Strontium diffusion in feldspars—a laboratory study

Sr⁹⁰ Radiotracer diffusion studies have been carried out on crystals of orthoclase and microcline using an ion implantation method. The activation energies are consistent with calculations based on mineral age data.     

Development of microporosity,diffusion channels and deuteric coarsening in perthitic alkali feldspars

Turbidity is an almost universal feature of alkali feldspars in plutonic rocks and has been investigated by us in alkali feldspars from the Klokken syenite using SEM and TEM. It is caused by the presence of myriads of tubular micro-inclusions, either fluid-filled micropores or sites of previous fluid inclusions, and is associated with coarsening of microperthite and development of sub-grains. Micropores are abundant in coarsened areas, in which porosities may reach 4.5%, but are almost absent from uncoarsened, pristine braind-microperthite areas. The coarsening is patchy, and involves a scale increase of up to 10³ without change in the composition of the phases, low albite and low microcline, or in the bulk composition of the crystal. It occurs abruptly along an irregular front within individual crystals, which retain their original shapes. The coherent braid microperthite gives way across the front to an irregular semi-coherent film perthite over a few m and then to a highly coarsened irregular patch perthite containing numerous small sub-grains on scales of a few hundred nm, in both phases. The coarsening and micropore formation occured at a T400°–450° C and it is inferred to have been driven by the release of coherent strain energy, low-angle grain-boundary migration being favoured by a fluid. The patchy nature of the coarsening and the absence of a relationship with initial grain boundaries suggest that the fluid was of local origin, possibly arising in part through exsolution of water from the feldspar. The sub-grain texture and microporosity modify profoundly the permeability of the rock, and greatly enhance the subsequent reactivity of the feldspars.     

Oxygen diffusion in anhydrous sanidine feldspar

Oxygen exchange experiments have been performed between single crystals of sanidine feldspar and oxygen gas enriched in ¹⁸O, at temperatures in the range 869–1053 °C, total pressure 1 atmosphere, for times up to 28 days. Oxygen isotope diffusion profiles in a direction perpendicular to (001) were determined with an ion microprobe. The experimental data obey a single Arrhenius relationship of the form D = 8.4 × 10⁻¹¹ exp. (−245 ± 15 kJ mol⁻¹/RT) m²s⁻¹. The results indicate that oxygen diffusion in anhydrous sanidine feldspar is marginally slower than oxygen diffusion in anhydrous anorthite. Comparison with published atomistic simulation studies suggests that oxygen transport in feldspar is by an interstitial mechanism. Received: 17 October 1997 / Accepted: 6 July 1998     

Partitioning of Pb between volcanic glass and coexisting sanidine and plagioclase feldspars

Pb contents were determined by isotope dilution in separated glass, sanidine, and plagioclase from 18 rocks ranging in composition from basalt to rhyolite. These data indicate that Pb is partitioned into silicate melt relative to plagioclase, but is equally distributed between melt and sanidine. Plagioclase/glass distribution coefficients increase from 0.1 to 0.7 in going from basalt to rhyolite. This relationship suggests that the distribution coefficient is dependent upon bulk composition, temperature, or both. Sanidine/glass distribution coefficients are close to unity in rocks ranging in composition from quartz latite to rhyolite. The variation in Pb contents in a natural magma series from Craters of the Moon National Monument, Idaho, indicates that minerals (olivine, plagioclase, magnetite, apatite and clinopyroxene) fractionated from these magmas all have very low crystal/liquid distribution coefficients for Pb.     

Non-equilibrium mixing in natural alkali feldspars

Chemical-optical and X-ray analysis of some perthite groups, from cristalline rock massifs, came into evidence that in perthites with the same order degree of Si/Al distribution, the observed variations of 2V_X are strictly related to the Na content in the potassic phase; i.e. 2V_X decreases when Ab mixed in the K-phase increases.This fact suggests that for any Si/Al, distribution, not in equilibrium, exists a certain range of non equilibrium mixing between Or and Ab.     

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.     

