-feldspar with a sharp interface on a nanoscale which moves into the parent albite with increasing reaction time. Transmission electron microscopy (TEM) diffraction contrast and X-ray powder diffraction (XRD) show that the K-feldspar has a very high defect concentration and a disordered Al, Si distribution, compared to the parent albite. Raman spectroscopy shows a frequency shift of the Si-O-Si bending vibration from ~476 cm⁻¹ in K-feldspar formed in normal ¹⁶O aqueous solution to ~457 cm⁻¹ in the K-feldspar formed in ¹⁸O-enriched solution, reflecting a mass-related frequency shift due to a high enrichment of ¹⁸O in the K-feldspar silicate framework. Raman mapping of the spatial distribution of the frequency shift, and hence ¹⁸O content, compared with major element distribution maps, show a 1:1 correspondence between the reaction rim formed by the replacement of albite by K-feldspar, and the oxygen isotope re-equilibration. The textural and chemical characteristics as well as the kinetics of the replacement of albite by K-feldspar are consistent with an interface-coupled dissolution-reprecipitation mechanism.     

An experimental study of alkali metal distributions in feldspars and micas

K and Rb distributions between aqueous alkali chloride vapour phase (0.7 molar) and coexisting phlogopites and sanidines have been investigated in the range 500 to 800°C at 2000 kg/cm² total pressure.Complete solid solution of RbMg₃AlSi₃O₁₀(OH)₂ in KMg₃AlSi₃O₁₀(OH)₂ exists at and above 700°C. At 500°C a possible miscibility gap between approximately 0.2 and 0.6 mole fraction of the Rb end-member is indicated.Only limited solid solution of Rb AlSi₃O₈ in KAlSi₃O₈ has been found at all temperatures investigated.Distribution coefficients, expressed as $\text{K}{}_{\mathrm{d}}\text{= (}\text{Rb/K}\text{)}$ in solid/(Rb/K) in vapour, are appreciably temperature-dependent but at each temperature are independent of composition for low Rb end-member mole fractions in the solids. The determined $\text{K}{}_{\mathrm{D}}$ values and their approximate Rb end-member mole fraction ($\text{X}{}_{\mathrm{RM}}$) ranges of constancy are summarized as follows: (°C)$\text{T}$$\text{K}{}_{\mathrm{D}}{}^{\mathrm{Phlog/Vap.}}$$\text{X}{}_{\mathrm{RM}}$$\text{K}{}_{\mathrm{D}}{}^{\mathrm{Sandi/Vap.}}$$\text{X}{}_{\mathrm{rm}}$

     

17.

Intracrystalline microstructures in alkali feldspars from fluid-deficient felsic granulites: a mineral chemical and TEM study     

Lucie?Taj?manováEmail author  Rainer?Abart  Richard?Wirth  Gerlinde?Habler  Dieter?Rhede 《Contributions to Mineralogy and Petrology》2012,164(4):715-729

Samples of essentially “dry” high-pressure felsic granulites from the Bohemian Massif (Variscan belt of Central Europe) contain up to 2-mm-large perthitic alkali feldspars with several generations of plagioclase precipitates in an orthoclase-rich host. The first generation takes the form of lenses homogeneous in size, whereas the size of a second generation of very thin albite-rich precipitates is more variable with comparatively high aspect ratios. In the vicinity of large kyanite, garnet or quartz inclusions, the first generation of plagioclase precipitates is significantly less abundant, the microstructure is coarser than in the remainder of the perthitic grain and the host is a tweed orthoclase. The first generation of precipitates formed at around 850 °C during the high-pressure stage (16–18 kbar) of metamorphism. Primary exsolution was followed by primary coarsening of the plagioclase precipitates, which still took place at high temperatures (850–700 °C). The coarsening was pronounced due to the access of fluids in the outer portions of the perthitic alkali feldspar and in more internal regions around large inclusions. The second generation of albite-rich precipitates was formed at around 570 °C. TEM investigations revealed that the interfaces between the second-generation plagioclase lamellae and the orthoclase-rich host are coherent or semi-coherent. During late evolutionary stages of the perthite, albite linings were formed at phase boundaries, and the perthitic microstructure was partially replaced by irregularly shaped precipitates of pure albite with incoherent interfaces. The albitization occurred below 400 °C and was linked to fluid infiltration in the course of deuteric alteration. Based on size-distribution analysis, it is inferred that the precipitates of the first generation were most probably formed by spinodal decomposition, whereas the precipitates of the second generation rather were formed by nucleation and growth.     

