On micas from magmatic and metamorphic rocks

Micas from magmatic and metamorphic rocks differ from one another in chemical composition and in trace element content. The chemical composition of micas is discussed in relation to their occurrence, paragenesis and sequence of crystallization. On the basis of previous studies of the relationship between the physical properties and the chemical composition of 34 chemically analysed micas, reliable physical methods have been established which permit identification of different mica varieties in the same rock. Structural formulae and trace element content of micas from basic and granitic rocks, as well as from skarns, schists, ortho- and paragneisses are discussed. The relationship between the components of the tetrahedral and octahedral layers and of the interlayer are illustrated as ratios. Poorly differentiated, hybrid and metasomatic rocks often contain more than one variety of mica. Some prophyritic basalts and lamprophyres contain an early phlogopite which is paragenetically related to pyroxene phenocrysts and late biotite which occurs in the groundmass and in the fractures as a result of the crystallization of residual magma. The biotitemuscovite assemblage was observed in granodiorites, quartz-monzonites, schists and gneisses. In the albite-K-feldspar granites, muscovite predominates and the biotite is usually altered. The chemical composition of micas from metamorphic rocks depends on the grade of metamorphism and on the nature of associated minerals. The biotite from paragneisses contains considerable quantities of octahedral alumina. Pre-metamorphic micas show variable deficiencies of the (OH, F) group. The micas are useful minerals in determining the degree of differentiation and subsequent alteration of igneous rocks. The present study was carried out on the basis of 34 recent complete chemical analyses andca 100 X-ray fluorescence analyses. Dedicated to Professor Dr.Carl W. Correns on the occasion of his 70th birthday.     

Zoning and recrystallization of phengitic micas: implications for metamorphic equilibration

White micas (phengites) in the metasediments of the Scottish Dalradian display a large range of compositions within single samples. The variations in the composition of these phengites are strongly controlled by their structural age, with early fabrics containing a paragonite-poor, celadonite-rich phengite whereas in later fabrics the micas are generally paragonite-rich and celadonite-poor. Retrograde phengite growth, identified using back scattered electron imaging, occurs as celadonite-rich rims on micas within all existing fabrics and appears to be preferentially developed along existing white mica-plagioclase grain boundaries. The presence of these chemically distinct phengite populations within single samples implies that chemical exchange between the individual micas was inefficient. It is proposed that diffusion-controlled exchange reactions in phengites have relatively high closure temperatures below which major element exchange is effectively impossible. This closed system behaviour of micas questions the ease with which phengites may equilibrate with other phases during prograde greenschist and lower amphibolite facies metamorphism. Many of the chemical variations preserved in phengites from such metamorphic rocks may reflect deformation/recrystallization controlled equilibria.     

Distribution of Al between coexisting micas in metamorphic rocks from the Central Alps

In 61 pairs of coexisting biotites and muscovites from the Central Alps total Al scatters considerably, but in both series a gradual increase is noticed with increasing metamorphic grade. The ratio Al _Mu ^tot /Al _Bi ^tot remains virtually constant (1.61 average for greenschist facies, 1.57 for amphibolite facies). Tetrahedral Al varies little in biotites and increases in muscovites-phengites with rising metamorphic grade; accordingly the ratio Al _Mu ^IV /Al _Bi ^IV increases slightly with grade. Far the best control of metamorphism is evidenced by octahedral Al. In the muscovite series, and still more pronounced in the biotite series, Al^VI increases with increasing metamorphic grade. Consequently 1 $$K_D = \frac{{Al_{Mu}^{VI} }}{{Al_{Bl}^{VI} }}$$ decreases from 14 to 3. A map (Fig. 6) representing the regional distribution of the K_D values locates a 100 km long and 23 km broad central zone with low K_D. The outline of this central core almost coincides with the isograds anorthite-diopside-calcite and labradorite-pyroxene-hornblende of the Tertiary regional metamorphism; with some deviations this core also agrees with the zone in which phenomena of partial anatexis are observed. The K_D values of micas from anateotic pegmatites agree with those of associated gneisses and schists. The study demonstrates that in the course of progressive regional metamorphism equilibrium has been approached to an unexpected extent and that the two micas coexisted in a strict sense.     

