Rubidium mineralization in rare-element granitic pegmatites of the Voron’i tundras,Kola Peninsula,Russia

Rare-element pegmatites in the Voron’i tundras, Kola Peninsula, Russia, contain late abundant Rb mineralization. Individual Rb minerals are Rb-dominant feldspars and micas that form continuous solid solution series with K analoques. The feldspars contain from 17 to 86 mol % RbAlSi₃O₈ (5.5–25 wt % Rb₂O) and 1–5 mol % CsAlSi₃O₈, and the muscovite contains 2.6–9.4 wt % Rb₂O. The Li micas are members of the lepidolite-polylithionite series and their Rb-dominant analogues. They form a continuous series of solid solutions with the Rb concentrations varying from 0.09 to 0.54 apfu., K concentrations varying from 0.82 to 0.33 apfu, and Cs concentrations varying from 0.02 to 0.18 apfu The maximum Rb₂O concentration in the newly found mineral voloshinite, an Rb analogue of lepidolite, is 12.2 wt %. The Rb-rich feldspars and micas sometimes crystallized directly or were formed via cation exchange with the young fluid. The Rb minerals are spatially and genetically closely associated with pollucite. It is supposed that initially Rb was contained in a high-temperature pollucite solid solution and was released from it at decreasing temperature as a result of a reaction with the aqueous fluid and notably enriched the latter. It is shown that Rb mineralization is generally typical of pollucite-bearing pegmatites.     

Activity/composition relations in the ternary feldspars

Activity/composition relations are presented for high-structural state feldspars whose bulk compositions lie within the ternary system NaAlSi₃O₈ CaAl₂Si₂O₈-KAlSi₃O₈. The expressions are parameterized from the data for coexisting feldspars of Seck (1971a) using an asymmetric regular solution approximation for the excess Gibbs free energy of mixing and an Al-avoidance model for the configurational entropy of solution. The solution properties of the plagioclase and alkali-feldspar binaries have been made to conform to the recent work of Thompson and Hovis (1979) and Newton et al. (1980). Using the proposed model the ternary feldspar solvus is extrapolated in temperature (up to 1,500° C) and pressure (up to 5kbars). A new two-feldspar geothermometer is presented which provides somewhat more reasonable estimates of crystallization temperatures than the equations and graphs of Stornier (1975), Powell and Powell (1977), Brown and Parsons (1981) and Haselton et al. (1983). In conjunction, some criteria are suggested for establishing the existence of equilibrium tie-lines between coexisting ternary feldspars in rhyolites and trachytes. Calculated values of the activity of KAlSi₃O₈ in plagioclase are examined in some detail. These compare favorably with independent estimates obtained from experimentally grown plagioclases precipitating at liquidus temperatures from igneous rocks of widely varying alkali contents.     

Rapid open-system assembly of a large silicic magma body: time-resolved evidence from cored plagioclase crystals in the Oruanui eruption deposits, New Zealand

Rhyolitic pumices in the 26.5 ka Oruanui eruption (Taupo volcano, New Zealand) contain an average of 10 wt% crystals. About 2 wt% of the crystal population is feldspar crystals that display bluish–grey cloudy cores, the colour being imparted by exsolved needles of rutile. The volume of cloudy-cored feldspars thus amounts to ~1.0 km³ in a total magma volume of ~530 km³. The cored feldspars show great variability in detail, but in general have a rounded cloudy core bounded by a zone rich in glass and mineral inclusions, that was then overgrown by a euhedral clear rim. Sr-isotopic variations in eight representative crystals were measured on micromilled samples of selected growth zones in the cores and rims, and linked to feldspar compositions through microprobe traverses. The cloudy cores range from ⁸⁷Sr/⁸⁶Sr = 0.70547 to 0.70657, with compositions of An₄₃ to An₇₈. The overgrowth rims display wider variations: inner parts show extreme ranges in composition (maxima ⁸⁷Sr/⁸⁶Sr = 0.70764 and An₇₈), while outer parts in seven of eight crystals are zoned, with outward-decreasing Sr-isotopic and An values to figures that are in accord with the bulk pumice and other, clear-feldspar values, respectively. The three parts of the crystals represent distinct regimes. The cloudy cores are inherited from an intermediate plutonic protolith that has been subjected to melting. The inner overgrowth rims were crystallised from a high temperature, relatively radiogenic melt derived from Mesozoic-Palaeozoic metasedimentary rocks (“greywacke”). The outer euhedral rims reflect mixing into and continued growth within the growing Oruanui magma body. The cloudy-cored feldspars also contain rare zircon inclusions. Twenty one zircons were recovered by HF digestion of a bulk sample of cloudy feldspars and analysed by SHRIMP for U–Th isotopes with which to calculate model ages. Eighteen of 21 crystals returned finite ages, the model-age spectrum of which is similar to the age spectra from free zircons in Oruanui pumices. Assembly of the Oruanui magma body was not only rapid (over ~40 kyr, as shown by other data) but involved a wide open system, with significant contributions from partly-melted intermediate-composition igneous intrusions (cloudy cores) and greywacke melts (inner overgrowths) being introduced into the magma body up to the point of eruption. Such open system behaviour contrasts with that proposed in models for comparably voluminous silicic magmas derived dominantly by fractionation (such as the Bishop Tuff) where the magma and its crystal cargo were better insulated thermally and chemically from country-rock interaction.     