18.

Mutual replacement reactions in alkali feldspars I: microtextures and mechanisms   总被引：4，自引：1，他引：4  

Ian Parsons  Martin R. Lee 《Contributions to Mineralogy and Petrology》2009,157(5):641-661

Intracrystal microtextures formed by a process of mutual replacement in alkali feldspars record fluid–rock reactions that have affected large volumes of the Earth’s crust. Regular, ≤1 μm-scale ‘strain-controlled’ perthitic microtextures coarsen, by up to 10³, by a dissolution–reprecipitation process, producing microporous patch or vein perthites on scales >100 μm. We have developed earlier studies of such reactions in alkali feldspar cm-scale primocrysts in layered syenites from the Klokken intrusion, South Greenland. We present new hyperspectral CL, SEM images, and laser ICPMS analytical data, and discuss the mechanism of such replacement reactions. The feldspars grew as homogeneous sodic sanidines which unmixed and ordered by volume diffusion during cooling into the microcline field at ~450°C, giving regular, fully coherent ‘braid’ cryptoperthite. At ≤450°C the crystals reacted with a circulating post-magmatic aqueous fluid. The braid perthite behaved as a single reactant ‘phase’ which was replaced by two product phases, incoherent subgrains of low albite and microcline, with micropores at their boundaries. The driving force for the reactions was coherency strain energy, which was greater than the surface energy in the subgrain mosaic. The external euhedral crystal shapes and bulk major element composition of the primocrysts were unchanged but they became largely pseudomorphs composed of subgrains usually with the ‘pericline’ and ‘adularia’ habits (dominant {110} and subordinate {010} morphology) characteristic of low T growth. The subgrains have an epitactic relationship with parent braid perthite. Individual subgrains show oscillatory zoning in CL intensity, mainly at blue wavelengths, which correlates with tetrahedral Ti. Regular zoning is sometimes truncated by irregular, discordant surfaces suggesting dissolution, followed by resumption of growth giving regular zoning. Zones can be traced through touching subgrains, of both albite and microcline, for distances up to ~500 μm. At ≤340°C, the microcline subgrains underwent a third stage of unmixing to give straight lamellar film perthites with periodicities of ~1 μm, which with further cooling became semicoherent by the development of spaced misfit dislocations. Sub-grain growth occurred in fluid films that advanced through the elastically strained braid perthite crystals, which dissolved irreversibly. Braid perthite was more soluble than the strain-free subgrain mosaics which precipitated from the supersaturated solution. Some volumes of braid texture have sharp surfaces that suggest rapid dissolution along planes with low surface energies. Others have complex, diffuse boundaries that indicate a phase of coherent lamellar straightening by volume diffusion in response to strain relief close to a slowly advancing interface. Nucleation of strain-free subgrains was the overall rate-limiting step. To minimise surface energy subgrains grew with low energy morphologies and coarsened by grain growth, in fluid films whose trace element load (reflected in the oscillatory zoning) was dictated by the competitive advance of subgrains over a range of a few tens of mm. The cross-cutting dissolution surfaces suggest influxes of fresh fluid. Removal of feldspar to give 2 vol% porosity would require a feldspar:fluid ratio of ~1:26 (by wt). The late reversion to strain-controlled exsolution in microcline subgrains is consistent with loss of fluid above 340°C following depressurization of the intrusion. A second paper (Part II) describes trace element partitioning between the albite and microcline subgrains, and discusses the potential of trace elements as a low-T geothermometer. This paper and the Part II are dedicated in memory of J.V. Smith and W.L. Brown, both of whom died in 2007, in acknowledgement of their unrivalled contributions to the study of the feldspar minerals over more than half a century.     

19.