The petrological and geological significance of theb 0 values of potassic white micas in low-grade metamorphic rocks. An application to the Eastern Alps

Summary In the Eastern Alps theb ₀ values of potassic white micas of Hercynian low-grade schists differ sharply from those of Alpine isograde and isochemical rocks. These differences, which indicate variations in the phengite content present as solid solution in the white micas, are to be referred to differences in pressure. In this way it is possible to recognize, in the low-grade metamorphic rocks of different tectonic units of the Eastern Alps, the lowpressure character of the Hercynian metamorphism, and the higher-pressure character of the Alpidic thermic event; this recognition is not possible using traditional methods, owing to the lack of characteristic minerals in the lowgrade metamorphic rocks. The results of the present report allow us to state that generally, when studying low-grade metamorphic complexes, theb ₀ measurements can supply valuable data which are not obtainable in any other way at the present time. These data are useful both for estimating recrystallization pressure and for recognizing the age of metamorphism.

---

La signification pétrologique et géologique des valeurs b₀ des micas blancs potassiques dans les roches de faible metamorphisme

Résumé Dans les Alpes orientales les valeursb ₀ des micas blancs potassiques des schistes épimétamorphiques d'age hercynien diffèrent nettement de celles de roches isogrades et isochimiques d'age alpin. Ges différences, qui indiquent des variations de la quantité de phengite présente en solution solide dans les micas blancs, sont référables à différences de pression. Par cette méthode on a reconnu, dans les schistes épimétamorphiques appartenant à de différentes unités tectoniques des Alpes orientales, le caractère alpinotype du métamorphisme morphisme hercynien, et d'autre part le caractère alpinotype du métamorphisme alpin; cette distinction est impossible à faire à faire à l'aide des méthodes traditionelles, à cause de l'absence de minéraux caractéristiques dans les schistes épimétamorphiques. Les résultats de cette étude ont permis d'établir que, au cours de l'analyse des complexes épimétamorphiques, les mesures deb ₀ peuvent fournir des données précieuses qu'à présent il est impossible d'obtenir autrement. Ces recnées sont utiles soit pour évaluer la pression de recrystallisation, soit pour reconnaître l'age du métamorphisme.

---

---

With 2 Figures     

40Ar/39Ar dating of white micas from an Alpine high-pressure metamorphic belt on Naxos (Greece): the resetting of the argon isotopic system

Overprinting of white micas from high pressure, low to medium temperature (M ₁) metamorphic assemblages in pelitic schists on Naxos during subsequent thermal dome (M ₂) metamorphism ranges from minor in the southeast of the island to complete recrystallization in the amphibolite facies rocks near the migmatites in the centre of the dome. The original (M ₁) minerals are phengites (Si⁴⁺=6.7–7.0) and the overprinting minerals are muscovites (Si⁴⁺=6.0–6.45). ⁴⁰Ar/³⁹Ar step heating analyses of white mica separates from rocks in the area where phengite and muscovite occur together yield complex age spectra, characterized by low apparent ages in the first and the last stages of gas release and high apparent ages in between. These upward-convex age spectra are shown to be caused by mixing of two generations of micas, each of which has a different age spectrum and argon release pattern. Seemingly good plateaus in some age spectra from white micas of the area must be interpreted as providing meaningless intermediate ages. Further, the upward-convex age spectra have been used to trace the isotopic signature of phengites toward increasing M ₂ metamorphic grade, and suggest that as long as phengites can be observed in the rocks upward-convex age spectra occur. On Naxos, crystallization of muscovite at the expense of phengite appears to be the main mechanism of resetting argon isotopic ages in white micas. However, there is also good evidence for argon loss by volume diffusion from phengites. Simple diffusion calculations suggest that the M ₂ metamorphism was caused by a shortlived heat source.Now at Department of Geology, University of Alberta, Edmonton T6G 2E3, Canada     