Ternary feldspars: Kinetics and possible equilibria at 800° C

The ternary feldspar system KAlSi₃O₈ - NaAlSi₃O₈ - CaAl₂Si₂O₈ was reinvestigated at 650 ° C and 800 ° C (P _H2O = 1 kb) using mixtures of crystalline plagioclases and alkali feldspars as starting materials. The compositions of plagioclases and alkali feldspars of the run products were determined by X-ray means. The Or-content of the feldspar phases was determined by measuring the position of the (201) X-ray peak of the unexchanged feldspars, whereas the An-content was determined by measuring the same X-ray peak of the K-exchanged feldspars. The reaction rate of a reaction leading to a more An-rich plagioclase (type II reaction) is much faster than a reaction producing a more Ab-rich plagioclase (type I). In a type II reaction run times of approximately 20 days are needed to reach new constant plagioclase and alkali feldspar compositions at 650 ° C, and 10 days are needed to reach constant compositions at 800 ° C. In a reaction of type I only the outer zone of the plagioclases reacts to more Abrich compositions. A diffuse zone with a wide range of compositions was observed in 650 ° C runs. Equilibrium could not be reached in these experiments within 45 days. At 800 ° C a new zone having a specific composition develops in 42 days. This new zone is believed to be in equilibrium with the coexisting alkali feldspar. The depth of reaction is calculated as 0.03 μm after 42 days (800 ° C, P _f= 1 kb). The reaction between the two feldspar phases could be reversed at 800 ° C. The following compositions are considered to represent equilibrium data at 800 ° C and P _t = 1 kb:

An 43 Ab 51 Or 6 coexisting with Or 79 Ab 20 An 1, and

An 40 Ab 54 Or 6 coexisting with Or 75 Ab 24 An 1.

Recent data obtained with gels of ternary feldspar composition as starting materials do not agree with the results presented in this paper. Gels obviously crystallize spontaneously forming coexisting feldspars of non - equilibrium composition - alkali feldspars too rich in Ab and plagioclases too rich in An.     

Enthalpies and Volumes Related to K--Na Mixing and Al-Si Order/Disorder in Alkali Feldspars

In order to investigate the thermodynamic properties of alkalifeldspars, three new feldspar ion-exchange series have beensynthesized, two based on monoclinic parent materials havingintermediate degrees of Al—Si order, the other on Amelialow albite. Acid solution calorimetric measurements have beencarried out in 20?1% HF at 50?C under isoperibolic conditionson 30 members of the three series, and compared with revisedvalues for a previously reported sanidine—analbite series.Molar volumes have been determined for all feldspars, and foran additional series based on Eifel sanidine. Enthalpies of K—Na mixing (A_ex) calculated from the 50?Cheats of solution are dependent on Al—Si distributionfor both topochemically monoclinic and triclinic alkali feldspars,and in general can be expressed as where N_Or and N_Ab are mole fractions of KAlSi₃O₈ and NaAlSi₃O₈,respectively, and Z is an ordering parameter defined as twicethe difference in the mole fraction of Al in the T1 vs the T2tetrahedral sites. A_ex values for all but the most disorderedseries are maximized toward sodic compositions, and increaseboth in magnitude and asymmetry as ordering increases. For topochemically monoclinic alkali feldspar series, volumesof K—Na mixing(V_ex) are asymmetric with N_Or, but withinthe precision of present data do not depend on Al—Si distribution: Microcline-low albite feldspars appear to have volumes of mixingwith the opposite asymmetry, but expressions of for these differ somewhat among various investigators. Since no single thermodynamic mixing property is markedly asymmetricwith respect to composition, the excess Gibbs energies impliedfrom solvus data for alkali feldspars, and maximized at sodiccompositions, are apparently the result of additive effectsof subtle asymmetries in the volumes, enthalpies, and entropiesof K—Na mixing in these minerals. The thermodynamic properties of an alkali feldspar at any compositionare significantly affected by the distribution of Al and Sibetween T1 and T2 tetrahedral sites. The enthalpy of formationat 50?C of a monoclinic potassium feldspar with perfect order(Z=1) differs by 2?19 kcal/mol from one with a completely randomAl—Si distribution (Z=0), while a value of 2?86 kcal/molapplies to analagous sodium end members. ConverselyY-ordering(between T1O andT1m sites) seems to have little or no effecton the enthalpy of formation of either end member, evidencedby the fact that most of the enthalpy differences for the lowmicrocline to sanidine and corresponding low albite to analbitetransitions (1?73 and 2?79 kcal/mol, respectively) can be attributedto Al—Si exchanges between T1 and T2 sites. Observed enthalpydifferences in alkali feldspars are probably related to strainat domain boundaries, whether the domains are extremely small,or somewhat larger as in modulated structures. Neither Z-nor Y-ordering has a substantial effect on the molarvolumes of alkali feldspars.     