二长石地质温度计在估算乌拉山金矿碱性长石形成温度中的应用   总被引：1，自引：0，他引：1  

胡萍赵令湖  边秋娟 《岩石矿物学杂志》2004,23(4):327-336

内蒙古乌拉山金矿田内主要出露晚太古代乌拉山群区域变质岩和规模不一的花岗岩体以及不同时代、不同种类的脉状地质体。含金矿脉中主要矿物共生组合为碱性长石、石英、斜长石、碳酸盐矿物(方解石、白云石)和少量金属硫化物。矿床的显著特征为碱性长石交代作用强烈，碱性长石也广泛产于该地区其他各种类型的岩石中。本文采用电子显微探针分析了共生碱性长石和斜长石的化学成分，并采用三元二长石温度模型估计了碱性长石的平衡温度。结果表明，第一成矿阶段的碱性长石一石英含金矿脉中碱性长石的形成温度为353℃，第二成矿阶段石英含金矿脉中碱性长石的形成温度为281℃，矿脉碱性长石形成压力约为5kbar。这些结果与同类矿石中平衡共生的碳酸盐矿物和云母类矿物的地质温度计估计的形成温度以及共生石英中流体包裹体的均一温度非常一致。因此，乌拉山金矿床形成和富集的温度可估测为260～380℃，压力约为5kbar。此外，应用二长石温度计计算了本地区区域变质片麻岩和花岗岩中碱性长石的平衡温度，所得温度比采用共生铁铝榴石和黑云母温度计估计的温度要低约250℃。这表明共生的铁铝榴石和黑云母的平衡温度可能代表其寄主变质岩变质期温度及寄主花岗岩原生温度，而区域变质岩和花岗岩中的碱性长石在经历了随后多次热液作用后，可能重新平衡再生，这也与前人对乌拉山金矿的矿床地质和同位素研究的结果一致。     

20.

An elevated temperature X-ray study of synthetic disordered Na-K alkali feldspars     

C. M. B. Henderson 《Contributions to Mineralogy and Petrology》1979,70(1):71-79

The temperature dependence of cell parameters for three disordered, synthetic alkali feldspars (Or₁₉, Or₃₈, and Or₁₀₀) has been determined up to 1,000 °C. The samples show no change in composition or degree of Si-Al disorder during the experiments. The triclinic-monoclinic inversion in the sample of composition Or₁₉ occurs at 560 °±10 °C and is accompanied by changes in the rates of expansion of a, b and c; the rate for a increases and those for b and c decrease above the inversion. The b and c parameters in Or₁₀₀ show small decreases with increasing temperature and this may be due to thermal motion effects causing a contraction of cell directions that are fully expanded at room temperature. Calculation of the thermal expansion ellipsoids for the monoclinic phases shows that the major expansion coefficients (₁) for all three samples are more than an order of magnitude greater than the intermediate (₂) and minor (₃) coefficients. Thus the thermal expansion of these phases is dominated by that of ₁ which makes an angle of 22 ± 4 ° with+a; this orientation is parallel to that of the short M-OA2 bonds. The thermal expansion mechanism for monoclinic, disordered alkali feldspars may involve tilting within the framework releasing compression along this direction and allowing the M-OA2 bonds to show high expansion rates. The stretching of the crankshaft units, which are parallel to a, may only play a subordinate role in controlling the expansion of the feldspar framework.     

(°C)T	$\text{K}{}_{\mathrm{D}}{}^{\mathrm{Phlog/Vap.}}$	$\text{X}{}_{\mathrm{RM}}$	$\text{K}{}_{\mathrm{D}}{}^{\mathrm{Sanid/Vap.}}$	$\text{X}{}_{\mathrm{RM}}$
500	$\text{0.64 ± 0.11}$	0–0.2	$\text{0.17 ± 0.04}$	0–0.07
700	$\text{1.11 ± 0.11}$	0–0.2	$\text{0.33 ± 0.04}$	0–0.1
800	$\text{1.28 ± 0.03}$	0–0.2	$\text{0.45 ± 0.06}$	0–0.1

Intracrystalline microstructures in alkali feldspars from fluid-deficient felsic granulites: a mineral chemical and TEM study