Dislocation-assisted diffusion of oxygen in albite

Oxygen diffusion in albite has been determined by the integrating (bulk ¹⁸O) method between 750° and 450° C, for a P _H2O of 2 kb. The original material has a low dislocation density (<10⁶ cm^?2), and its lattice diffusion coefficient (D ₁), given below, agrees well with previous determinations. A sample was deformed at high temperature and pressure to produce a uniform dislocation density of 5 × 10⁹ cm^?2. The diffusion coefficient (D _a) for this deformed material, given below, is about 0.5 and 0.7 orders of magnitude larger than D ₁ at 700° and 450° C, respectively. This enhancement is believed due to faster diffusion along the cores of dislocations. Assuming a dislocation core radius of 4 Å, the calculated pipe diffusion coefficient (D _p), given below, is about 5 orders of magnitude larger than D ₁. These results suggest that volume diffusion at metamorphic conditions may be only slightly enhanced by the presence of dislocations. $$\begin{gathered} D_1 = 9.8 \pm 6.9 \times 10^{ - 6} (cm^2 /\sec ) \hfill \\ {\text{ }} \cdot \exp [ - 33.4 \pm 0.6(kcal/mole)/RT] \hfill \\ \end{gathered} $$ $$\begin{gathered} D_a = 7.6 \pm 4.0 \times 10^{ - 6} (cm^2 /\sec ) \hfill \\ {\text{ }} \cdot \exp [ - 30.9 \pm 1.1(kcal/mole)/RT] \hfill \\ \end{gathered} $$ $$\begin{gathered} D_p \approx 1.2 \times 10^{ - 1} (cm^2 /\sec ) \hfill \\ {\text{ }} \cdot \exp [ - 29.8(kcal/mole)/RT]. \hfill \\ \end{gathered} $$      

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     

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.     

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.     

Strontium and samarium diffusion in diopside

The volume chemical diffusion of trace amounts of Sr in diopside has been measured as a function of temperature (1100–1300°C), pressure (1 bar–20 kbar), crystallographic direction, and composition. Three experimental/analytical techniques were employed: radiotracer and sectioning; stable tracer and ion microprobe; and Rutherford back-scattering spectroscopy. Comparison of the three yielded excellent agreement. Both natural and synthetic single crystal samples were used with results in the natural diopside giving diffusivities approximately two orders of magnitude greater than those in the man-made crystals. Samarium diffusion in the synthetic crystals was also examined with the ion probe technique with results similar to Sr.Arrhenius relations for diffusion (D = D₀exp[?ΔH_a/RT]) were calculated for different pressures and analytical techniques, and activation volumes (gDV_a) were derived from the equation D = D' exp[?PΔV_a/ RT]. Values of ΔV_a were negative for Sr diffusion. An empirical relation describing the temperature and pressure dependence of D for Sr in the c direction of the synthetic samples is: D(P, T) = 1200 (cm²/sec) exp[?122 (Kcal/mol)/RT (°K)]exp[?P (bar)/(2.94T ? 4640)R]. The expression for D_Sr in the natural samples (c direction) at one atmosphere is: D(0, T) = 54 (cm²/sec) exp[?97 (Kcal/mol)/RT (°K)]. A single compensation trend for all the data was evident for all values of D₀ and ΔH_a in the synthetic crystals.A number of models of geologic processes were investigated in light of the present data. Closure temperatures (T_c) were calculated for examples of mineral-mineral age-dating and trace element geothermometry. High values of T_c indicate that pyroxenes record emplacement events and are generally not disturbed unless a fluid enters the system. Isotopic equilibration times were examined for lower crustal xenoliths and the mantle source region for MORB using the formula of Hofmann and Hart (1978). Equilibration was shown to be too fast for production of isotopic anomalies in MORB via disequilibrium melting. Also. reasonable residence times at lower crustal temperatures were shown to produce the mineralogical-scale isotopic homogeneity observed in a crustal xenolith from Kilbourne Hole, New Mexico.     

Coexisting alkali feldspars in felsic members of the Cauro-Bastelica ring complex,Corsica

The granodioritic and gneissic Hercynian basement in Corsica was intruded, in the Triassic, by non-orogenic ring complexes in which the association early rhyolite-hypersolvus granite-granophyre-late subsolvus granite is clearly developed. The association of low albite and maximum microcline in mesoperthites cannot be attributed to Alpine low-grade metamorphism, restricted to fault zones. On a number of lines of evidence, the development of ordered, almost pure K-feldspar in this rapidly cooled complex appears related to an episode of mild reheating attending emplacement of late subsolvus granites, rocks formed from melts enriched, perhaps even saturated in aqueous fluids.     