云母的命名

根据容许的化学成分范围，给出了纯云母类（true micas)，脆云母类（brittle micas)和层间阳离子亏损的云母类（interlayer-cation-deficient micas)的端元矿物和矿物种，概括介绍了利用现有的各种化学分析数据计算云母晶体化学式的方法，以及描述不常见化学元素代换或多型堆积的一系列修饰词和后缀，列出了云母的同义词和变种、定名有误的物质，以及过去使用或误用的云母名称。     

Non-stoichiometry of interlayer cations in micas from low- to middle-grade metamorphic rocks in the Ryoke and the Sanbagawa belts,Japan

Micas in 17 pelitic (K-feldspar-free) and 8 psammitic (K-feldspar-bearing) rocks from the Wazuka and the Asemi-gawa areas in the Ryoke and the Sanbagawa metamorphic terrains, respectively, were analyzed on an electron-probe microanalyzer. The deficiency of alkali cations in the low- to middle-grade metamorphic micas is ascribed to the illite substitution, K^XII+Al^IV=^XII (vacancy)+Si^IV.At the same metamorphic grade, the deficiency of interlayer cations in micas from the pelitic rocks is greater than that from the psammitic rocks. However, it decreases with rising temperature in both rock-types, irrespective of the pressure of metamorphism.K-feldspar and biotite buffer the illite substitution. Two reactions are proposed to explain the decrease of the alkali-cation deficiency in both muscovite and biotite.     

The b 0 value of the potassic white micas as a barometric indicator in low-grade metamorphism of pelitic schists

The b ₀ of the potassic white micas was measured in 410 samples of low-grade pelitic schists from the Central Pyrenees, the Abukuma belt, Northern New Hampshire, the Eastern Alps, Otago, the Sanbagawa belt and the Central Pontic Chain. Temperature and rock bulk composition can be considered substantially constant all over the sample range, so that the differences in the b ₀ values depend primarily on differences in pressure. The analytical data demonstrate that the b ₀ increases for increasing pressure, and that it is practically identical in the micas from very different regions belonging to the same baric type of metamorphism. With the help of other analytical data (about 600), a b ₀ scale was prepared, which makes the distinction of six different facies series possible. The writers, proposing this very rapid new method of barometric analysis, draw attention to its limitations and point out the main fields of its application.     

A K-Ar and 40Ar/39Ar study on white micas from the Brixen Quartzphyllite,Southern Alps

The Brixen Quartzphyllite, basement of the Southern Alps (Italy), consists of metasediments which had suffered progressive deformation and low grade metamorphism (p _max4 kbar, T _max375±25° C) during the Palaeozoic. It has been excavated by pre-Permian erosion, buried again beneath a pile of Permo-mesozoic to Cainozoic sediments (estimated T _max150° C), and is now exposed anew due to late Alpine uplift and erosion. The behavior of the K-Ar system of white micas is investigated, taking advantage of the narrow constraints on their thermal history imposed by the geological/stratigraphic reference systems.The six structurally and petrographically differing samples come from a single outcrop, whose position is roughly two kilometers beneath the Permian land-surface. White mica concentrates from five grain size fractions (<2 , 2–6 , 6–20 , 20–60 , 60–75 ) of each sample have been analyzed by the conventional K-Ar method, four selected concentrates additionally by the ⁴⁰Ar/³⁹Ar stepwise heating technique; furthermore, Ar content and isotopic composition of vein quartz were determined.The conventional ages of the natural grain size fractions (20–60 , 60–75) are in the range 316±8 Ma, which corresponds to the ⁴⁰Ar/³⁹Ar plateau age of 319.0±5.5 Ma within the error limits. The finer grain size fractions yield significantly lower ages, down to 233 Ma for fractions <2 . Likewise low apparent ages (down to 83 Ma) are obtained for the low temperature ⁴⁰Ar/³⁹Ar degassing steps.There is no correlation between microstructural generation of white mica prevailing in the sample and apparent age. This favours an interpretation of the 316±8 Ma values as cooling age; progressive deformation and metamorphism must be respectively older and their timing cannot be resolved by these methods. The data preclude any significant influence of a detrital mica component as well as of excess argon.The lower ages found for the fine grain-size fractions (respectively the low-T degassing steps) correspond to a near-surface period (p-T-minimum); the values are geologically meaningless. The effect is interpreted to result from partial Ar loss due to reheating during Mesozoic-Cainozoic reburial. A model based on diffusion parameters derived from the outgassing experiments and Dodson's (1979) equation yields a closure temperature of 284±40 °C for a cooling rate of 18° C/Ma. Furthermore, this model suggests that the observed argon loss of up to 5% may in fact have been induced by reheating to 150 °C for 50 Ma.     