Chemical composition of spinel from Uralian-Alaskan-type Mafic–Ultramafic complexes and its petrogenetic significance

Uralian-Alaskan-type mafic–ultramafic complexes are recognized as a distinct class of intrusions regarding lithologic assemblage, mineral chemistry and petrogenetic setting. In the present study, we discuss new data on the distribution of major elements in minerals of the spinel group in rocks from Uralian-Alaskan-type complexes in the Ural Mountains, Russia. Cr-rich spinel (Cr₂O₃ = 20–53 wt%) in dunite with interstitial clinopyroxene and in wehrlite cumulates indicate that it reacted with interstitial liquid resulting in the progressive substitution of Al₂O₂ and Cr₂O₃ by Fe₂O₃ and TiO₂. A distinct change in the spinel chemistry in dunite (Cr₂O₃ = 47–53 wt%), towards Al₂O₃- and Cr₂O₃-poor but Fe₂O₃-rich compositions monitors the onset of clinopyroxene fractionation in wehrlite (Cr₂O₃ = 15–35 wt%, Al₂O₃ = 1–8 wt%, Fe₂O₃ = 25–55 wt%). In more fractionated mafic rocks, the calculated initial composition of exsolved spinel traces the sustained crystallization of clinopyroxene by decreasing Cr₂O₃ and increasing FeO, Fe₂O₃ and fO₂. Finally, the initiation of feldspar crystallization buffers the Al₂O₃ content in most of the spinels in mafic rocks at very low Cr₂O₃ contents (<5 wt%). The fractionation path all along and the reaction with interstitial liquid are accompanied by increasing Fe₂O₃ contents in the spinel. This likely is caused by a significant increase in the oxygen fugacity, which suggests closed system fractionation processes. Spinel with Cr₂O₃ < 27 wt% is exsolved into a Fe₂O₃-rich and an Al₂O₃-rich phase forming a variety of textures. Remarkably, exsolved spinel in different lithologies from complexes 200 km apart follows one distinct solvus line defining a temperature of ca. 600°C. This indicates that the parental magmas were emplaced and eventually cooled at similar levels in the lithosphere, likely near the crust–mantle boundary. Eventually, these 600°C hot bodies were rapidly transported into colder regions of the upper crust during a regional tectonic event, probably during the major active phase of the Main Uralian Fault.     

Experimental constraints on the storage conditions of phonolites from the Kerguelen Archipelago

Phase relations of a phonolite (K1) and a tephri-phonolite (K2) from the Upper Miocene lavas in the Southeast Province of the Kerguelen Archipelago have been investigated in the P/T range 100–500 MPa and 700–900 °C at two fO₂ conditions (~ NNO and ~ NNO+2.3) to clarify the differentiation and pre-eruptive conditions of these magmas. Crystallization experiments were performed in cold seal pressure vessels (CSPV) and internally heated pressure vessels (IHPV) at various X_H2O, under reducing (log fO₂ ~ NNO) and oxidizing conditions (log fO₂ ~ NNO+2.3). Under reducing conditions, the resulting phase assemblage for K1 was: titanomagnetite, nepheline, alkali feldspar, clinopyroxene and biotite; under oxidizing conditions, the assemblage was: magnetite, plagioclase, alkali feldspar, nepheline, titanite (minerals given in the order of appearance with decreasing T at 200 MPa for 4 wt% water in the melt). It is emphasized that an effect of fO₂ on the phase stability of feldspars and feldspathoides was observed. Comparison of the natural and experimental phase assemblages shows that the pre-eruptive conditions for K1 must have been in the log fO₂ range NNO+1–NNO+2, at pressures above 200–250 MPa. Assuming a temperature of 800 °C, the water content of the melt is constrained to be between 4 and 6 wt% H₂O. The pre-eruptive fO₂ conditions for the less evolved sample K2 are more oxidizing with log fO₂ close to NNO+2.3. The experimental results show that the enrichment of alkalis in residual melts during differentiation of tephri-phonolites is enhanced at high fO₂.Editorial responsibility: J. Hoefs     

Experiments on the kinetics of partial melting of a leucogranite at 200 MPa H<Subscript>2</Subscript>O and 690–800°C: compositional variability of melts during the onset of H<Subscript>2</Subscript>O-saturated crustal anatexis