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.     

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}}$

     

15.

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

J. Garcia-Guinea  P. D. Townsend  L. Sanchez-Muñoz  J. M. Rojo 《Physics and Chemistry of Minerals》1999,26(8):658-667

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     

16.

The effect of dislocations on bulk diffusion in feldspars during metamorphism   总被引：1，自引：0，他引：1  

R. A. YUND  J. QUIGLEY  J. TULLIS 《Journal of Metamorphic Geology》1989,7(3):337-341

ABSTRACT There is no significant difference in the diffusion profiles across albite-adularia bicrystals that were simultaneously deformed at a strain rate of 10^-6S^-1 and those from hydrostatic experiments at the same conditions (1500 MPa and 1000°C for 156 h). This indicates that the bulk alkali diffusion rate, which is the sum of lattice diffusion (D, ₁) and dislocation pipe diffusion (Dp), is not significantly enhanced by dislocations at these conditions, and that the maximum value for the ratio of D_p/D₁ is about 10⁵. This is equal to the value previously reported for‘oxygen’diffusion in albite. If this ratio is independent of temperature, the contribution of either static (pre-deformed) or moving (syn-deformed) dislocations to the bulk diffusion rate of alkalis is probably minor at all metamorphic conditions. For Al and Si diffusion the ratio of D_p/D₁ may be larger if D₁ is lower. Thus a significant contribution from dislocations to bulk diffusion cannot be ruled out, especially during simultaneous deformation.     

17.

The causes and petrological significance of cathodoluminescence emissions from alkali feldspars     

Adrian A. Finch  Jeanette Klein 《Contributions to Mineralogy and Petrology》1999,135(2-3):234-243

The cathodoluminescence (CL) of a variety of alkali feldspars from South Greenland has been examined in an attempt to understand the causes of the CL and its petrological significance. Analytical methods have included CL spectroscopy, secondary ion mass spectrometry (SIMS) and electron paramagnetic resonance (EPR) to correlate the presence of certain CL emissions to the presence of certain trace element and point defects. Where possible, blue and red luminescent fractions of the same rock samples have been separated and analysed separately. Blue CL appears to relate to the presence of electron holes on bridging oxygens, particularly on the Al-O-Al bridge, as determined from EPR studies. No correlation with other proposed activators for blue CL such as Eu²⁺, Ga³⁺ or Ti⁴⁺ was observed. Some blue luminescent feldspars also have an emission in the infra-red (IR), invisible during normal visible CL petrography. The red and IR CL emissions correspond to features in EPR spectra attributed to Fe³⁺ and support previous suggestions that Fe³⁺ is related to this emission. However, our studies indicate that the visible red CL relates specifically to Fe³⁺ on the T1 site, whereas the equivalent CL from disordered feldspars lies in the IR. The difference between red and IR CL emissions therefore relates to the state of Fe³⁺ order across the tetrahedral sites. These data allow more meaningful interpretations of CL as a petrographic tool in alkali feldspar-bearing rocks. Received: 5 March 1998 / Accepted: 23 November 1998     

18.

Eight-phase alkali feldspars: low-temperature cryptoperthite, peristerite and multiple replacement reactions in the Klokken intrusion   总被引：1，自引：0，他引：1  

Ian Parsons  John D. Fitz Gerald  Matthew T. Heizler  Lynn L. Heizler  Tim Ivanic  Martin R. Lee 《Contributions to Mineralogy and Petrology》2013,165(5):931-960