Chemistry of micas from kimberlites and xenoliths—II. Primary- and secondary-textured micas from peridotite xenoliths

Micas from coarse granular Iherzolites in S. African kimberlites may be separated into two groups; those showing primary textural relationships with coexisting silicates and those with secondary, alteration relationships with other silicates. Primary-textured micas form a tight cluster with a mean composition from 10 coarse garnet lherzolites of: SiO₂ 41.0, TiO₂ 0.18, Al₂O₃ 13.5, Cr₂O₃ 0.82, total Fe as FeO 2.60, MnO 0.02, MgO 26.0, NiO 0.22, CaO 0.01, BaO 0.29, Na₂O 0.31, K₂O 10.0, Rb₂O 0.028, Cl 0.08, F 0.43 wt%. Primary-textured micas in aggregates with clinopyroxene have higher TiO₂ and four specimens which look similar to the primary group but have textural ambiguities have still higher TiO₂Micas with secondary textures have wide ranges of composition which may be correlated with details of the textural parageneses. Micas from kelyphitic rims around garnets tend to be Cr-rich while those from veinlets are Cr-poor. Both groups tend to have higher FeO and TiO₂ than the primary group. Micas produced by alteration of, or filling veinlets through, orthopyroxene have a wide compositional range which overlaps that of the primary-textured micas, especially for harzburgite specimens.The primary-textured micas show a positive correlation with coexisting pyroxenes for MgO/(MgO + FeO) and TiO₂, but not for Cr₂O₃. Secondary-textured micas do not show correlations with coexisting pyroxenes for any elements.The ‘primary-metasomatic’ micas described by Harte and Gurney (1975) and metasomatic and other micas described by Boettcher et al. (1979) and Boettcher and O'neil (1979) are richer in FeO and TiO₂ than the present primary-textured micas, and are attributed to crystallization from fractionated fluids.     

A thermodynamic model for Fe–Mg dioctahedral K white micas using data from phase-equilibrium experiments and natural pelitic assemblages

The purpose of this study is to derive a solid-solution model for potassic white micas (KWM) encountered in rocks of various bulk compositions, over a wide range of P-T conditions. A compilation of phengite compositions lead us to propose a seven-thermodynamic-component (muscovite, Fe²⁺-Al-celadonite, Mg-Al-celadonite, annite, phlogopite, pyrophyllite and paragonite) ionic solid-solution model which accounts for the Tschermak, Fe-Mg, di/trioctahedral, pyrophyllitic and paragonitic substitutions observed in nature. A four-site mixing model with symmetric Margules parameters to model the Tschermak substitutions, asymmetric Margules parameters to model the other substitutions, and ideal intersite interaction has been adopted. In contrast to previous models, the relevant thermodynamic data and solid-solution properties are calibrated with independent sets of published experiments conducted for the KMASH, KFASH, KFMASH, and KNASH systems, as well as about 200 natural data involving KWM assemblages. The constraints span a wide range of pressure and temperature conditions (150 to 750 °C, 0.5 to 30 kbar), so that our model does not need to be extrapolated outside the calibration range to be used for P-T thermobarometric purposes. The calculated thermodynamic data are interconsistent with the TWQ thermodynamic database and solid-solution models, including that recently published for chlorites.     