We have experimentally investigated the kinetics of melting of an aplitic leucogranite (quartz+sodic plagioclase of ≈Ab₉₀+K-feldspar+traces of biotite) at 690, 740, and 800°C, all at 200 MPa H₂O. Leucogranite cylinders, 3.5 mm in diameter and 7 mm in length, were run in the presence of excess H₂O using cold-seal pressure vessels for 11–2,925 h. At 690 and 740°C and any experimental time, and 800°C and short run times, silicate glass (melt at run conditions) occurs as interconnected films along most of the mineral boundaries and in fractures, with the predominant volume occurring along quartz/feldspars boundaries and quartz/plagioclase/K-feldspar triple junctions. Glass film thickness is roughly constant throughout a given experimental charge and increases with experimental temperature and run duration. The results indicate that H₂O-saturated partial melting of a quartzo-feldspathic protolith will produce an interconnected melt phase even at very low degrees (<5 vol%) of partial melting. Crystal grain boundaries are therefore completely occluded with melt films even at the lowest degrees of partial melting, resulting in a change in the mechanism of mass transport through the rock from advection of aqueous vapor to diffusion through silicate melt. At 690 and 740°C the compositions of glasses are homogeneous and (at both temperatures) close to, but not on, the H₂O-saturated 200 MPa haplogranite eutectic; glass compositions do not change with run duration. At 800°C glasses are heterogeneous and plot away from the minimum, although their molar ratios ASI (=mol Al₂O₃/CaO+Na₂O+K₂O) and Al/Na are constant throughout the entire charge at any experimental time. Glass compositions within individual 800°C experiments form linear trends in (wt%) normative quartz–albite–orthoclase space. The linear trends are oriented perpendicular to the 200 MPa H₂O haplogranite cotectic line, reflecting nearly constant albite/orthoclase ratio versus variable quartz/feldspar ratio, and have endpoints between the 800°C isotherms on the quartz and feldspar liquidus surfaces. With increasing experimental duration the trends migrate from the potassic side of the minimum toward the bulk rock composition located on the sodic side, due to more rapid (and complete) dissolution of K-feldspar relative to plagioclase. The results indicate that partial melting at or slightly above the solidus (690–740°C) is interface reaction-controlled, and produces disequilibrium melts of near-minimum composition that persist metastably for up to at least 3 months. Relict feldspars show no change in composition or texture, and equilibration between melt and feldspars might take from a few to tens of millions of years. Partial melting at temperatures well above the solidus (800°C) produces heterogeneous, disequilibrium liquids whose compositions are determined by the diffusive transport properties of the melt and local equilibrium with neighboring mineral phases. Feldspars recrystallize and change composition rapidly. Partial melting and equilibration between liquids and feldspars might take from a few to tens of years (H₂O-saturated conditions) at these temperatures well above the solidus.     

High pressure behaviour of lead feldspar (PbAl2Si2O8)

An in situ high pressure powder diffraction study, using high-brilliance synchrotron radiation, on lead feldspar (PbAl₂Si₂O₈) was performed. Two samples, with Q _od=0.68 and 0.76, were loaded in a diamond anvil cell and were compressed up to 11 GPa. Up to P=7.1 GPa the only phase present is lead feldspar. In the range 7.1–9.4 GPa sudden changes in the position of the reflections suggest the transformation of lead feldspar to a new phase (probably feldspar-like). The absence of split that would be compatible with triclinic symmetry rules out the monoclinic-triclinic transition, that was reported for the structurally similar strontium feldspar. At P>9.4 GPa some new extra reflections not indexable in the feldspar cell are present as well. During decompression the lead feldspar was the only phase present at P<6 GPa. Peak enlargement was observed with pressure, probably preliminary to amorphization. However almost complete amorphization was observed only after fortuitous shock compression at ∼18 GPa; the crystallinity was recovered at room pressure after decompression. The bulk modulus for lead feldspar was K=71.0(9) and 67.6(1.2) GPa for the two samples, in the range reported for feldspars. The cell parameters show a compression pattern which is similar to that observed in anorthite, with Δa/a ₀>Δc/c ₀>Δb/b ₀; comparison with the high temperature behaviour shows that for lead feldspar the strain tensor with pressure is more isotropic and the deformation along a is less prominent. A turnover in the behaviour of the β angle with pressure suggests a change in the compression behaviour at P∼2 GPa. Rietveld refinement of the Pb coordinates was performed in a series of spectra with pressure ranging from 0.6 to 6.5 GPa. The combined analysis of cell parameters and Pb coordinates with pressure showed that the compression of the structure is mainly achieved by an approach of Pb atoms along a *. Received: 21 July 1998 / Revised, accepted: 13 October 1998     