Samples of essentially “dry” high-pressure felsic granulites from the Bohemian Massif (Variscan belt of Central Europe) contain up to 2-mm-large perthitic alkali feldspars with several generations of plagioclase precipitates in an orthoclase-rich host. The first generation takes the form of lenses homogeneous in size, whereas the size of a second generation of very thin albite-rich precipitates is more variable with comparatively high aspect ratios. In the vicinity of large kyanite, garnet or quartz inclusions, the first generation of plagioclase precipitates is significantly less abundant, the microstructure is coarser than in the remainder of the perthitic grain and the host is a tweed orthoclase. The first generation of precipitates formed at around 850 °C during the high-pressure stage (16–18 kbar) of metamorphism. Primary exsolution was followed by primary coarsening of the plagioclase precipitates, which still took place at high temperatures (850–700 °C). The coarsening was pronounced due to the access of fluids in the outer portions of the perthitic alkali feldspar and in more internal regions around large inclusions. The second generation of albite-rich precipitates was formed at around 570 °C. TEM investigations revealed that the interfaces between the second-generation plagioclase lamellae and the orthoclase-rich host are coherent or semi-coherent. During late evolutionary stages of the perthite, albite linings were formed at phase boundaries, and the perthitic microstructure was partially replaced by irregularly shaped precipitates of pure albite with incoherent interfaces. The albitization occurred below 400 °C and was linked to fluid infiltration in the course of deuteric alteration. Based on size-distribution analysis, it is inferred that the precipitates of the first generation were most probably formed by spinodal decomposition, whereas the precipitates of the second generation rather were formed by nucleation and growth.     

Mutual replacement reactions in alkali feldspars I: microtextures and mechanisms

Intracrystal microtextures formed by a process of mutual replacement in alkali feldspars record fluid–rock reactions that have affected large volumes of the Earth’s crust. Regular, ≤1 μm-scale ‘strain-controlled’ perthitic microtextures coarsen, by up to 10³, by a dissolution–reprecipitation process, producing microporous patch or vein perthites on scales >100 μm. We have developed earlier studies of such reactions in alkali feldspar cm-scale primocrysts in layered syenites from the Klokken intrusion, South Greenland. We present new hyperspectral CL, SEM images, and laser ICPMS analytical data, and discuss the mechanism of such replacement reactions. The feldspars grew as homogeneous sodic sanidines which unmixed and ordered by volume diffusion during cooling into the microcline field at ~450°C, giving regular, fully coherent ‘braid’ cryptoperthite. At ≤450°C the crystals reacted with a circulating post-magmatic aqueous fluid. The braid perthite behaved as a single reactant ‘phase’ which was replaced by two product phases, incoherent subgrains of low albite and microcline, with micropores at their boundaries. The driving force for the reactions was coherency strain energy, which was greater than the surface energy in the subgrain mosaic. The external euhedral crystal shapes and bulk major element composition of the primocrysts were unchanged but they became largely pseudomorphs composed of subgrains usually with the ‘pericline’ and ‘adularia’ habits (dominant {110} and subordinate {010} morphology) characteristic of low T growth. The subgrains have an epitactic relationship with parent braid perthite. Individual subgrains show oscillatory zoning in CL intensity, mainly at blue wavelengths, which correlates with tetrahedral Ti. Regular zoning is sometimes truncated by irregular, discordant surfaces suggesting dissolution, followed by resumption of growth giving regular zoning. Zones can be traced through touching subgrains, of both albite and microcline, for distances up to ~500 μm. At ≤340°C, the microcline subgrains underwent a third stage of unmixing to give straight lamellar film perthites with periodicities of ~1 μm, which with further cooling became semicoherent by the development of spaced misfit dislocations. Sub-grain growth occurred in fluid films that advanced through the elastically strained braid perthite crystals, which dissolved irreversibly. Braid perthite was more soluble than the strain-free subgrain mosaics which precipitated from the supersaturated solution. Some volumes of braid texture have sharp surfaces that suggest rapid dissolution along planes with low surface energies. Others have complex, diffuse boundaries that indicate a phase of coherent lamellar straightening by volume diffusion in response to strain relief close to a slowly advancing interface. Nucleation of strain-free subgrains was the overall rate-limiting step. To minimise surface energy subgrains grew with low energy morphologies and coarsened by grain growth, in fluid films whose trace element load (reflected in the oscillatory zoning) was dictated by the competitive advance of subgrains over a range of a few tens of mm. The cross-cutting dissolution surfaces suggest influxes of fresh fluid. Removal of feldspar to give 2 vol% porosity would require a feldspar:fluid ratio of ~1:26 (by wt). The late reversion to strain-controlled exsolution in microcline subgrains is consistent with loss of fluid above 340°C following depressurization of the intrusion. A second paper (Part II) describes trace element partitioning between the albite and microcline subgrains, and discusses the potential of trace elements as a low-T geothermometer. This paper and the Part II are dedicated in memory of J.V. Smith and W.L. Brown, both of whom died in 2007, in acknowledgement of their unrivalled contributions to the study of the feldspar minerals over more than half a century.     