Eight feldspar phases have been distinguished within individual alkali feldspar primocrysts in laminated syenite members of the layered syenite series of the Klokken intrusion. The processes leading to the formation of the first four phases have been described previously. The feldspars crystallized as homogeneous sodian sanidine and exsolved by spinodal decomposition, between 750 and 600 °C, depending on bulk composition, to give fully coherent, strain-controlled braid cryptoperthites with sub-μm periodicities. Below ~500 °C, in the microcline field, these underwent a process of partial mutual replacement in a deuteric fluid, producing coarse (up to mm scale), turbid, incoherent patch perthites. We here describe exsolution and replacement processes that occurred after patch perthite formation. Both Or- and Ab-rich patches underwent a new phase of coherent exsolution by volume diffusion. Or-rich patches began to exsolve albite lamellae by coherent nucleation in the range 460–340 °C, depending on patch composition, leading to film perthite with ≤1 μm periodicities. Below ~300 °C, misfit dislocation loops formed, which were subsequently enlarged to nanotunnels. Ab-rich patches (bulk composition ~Ab₉₁Or₁An₈), in one sample, exsolved giving peristerite, with one strong modulation with a periodicity of ~17 nm and a pervasive tweed microtexture. The Ab-rich patches formed with metastable disorder below the peristerite solvus and intersected the peristerite conditional spinodal at ~450 °C. This is the first time peristerite has been imaged using TEM within any perthite, and the first time peristerite has been found in a relatively rapidly cooled geological environment. The lamellar periodicities of film perthite and peristerite are consistent with experimentally determined diffusion coefficients and a calculated cooling history of the intrusion. All the preceding textures were in places affected by a phase of replacement correlating with regions of extreme optical turbidity. We term this material ultra porous late feldspar (UPLF). It is composed predominantly of regions of microporous very Or-rich feldspar (mean Ab_2.5Or_97.4An_0.1) associated with very pure porous albite (Ab_97.0Or_1.6An_1.4) implying replacement below 170–90 °C, depending on degree of order. In TEM, UPLF has complex, irregular diffraction contrast similar to that previously associated with low-temperature albitization and diagenetic overgrowths. Replacement by UPLF seems to have been piecemeal in character. Ghost-like textural pseudomorphs of both braid and film parents occur. Formation of patch perthite, film perthite and peristerite occurred 10⁴–10⁵ year after emplacement, but there are no microtextural constraints on the age of UPLF formation.     

19.

Strontium isotope and alkali element abundances in ultramafic rocks     

Alan M. Stueber  V. Rama Murthy 《Geochimica et cosmochimica acta》1966,30(12):1243-1259

The concentrations of the trace elements Na, K, Rb and Sr and the isotopic composition of Sr have been measured in a suite of ultramafic rocks, including alpine-type intrusions, inclusions in basalts and kimberlite pipes, zones from stratiform sheets, and a mica peridotite. From these data and those available in the literature the following conclusions can be drawn. Alpine-type ultramafic material appears to be residual in nature and can be neither the source material for the derivation of basalts nor the refractory residue of modern basalts. Alpine-type ultramafic intrusions appear to have no relationship with ultramafic zones in stratiform sheets and were probably derived from the upper mantle. A genetic relationship exists between basalts and their ultramafic inclusions, but it is extremely doubtful that this inclusion material could give rise to basalts by partial fusion. There is a possible genetic relationship between basalts and ultramafic inclusions in kimberlite pipes, and this ultramafic material is a potential source for the derivation of basalts. Ultramafic inclusions in basalts are probably not fragments of an alpine-type ultramafic zone in the mantle. An attempt has been made to synthesize the data and interpretations of this study by way of speculations on the role of ultramafic rocks in the differentiation history of the earth.     

20.

Mutual replacement reactions in alkali feldspars II: trace element partitioning and geothermometry     

Ian Parsons  Charles W. Magee  Charlotte M. Allen  J. M. G. Shelley  Martin R. Lee 《Contributions to Mineralogy and Petrology》2009,157(5):663-687