Aureoles of Pb(II)-enriched feldspar around monazite in paragneiss and anatectic pods of the Napier Complex,Enderby Land,East Antarctica: the roles of dissolution-reprecipitation and diffusion

Extraordinarily high Pb content in K-feldspar and plagioclase has been found contiguous to monazite in two occurrences in the ultrahigh-temperature Napier Complex of Antarctica. Monazite shows a variety of textures and compositions. In a garnet-sillimanite-orthopyroxene paragneiss at Mount Pardoe (Amundsen Bay), grains range 80–150 μm across and are anhedral; two grains are Th- and Si-dominant. In pods that crystallized from anatectic melts at 2500 Ma at Zircon Point, Casey Bay, monazite grains range 0.05 mm–1 cm in length and are highly variable in texture. The coarsest grains (>0.7 cm) are skeletal and euhedral, whereas the smallest grains are anhedral and associated with fine- to medium-grained quartz, K-feldspar, plagioclase, garnet, sillimanite and rutile in aggregates that form interstitial veinlets interpreted to be a second generation of anatexis during an event at 1100 Ma. The huttonite component (ThSiO₄) reaches 30 mole% in the cores of the coarsest skeletal grains, whereas other grains, particularly smaller ones, show complex and irregular zoning in Th and U. The latter zoning is attributed to dissolution-reprecipitation, which also resulted in complete Pb loss during the 1100 Ma event. In the paragneiss at Mount Pardoe, K-feldspar and myrmekitic plagioclase (An16) are found in a 70–80 μm band between monazite and orthopyroxene and contain up to 12.7 wt.% and 2.7 wt.% PbO, respectively, corresponding to 18.5% and 3.4% PbAl₂Si₂O₈ component, respectively. Cathodoluminescence of both feldspars increases with distance from a nearby monazite grain and is not correlated with Pb content. Incorporation of Pb in K-feldspar and plagioclase could be a result of diffusion, even though the monazite adjacent to feldspar apparently lost little Pb, i.e., Pb could have been transported by fluid from the Th-rich grains, which did lose Pb. In contrast to the paragneiss, cathodoluminescence correlates with Pb content of K-feldspar in aureoles surrounding skeletal monazite grains 0.7–1 cm across in anatectic pods at Zircon Point. Pb content of K-feldspar decreases monotonically to near detection limits within several millimetres of monazite grains; the greatest PbO concentration is attained in K-feldspar inliers and embayments in monazite, 8.8 wt.%, corresponding to 11.7% PbAl₂Si₂O₈ component. Fine-grained quartz in the K-feldspar suggests that the mechanism for Pb incorporation involved breakdown of feldspar: Pb²⁺ + 2(K,Na)AlSi₃O₈ → PbAl₂Si₂O₈ + 4SiO₂ + 2(K,Na)⁺ . The smooth decrease of Pb in the aureoles is not characteristic of dissolution-reprecipitation, which is characterized by abrupt changes of composition, and it seems more likely that Pb was incorporated in K-feldspar by diffusion at 1100 Ma. We suggest a model whereby fluid introduced during the 1100 Ma event flowed along grain boundaries and penetrated mineral grains. Temperatures were sufficiently high, i.e., 700°C, assuming burial in the mid-crust, for the fluid to induce localized melting of quartzofeldspathic matrix of the anatectic pods. Loss of radiogenic Pb was complete. Some penetration of K-feldspar by aqueous fluid is suggested by the presence of scattered galena specks and by rays of turbidity emanating from monazite. Aqueous fluid or water-rich granitic melt may have mediated the diffusion of Pb in feldspar, but it did not cause dissolution-reprecipitation. Although Pb was mobilized by aqueous fluid or water-rich granitic melt, it was not entirely flushed from the immediate vicinity of the monazite, but nearly half was incorporated in adjacent feldspar. Fluid activity that could cause Pb loss in monazite does not always leave an obvious trace, i.e., hydrous minerals, such as sericite, are very sparse, and biotite is absent in the anatectic pods at Zircon Point. Nonetheless, electron microprobe dating of monazite from the pods could not detect the 2500 Ma age of original crystallization determined by isotopic dating.     

The evolution of spinel lherzolite xenoliths and the nature of the mantle at Kilbourne Hole,New Mexico