二长石地质温度计在估算乌拉山金矿碱性长石形成温度中的应用

内蒙古乌拉山金矿田内主要出露晚太古代乌拉山群区域变质岩和规模不一的花岗岩体以及不同时代、不同种类的脉状地质体。含金矿脉中主要矿物共生组合为碱性长石、石英、斜长石、碳酸盐矿物(方解石、白云石)和少量金属硫化物。矿床的显著特征为碱性长石交代作用强烈，碱性长石也广泛产于该地区其他各种类型的岩石中。本文采用电子显微探针分析了共生碱性长石和斜长石的化学成分，并采用三元二长石温度模型估计了碱性长石的平衡温度。结果表明，第一成矿阶段的碱性长石一石英含金矿脉中碱性长石的形成温度为353℃，第二成矿阶段石英含金矿脉中碱性长石的形成温度为281℃，矿脉碱性长石形成压力约为5kbar。这些结果与同类矿石中平衡共生的碳酸盐矿物和云母类矿物的地质温度计估计的形成温度以及共生石英中流体包裹体的均一温度非常一致。因此，乌拉山金矿床形成和富集的温度可估测为260～380℃，压力约为5kbar。此外，应用二长石温度计计算了本地区区域变质片麻岩和花岗岩中碱性长石的平衡温度，所得温度比采用共生铁铝榴石和黑云母温度计估计的温度要低约250℃。这表明共生的铁铝榴石和黑云母的平衡温度可能代表其寄主变质岩变质期温度及寄主花岗岩原生温度，而区域变质岩和花岗岩中的碱性长石在经历了随后多次热液作用后，可能重新平衡再生，这也与前人对乌拉山金矿的矿床地质和同位素研究的结果一致。     

An elevated temperature X-ray study of synthetic disordered Na-K alkali feldspars

The temperature dependence of cell parameters for three disordered, synthetic alkali feldspars (Or₁₉, Or₃₈, and Or₁₀₀) has been determined up to 1,000 °C. The samples show no change in composition or degree of Si-Al disorder during the experiments. The triclinic-monoclinic inversion in the sample of composition Or₁₉ occurs at 560 °±10 °C and is accompanied by changes in the rates of expansion of a, b and c; the rate for a increases and those for b and c decrease above the inversion. The b and c parameters in Or₁₀₀ show small decreases with increasing temperature and this may be due to thermal motion effects causing a contraction of cell directions that are fully expanded at room temperature. Calculation of the thermal expansion ellipsoids for the monoclinic phases shows that the major expansion coefficients (₁) for all three samples are more than an order of magnitude greater than the intermediate (₂) and minor (₃) coefficients. Thus the thermal expansion of these phases is dominated by that of ₁ which makes an angle of 22 ± 4 ° with+a; this orientation is parallel to that of the short M-OA2 bonds. The thermal expansion mechanism for monoclinic, disordered alkali feldspars may involve tilting within the framework releasing compression along this direction and allowing the M-OA2 bonds to show high expansion rates. The stretching of the crankshaft units, which are parallel to a, may only play a subordinate role in controlling the expansion of the feldspar framework.