Perthitic alkali feldspar primocrysts in layered syenites in the Klokken intrusion in South Greenland, underwent dissolution–reprecipitation reactions in a circulating post-magmatic aqueous fluid at ~450°C, and are to a large degree pseudomorphs. These ‘mutual replacement’ reactions provide a perfect natural experiment with which to study trace element partitioning between sodium and potassium feldspars growing simultaneously. The reactant ‘phase’ was a cryptoperthitic feldspar consisting of low albite and low microcline in a coherent sub-μm ‘braid’ intergrowth and the product phases were ‘strain-free’ incoherent subgrains of low albite and low microcline forming microporous patch perthites on scales up to 200 μm. The driving force for the reaction was reduction of coherency strain energy. The mechanisms of this process are described in Part I. Five mixed braid perthite–patch perthite crystals were analysed for major and trace elements using laser ablation-inductively coupled plasma mass spectrometry with a 19 μm beam diameter. This gave bulk analyses of the braid texture, which were in the range Ab_73–54Or_45–27An_4.3–0.8, but could resolve Ab- and Or-rich patches in patch perthite. The major element bulk compositions of the crystals were retained during the replacement reactions. Major components in patches plot on tielines in the Ab–Or–An ternary system that pass through or very close to the parent braid perthite composition and indicate local equilibrium on the scale of a few tens of mm. Many trace elements, including REE, were lost to the fluid during the deuteric reactions, but the effect is large only for Fe and Ti. Cs, Pb and Sr were added to some crystals. Plots of log distribution coefficient D for Rb, Ba, Pb, Eu²⁺, La and Ce between Or- and Ab-rich patches against ionic radius are straight lines, assuming eightfold coordination, and to a first approximation are independent of ionic charge. K also lies on these lines, and the smaller ions Na and Ca lie close to them. The best linear fits were obtained using ionic radii for ^[8]K and ^[8]Ca, but there is ambiguity as to whether ^[7]Na or ^[5]Na is most appropriate. The linear relationship shows that the listed trace elements are in the feldspar M-site rather than in inclusions. Tl is in M although an exact D could not be obtained. The very large Cs ion partitions strongly into the Or-rich phase but its D value appears to be less than predicted by extrapolation. The near-linearity arises because partitioning is occurring between two solids into sites which have similar Young’s moduli, so that the parabolas that normally represent trace element partitioning between crystals and liquids (which have negligible shear strength) approximately cancel out. Ga and Be are in T-sites, as well as some of the Fe and Ti present, although part is in oxide inclusions. The site of Sc is unclear, but if structural it is likely to be T. Partitioning on M-sites is a potential geothermometer but because the effective size of the irregular M-site is defined by its K and (Na + Ca) contents, which are controlled by ternary solvus relationships, its calibration is not independent of conventional two-feldspar geothermometers. Trace elements may however provide a useful means of confirming that feldspar pairs are in equilibrium, and of recognising feldspar intergrowths produced by non-isochemical replacement rather than exsolution. Two-feldspar geothermometry for the ternary phases in the low-albite microcline patch perthites gives temperatures above the stability range of microcline, markedly so if a correction is made for Si–Al ordering. This is probably because current geothermometers are too sensitive to low concentrations of An in ordered Or-rich feldspars. This interpretation is supported by two-feldspar assemblages growing at known temperatures in geothermal systems and sedimentary basins. This paper and the earlier Part I are dedicated in the 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. An erratum to this article can be found at     

(°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

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     

The effect of dislocations on bulk diffusion in feldspars during metamorphism

ABSTRACT There is no significant difference in the diffusion profiles across albite-adularia bicrystals that were simultaneously deformed at a strain rate of 10^-6S^-1 and those from hydrostatic experiments at the same conditions (1500 MPa and 1000°C for 156 h). This indicates that the bulk alkali diffusion rate, which is the sum of lattice diffusion (D, ₁) and dislocation pipe diffusion (Dp), is not significantly enhanced by dislocations at these conditions, and that the maximum value for the ratio of D_p/D₁ is about 10⁵. This is equal to the value previously reported for‘oxygen’diffusion in albite. If this ratio is independent of temperature, the contribution of either static (pre-deformed) or moving (syn-deformed) dislocations to the bulk diffusion rate of alkalis is probably minor at all metamorphic conditions. For Al and Si diffusion the ratio of D_p/D₁ may be larger if D₁ is lower. Thus a significant contribution from dislocations to bulk diffusion cannot be ruled out, especially during simultaneous deformation.     