In peridotites, olivine, clinopyroxene, and orthopyroxene are complex solid solutions with wide stability fields. Depending mostly on bulk composition and pressure, these minerals may be accompanied by plagioclase (low pressure), spinel (moderate pressure), or garnet (high pressure), resulting in 4-phase and rarer 5-phase assemblages. Although a particular mineral assemblage is stable over a range of P–T, the compositions of the individual minerals vary with changing P–T conditions. Application of standard geothermobarometers to olivine–clinopyroxene–orthopyroxene–spinel peridotites is problematic. An alternative approach is to use a bulk rock composition to calculate equilibrium phase diagrams to determine the conditions under which a particular assemblage is stable. This requires consideration of the 7-component system SiO₂–Al₂O₃–Cr₂O₃–FeO–MgO–CaO–Na₂O, internally consistent thermodynamic data for end members, and reliable mixing models for all mineral solutions. Experimental studies in simpler systems, and solution models from the literature, permit derivation of multicomponent thermodynamic mixing models for the key minerals. The models, when applied to xenoliths from Kilbourne Hole, constrain P and T of equilibration and are less sensitive to mineral compositional variations, or uncertainty in activity models, than standard thermobarometry. Our modeling provides the first tightly constrained pressure estimates for Kilbourne Hole, placing the xenoliths in the spinel stability field at depths (30–45 km) that correspond to the uppermost mantle beneath the Rio Grande Rift. The fine-grained equigranular lherzolite, porphyroclastic lherzolite, and some harzburgite-dunite specimens equilibrated at average conditions of 11.5 Kbar-930°C, 12 Kbar-990°C, and 13 Kbar-1,080°C, respectively. The mantle beneath the Rio Grande Rift is layered; the fine-grained equigranular lherzolite derives from relatively shallow depth (35 km average), and the porphyroclastic lherzolite from slightly deeper levels. Lying 5–10 km beneath both lherzolites, the harzburgite-dunite represents a depth where melt extraction has significantly altered mantle chemistry and where local thermodynamic equilibrium has not been maintained.     

Heat capacity and phase equilibria of hollandite polymorph of KAlSi3O8

The low-temperature heat capacity (C _p ) of KAlSi₃O₈ with a hollandite structure was measured over the range of 5–303 K with a physical properties measurement system. The standard entropy of KAlSi₃O₈ hollandite is 166.2±0.2 J mol⁻¹ K⁻¹, including an 18.7 J mol⁻¹ K⁻¹ contribution from the configurational entropy due to disorder of Al and Si in the octahedral sites. The entropy of K₂Si₄O₉ with a wadeite structure (Si-wadeite) was also estimated to facilitate calculation of phase equilibria in the system K₂O–Al₂O₃–SiO₂. The calculated phase equilibria obtained using Perple_x are in general agreement with experimental studies. Calculated phase relations in the system K₂O–Al₂O₃–SiO₂ confirm a substantial stability field for kyanite–stishovite/coesite–Si-wadeite intervening between KAlSi₃O₈ hollandite and sanidine. The upper stability of kyanite is bounded by the reaction kyanite (Al₂SiO₅) = corundum (Al₂O₃) + stishovite (SiO₂), which is located at 13–14 GPa for 1,100–1,400 K. The entropy and enthalpy of formation for K-cymrite (KAlSi₃O₈·H₂O) were modified to better fit global best-fit compilations of thermodynamic data and experimental studies. Thermodynamic calculations were undertaken on the reaction of K-cymrite to KAlSi₃O₈ hollandite + H₂O, which is located at 8.3–10.0 GPa for the temperature range 800–1,600 K, well inside the stability field of stishovite. The reaction of muscovite to KAlSi₃O₈ hollandite + corundum + H₂O is placed at 10.0–10.6 GPa for the temperature range 900–1,500 K, in reasonable agreement with some but not all experiments on this reaction.     

An investigation of Malaysian granitic rocks as suitable sources of feldspar

Medium- to coarse-grained leucocratic granitic bodies containing more than 60% feldspar and less than 10% mafic minerals are found to be appropriate and potential source materials of local feldspar. Out of the 72 granite quarries/outcrops studied in Peninsular Malaysia, 31 have been identified as “ideal” sources of feldspar conforming to the “preferred” feldspar specification of >18% Al₂O₃, >11% (Na₂O+K₂O) and <0.3% Fe₂O₃. A feldspar recovery efficiency exceeding 60% was achieved in this study. Despite the positive and encouraging indication that the extracted feldspar samples of different chemical composition are found to be suitable for the general purpose of making ceramic bodies and glaze, the chemical content of the feldspar, nevertheless, could be critical for the manufacture of specific end products. At 1250°C all extracted feldspar samples were fused; however, at the lower temperature of 1170°C feldspar samples extracted from some “Central Belt granites” remained unfused. The Eastern Province granites generally yielded feldspars which show better fusion characteristics i.e. (unblemished) than those extracted from the Main Range Province. A valuable by-product of the feldspar extraction process is silica sand.     