The causes and petrological significance of cathodoluminescence emissions from alkali feldspars

The cathodoluminescence (CL) of a variety of alkali feldspars from South Greenland has been examined in an attempt to understand the causes of the CL and its petrological significance. Analytical methods have included CL spectroscopy, secondary ion mass spectrometry (SIMS) and electron paramagnetic resonance (EPR) to correlate the presence of certain CL emissions to the presence of certain trace element and point defects. Where possible, blue and red luminescent fractions of the same rock samples have been separated and analysed separately. Blue CL appears to relate to the presence of electron holes on bridging oxygens, particularly on the Al-O-Al bridge, as determined from EPR studies. No correlation with other proposed activators for blue CL such as Eu²⁺, Ga³⁺ or Ti⁴⁺ was observed. Some blue luminescent feldspars also have an emission in the infra-red (IR), invisible during normal visible CL petrography. The red and IR CL emissions correspond to features in EPR spectra attributed to Fe³⁺ and support previous suggestions that Fe³⁺ is related to this emission. However, our studies indicate that the visible red CL relates specifically to Fe³⁺ on the T1 site, whereas the equivalent CL from disordered feldspars lies in the IR. The difference between red and IR CL emissions therefore relates to the state of Fe³⁺ order across the tetrahedral sites. These data allow more meaningful interpretations of CL as a petrographic tool in alkali feldspar-bearing rocks. Received: 5 March 1998 / Accepted: 23 November 1998     

Eight-phase alkali feldspars: low-temperature cryptoperthite, peristerite and multiple replacement reactions in the Klokken intrusion

Eight feldspar phases have been distinguished within individual alkali feldspar primocrysts in laminated syenite members of the layered syenite series of the Klokken intrusion. The processes leading to the formation of the first four phases have been described previously. The feldspars crystallized as homogeneous sodian sanidine and exsolved by spinodal decomposition, between 750 and 600 °C, depending on bulk composition, to give fully coherent, strain-controlled braid cryptoperthites with sub-μm periodicities. Below ~500 °C, in the microcline field, these underwent a process of partial mutual replacement in a deuteric fluid, producing coarse (up to mm scale), turbid, incoherent patch perthites. We here describe exsolution and replacement processes that occurred after patch perthite formation. Both Or- and Ab-rich patches underwent a new phase of coherent exsolution by volume diffusion. Or-rich patches began to exsolve albite lamellae by coherent nucleation in the range 460–340 °C, depending on patch composition, leading to film perthite with ≤1 μm periodicities. Below ~300 °C, misfit dislocation loops formed, which were subsequently enlarged to nanotunnels. Ab-rich patches (bulk composition ~Ab₉₁Or₁An₈), in one sample, exsolved giving peristerite, with one strong modulation with a periodicity of ~17 nm and a pervasive tweed microtexture. The Ab-rich patches formed with metastable disorder below the peristerite solvus and intersected the peristerite conditional spinodal at ~450 °C. This is the first time peristerite has been imaged using TEM within any perthite, and the first time peristerite has been found in a relatively rapidly cooled geological environment. The lamellar periodicities of film perthite and peristerite are consistent with experimentally determined diffusion coefficients and a calculated cooling history of the intrusion. All the preceding textures were in places affected by a phase of replacement correlating with regions of extreme optical turbidity. We term this material ultra porous late feldspar (UPLF). It is composed predominantly of regions of microporous very Or-rich feldspar (mean Ab_2.5Or_97.4An_0.1) associated with very pure porous albite (Ab_97.0Or_1.6An_1.4) implying replacement below 170–90 °C, depending on degree of order. In TEM, UPLF has complex, irregular diffraction contrast similar to that previously associated with low-temperature albitization and diagenetic overgrowths. Replacement by UPLF seems to have been piecemeal in character. Ghost-like textural pseudomorphs of both braid and film parents occur. Formation of patch perthite, film perthite and peristerite occurred 10⁴–10⁵ year after emplacement, but there are no microtextural constraints on the age of UPLF formation.     

Strontium isotope and alkali element abundances in ultramafic rocks

The concentrations of the trace elements Na, K, Rb and Sr and the isotopic composition of Sr have been measured in a suite of ultramafic rocks, including alpine-type intrusions, inclusions in basalts and kimberlite pipes, zones from stratiform sheets, and a mica peridotite. From these data and those available in the literature the following conclusions can be drawn. Alpine-type ultramafic material appears to be residual in nature and can be neither the source material for the derivation of basalts nor the refractory residue of modern basalts. Alpine-type ultramafic intrusions appear to have no relationship with ultramafic zones in stratiform sheets and were probably derived from the upper mantle. A genetic relationship exists between basalts and their ultramafic inclusions, but it is extremely doubtful that this inclusion material could give rise to basalts by partial fusion. There is a possible genetic relationship between basalts and ultramafic inclusions in kimberlite pipes, and this ultramafic material is a potential source for the derivation of basalts. Ultramafic inclusions in basalts are probably not fragments of an alpine-type ultramafic zone in the mantle. An attempt has been made to synthesize the data and interpretations of this study by way of speculations on the role of ultramafic rocks in the differentiation history of the earth.     

Mutual replacement reactions in alkali feldspars II: trace element partitioning and geothermometry

Perthitic alkali feldspar primocrysts in layered syenites in the Klokken intrusion in South Greenland, underwent dissolution–reprecipitation reactions in a circulating post-magmatic aqueous fluid at ~450°C, and are to a large degree pseudomorphs. These ‘mutual replacement’ reactions provide a perfect natural experiment with which to study trace element partitioning between sodium and potassium feldspars growing simultaneously. The reactant ‘phase’ was a cryptoperthitic feldspar consisting of low albite and low microcline in a coherent sub-μm ‘braid’ intergrowth and the product phases were ‘strain-free’ incoherent subgrains of low albite and low microcline forming microporous patch perthites on scales up to 200 μm. The driving force for the reaction was reduction of coherency strain energy. The mechanisms of this process are described in Part I. Five mixed braid perthite–patch perthite crystals were analysed for major and trace elements using laser ablation-inductively coupled plasma mass spectrometry with a 19 μm beam diameter. This gave bulk analyses of the braid texture, which were in the range Ab_73–54Or_45–27An_4.3–0.8, but could resolve Ab- and Or-rich patches in patch perthite. The major element bulk compositions of the crystals were retained during the replacement reactions. Major components in patches plot on tielines in the Ab–Or–An ternary system that pass through or very close to the parent braid perthite composition and indicate local equilibrium on the scale of a few tens of mm. Many trace elements, including REE, were lost to the fluid during the deuteric reactions, but the effect is large only for Fe and Ti. Cs, Pb and Sr were added to some crystals. Plots of log distribution coefficient D for Rb, Ba, Pb, Eu²⁺, La and Ce between Or- and Ab-rich patches against ionic radius are straight lines, assuming eightfold coordination, and to a first approximation are independent of ionic charge. K also lies on these lines, and the smaller ions Na and Ca lie close to them. The best linear fits were obtained using ionic radii for ^[8]K and ^[8]Ca, but there is ambiguity as to whether ^[7]Na or ^[5]Na is most appropriate. The linear relationship shows that the listed trace elements are in the feldspar M-site rather than in inclusions. Tl is in M although an exact D could not be obtained. The very large Cs ion partitions strongly into the Or-rich phase but its D value appears to be less than predicted by extrapolation. The near-linearity arises because partitioning is occurring between two solids into sites which have similar Young’s moduli, so that the parabolas that normally represent trace element partitioning between crystals and liquids (which have negligible shear strength) approximately cancel out. Ga and Be are in T-sites, as well as some of the Fe and Ti present, although part is in oxide inclusions. The site of Sc is unclear, but if structural it is likely to be T. Partitioning on M-sites is a potential geothermometer but because the effective size of the irregular M-site is defined by its K and (Na + Ca) contents, which are controlled by ternary solvus relationships, its calibration is not independent of conventional two-feldspar geothermometers. Trace elements may however provide a useful means of confirming that feldspar pairs are in equilibrium, and of recognising feldspar intergrowths produced by non-isochemical replacement rather than exsolution. Two-feldspar geothermometry for the ternary phases in the low-albite microcline patch perthites gives temperatures above the stability range of microcline, markedly so if a correction is made for Si–Al ordering. This is probably because current geothermometers are too sensitive to low concentrations of An in ordered Or-rich feldspars. This interpretation is supported by two-feldspar assemblages growing at known temperatures in geothermal systems and sedimentary basins. This paper and the earlier Part I are dedicated in the 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. An erratum to this article can be found at