Thermodynamic analysis of Fe and Mg partitioning between plagioclase and silicate liquid

 Thermodynamic analysis of Fe- and Mg-bearing plagioclase and silicate liquid was carried out based on reported element partitioning data between plagioclase and silicate liquid in reduced conditions, solution properties of ternary feldspar, standard state properties of plagioclase endmembers and solution properties of multicomponent silicate liquid. Derived mixing properties of Fe- and Mg-bearing plagioclase are in harmony with estimated results from synthetic experiments in the systems CaAl₂Si₂O₈-CaFeSi₃O₈ and CaAl₂Si₂O₈-CaMgSi₃O₈. Based on the determined solution properties of the plagioclase, a computer program to calculate the element partition relationships between Fe- and Mg-bearing plagioclase and multicomponent silicate liquid was developed. The FeO, MgO and MgO/(MgO + FeO) in plagioclase predicted from known liquid compositions and pressure are in agreement with measurements within 0.2 wt%, 0.1 wt% and 0.1 (mol ratio), respectively. The Fe³⁺ content in plagioclase crystallized at high oxygen fugacity can be estimated with this program. The Fe³⁺/total Fe ratio in plagioclase crystallized near the quartz-fayalite-magnetite buffer ranges from 0 to 0.5, which is consistent with previous study on natural plagioclase in submarine basalt. Derived solution properties of the Fe- and Mg-bearing plagioclase are also used to calculate equilibrium composition relationship between olivine and plagioclase. Change of X _Fo in olivine coexisting with plagioclase affects MgO and FeO contents in plagioclase greatly. The present model predicts X _Fo of coexisting olivine from the chemical composition of plagioclase to ±0.1 accuracy at given pressure and temperature. Received: 27 March 1998 / Accepted: 30 September 1999     

Sodic(–calcic) alteration in Fe-oxide–Cu–Au districts: an origin via unmixing of magmatic H2O–CO2–NaCl ± CaCl2–KCl fluids

Iron-oxide–Cu–Au deposits, particularly those formed in deeper level (plutonic) environments, are commonly characterized by regional scale sodic(–calcic) alteration, which typically formed pre- or syn-Cu–Au mineralization. The sodic(–calcic) assemblages include albite, scapolite, pyroxene, actinolite, apatite, titanite, epidote and calcite. The consistent presence of coexisting hypersaline aqueous and CO₂-rich fluids in minerals from sodic(–calcic) alteration and associated Fe-oxide–Cu–Au deposits is the result of unmixing of H₂O–CO₂–NaCl ± CaCl₂–KCl magmatic fluids. Experimental evidence indicates that the Na/(Na + K) ratio of fluids in equilibrium with two alkali feldspars in CO₃ ²⁻-bearing parent fluids would be significantly higher than in unmixed chloride-bearing aqueous fluids. Therefore, fluid unmixing caused by decreases in temperature and/or pressure, will result in albitization of wall rocks, as is observed in most deeper level Fe-oxide–Cu–Au deposits. This alteration style may be succeeded by K-feldspathization with decreasing temperature because of the increase in equilibrium Na/(Na + K) in chloride-bearing fluids buffered by alkali feldspars. Received: 26 May 1999 / Accepted: 8 June 2000     

TEM study of a special grain boundary in a synthetic K-feldspar bicrystal: Manebach Twin

 A monoclinic KAlSi₃O₈ feldspar Manebach twin boundary was synthesized by diffusion bonding and examined using high-resolution transmission electron microscopy. The sharp (001) twin boundary is straight and free of strain. The boundary width is smaller than d₀₀₁. There is no rigid body shift observed at the twin boundary, and the feldspar structure is arranged symmetrically across (001). The twin boundary structure consists of bridged tetrahedral crankshafts, which are characteristic of the feldspar lattice. The grain boundary structure is in good agreement with the geometrical model of Taylor et al. (1934). The grain boundary composition of K_1/2H_1/2AlSi₃O₈ differs from their model. Received: 13 February 2002 / Accepted: 24 December 2002 Acknowledgements We thank M. Rühle, S. Hutt, J. Mayer, A. Strecker and U. Salzberger at MPI, Stuttgart, for their support and valuable advice in preparing TEM sections of bicrystals.     

Monte Carlo simulation of mixing in Ca3Fe2Ge3O12–Ca4Ge4O12 garnets and implications for the thermodynamic stability of pyrope–majorite solid solution

Static lattice energy calculations, based on empirical pair potentials, were performed for a large set of structures differing in the arrangement of octahedral cations within the garnet 2 × 2 × 2 supercell. The compositions of these structures varied between Ca₃Fe₂Ge₃O₁₂ and Ca₄Ge₄O₁₂. The energies were cluster expanded using pair and quaternary terms. The derived ordering constants were used to constrain Monte Carlo simulations of temperature-dependent mixing properties in the ranges of 1,073–3,673 K and 0–10 GPa. The free energies of mixing were calculated using the method of thermodynamic integration. The calculations predict a wide miscibility gap between Fe-rich (cubic) and Fe-pure (tetragonal) garnets consistent with recent experimental observations of Iezzi et al. (Phys Chem Miner 32:197–207, 2005). It is shown that the miscibility gap arises due to a very strong cation ordering at the Fe-pure composition, driven by the charge difference between Ca²⁺ and Ge⁴⁺ cations. The structural and thermodynamic analogies between Ca–Ge and Mg–Si systems suggest that a similar miscibility gap should exist between pyrope and Mg–Si-majorite.     

Models of corundum origin from alkali basaltic terrains: a reappraisal

Corundums from basalt fields, particularly in Australia and Asia, include a dominant blue-green-yellow zoned “magmatic” suite (BGY suite) and subsidiary vari-coloured “metamorphic” suites. The BGY corundums have distinctive trace element contents (up to 0.04 wt% Ga₂O₃ and low Cr/Ga and Ti/Ga ratios <1). Different melt origins for BGY corundums are considered here from their inclusion and intergrowth mineralogy, petrologic associations and tectonic setting. Analysed primary inclusion minerals (over 100 inclusions) cover typical feldspars, zircon and Nb-Ta oxides and also include hercynite-magnetite, gahnospinel, rutile-ilmenite solid solution, calcic plagioclase, Ni-rich pyrrhotite, thorite and low-Si and Fe-rich glassy inclusions. This widens a previous inclusion survey; New England, East Australia corundums contain the most diverse inclusion suite known from basalt fields (20 phases). Zircon inclusion, intergrowth and megacryst rare earth element data show similar patterns, except for Eu which shows variable depletion. Temperature estimates from magnetite exsolution, feldspar compositions and fluid inclusion homogenization suggest that some corundums crystallized between 685–900 °C. Overlap of inclusion Nb, Ta oxide compositions with new comparative data from niobium-yttrium-fluorine enriched granitic pegmatites favour a silicate melt origin for the corundums. The feasibility of crystallizing corundum from low-volume initial melting of amphibole-bearing mantle assemblages was tested using the MELTS program on amphibole-pyroxenite xenolith chemistry from basalts. Corundum appears in the calculations at 720–880 °C and 0.7–1.1 GPa with residual feldspathic assemblages that match mineral compositions found in corundums and their related xenoliths. A model that generates melts from amphibole-bearing lithospheric mantle during magmatic plume activity is proposed for BGY corundum formation. Received: 3 January 1997 / Accepted: 8 July 1998     

The Stability of Sodalite in a Synthetic Syenite plus Aqueous Chloride Fluid System

Natural feldspathoidal syenites may be approximated by assemblagescontaining some or all of the phases sodalite, nepheline, oneor two alkali feldspars, and aqueous chloride fluid in the systemNaAISi₃O₈-KAISi₃O₈-NaAISiO₄-KAISiO₄-NaCI-KCI-H₂O. The stabilityof sodalite in these assemblages was studied in the range 500–700°C and 600–2000 bars fluid pressure. Sodalite appears to be a stable phase on the vapor-saturatedliquidus in this system over a wide range of pressure. At or near the vapor-saturated liquidus minimum in this system,three distinct types of sodalite-bearing syenite can crystallize.Nepheline-sodalite-one alkali feldspar rocks, nepheline-sodalite-twoalkali feldspars rocks and sodalite-analcime-bearing rocks crystallizebelow 1600 bars, between 1600 and 2750 bars and above 2750 barsfluid pressure, respectively. The effects of closed-system cooling on the assemblage sodalite-nepheline-twoalkali feldspars-aqueous fluid are different and distinguishablefrom the effects of metasomatism. Closed-system cooling resultsin replacement of K-feldspar by albite, feldspathoids remainingnearly unchanged, while metasomatism generally results in sismultaneousenrichment or impoverishment in sodalite plus K-feldspar.     

The red luminescence emission of feldspar and its wavelength dependence on K, Na, Ca – composition

Summary ?Feldspar specimens covering the whole Or–Ab–An ternary have been investigated by cathodoluminescence (CL), photoluminescence (PL), radioluminescence (RL) and radiophosphorescence (RP) spectrometry. A red luminescence emission, which is commonly explained by Fe³⁺ lattice defects, is a characteristic feature of all the spectra. Different shifts of the peak-wavelength between ∼680–750 nm (1.82–1.65 eV) were observed with varying feldspar composition. Despite the dependence of the peak position on the Ca/Na ratio, initially described for CL in the 1970s, there is also a shift induced by changing NaK composition. The observed effects can be explained by known relations that the peak position of the red luminescence emission in feldspars can be affected both by the structural state of the feldspar and the site occupancy of the trivalent iron. In the case of alkali feldspars another factor may influence the peak-shift. The incorporation of the larger potassium ion causes non-linear variations of the cell dimensions and therefore Fe–O bond distance. The behaviour of the red peak-shift dependent on the feldspar composition is not equal for all types of luminescence investigated. This is most likely caused by the different luminescence excitation mechanism. Received December 3, 2001; revised version accepted March 25, 2002