Thermal expansion and dehydroxylation of phengite micas

Phengite samples (2M ₁ and 3T politypes) and a synthetic end-member muscovite specimen were studied by in situ high-temperature synchrotron radiation X-ray diffraction. The measured volume thermal expansion of 2M ₁ phengite (<α _V> ≈ 36.6 × 10⁻⁶ K⁻¹) was systematically greater than <α _V> of the 3T polytype (≈33.3 × 10⁻⁶ K⁻¹). A positive linear correlation between the average thermal expansion on (001) plane and the mean tetrahedral rotation angle at ambient condition is proposed on the ground of new measurements and literature data. Dehydroxylation processes were observed in 2M ₁, starting at 1,000 K in 3T at 800 and 945 K in synthetic muscovite. Rietveld refinements allowed a determination of structural variations upon heating of phengite samples and their dehydroxylate phases. The phengite structure expands by regularizing the tetrahedral sheet and by reducing the bond length differences between the outer and inner coordination shell of the interlayer site. The dehydroxylate phase derived from 2M ₁ is characterized by fivefold polyhedra in the low temperature form as a consequence of two OH groups reacting to form H₂O + O (residual). The dehydroxylate exhibits an increase of the cation–cation distances along the M–Or–M bonds with respect to low-temperature phengite structures. For the 3T phase, we were unable to achieve completion of dehydroxylation. The refined structural model of the dehydroxylate phase shows two hydroxyl sites, but at a short distance from one another. This result suggests that the dehydroxylation reaction did not proceed to completion. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

K-Ar dating of white micas from the Ventersdorp Contact Reef of the Witwatersrand Basin, South Africa: timing of post-depositional alteration

Summary White micas from metamorphosed and hydrothermally-altered basaltic lavas, conglomerates, quartzites and shales in and around the Ventersdorp Contact Reef of the Witwatersrand Basin, South Africa, were dated by the K-Ar method to constrain post-depositional thermal and mineralization processes. The minerals were separated into various grain sizes between < 0.4 and 10m, and characterized in terms of composition, paragenetic sequence and texture, by XRD, SEM and TEM techniques. The K-Ar isochron of all white micas in the basaltic lavas suggests an age of 1994 ± 60 Ma, and that of the smaller mica particles (< 2m) in the quartzites defines a younger age of 1917 ± 66 Ma. This range is considered to reflect the timing of long-lived hydrothermal alteration in the Ventersdorp Contact Reef. The older age is slightly younger than the intrusion of the Bushveld Complex (2060–2054 Ma) and the Vredefort catastrophism (2020 Ma), which are well-documented events that were superimposed onto the Witwatersrand Basin. The younger age may be associated with the Eburnian orogenesis along the western edge of the Kaapvaal Craton resulting in continental-scale fluid migration and hydrothermal activity that extended throughout the Griqualand Basin and even into the Witwatersrand Basin. The K-Ar ages obtained here for the white mica fractions of the Ventersdorp Contact Reef in the Witwatersrand Basin confirm that the period between 2.0 and 1.9 Ga was significant, as far as alteration, and possibly also gold mobilization, was concerned.

---

K-Ar Datierung von Hellglimmern aus dem hentersdorp Contact Reef des Witwatersrand Beckens, Südafrika: die zeitliche Eingrenzung der nach der Sedimentablagerung erfolgten Alteration

Zusammenfassung Hellglimmer von metamorph und hydrothermal überprägtem Basalt, Konglomerat, Quarzit und Pelit aus dem Ventersdorp Contact Reef im Witwatersrand Becken, Südafrika, wurden mittels der K-Ar Methode datiert, um das Alter der postsedimentären thermischen Überprägung einzugrenzen. Mineralkörner wurden in einzelne Fraktionen zwischen < 0.4 und 10m separiert und auf deren Zusammensetzung, Paragenese und Textur mittels Röntgendiffraktometrie und Elektronenmikroskopie untersucht. Das Isochronenalter für alle Hellglimmerproben aus dem Metabasalt liegt bei 1994 ± 60 Ma, jenes für die Glimmer mit einer Korngröße < 2m im Quarzit bei 1917 ± 66 Ma. Diese Altersspanne wird als Ausdruck einer lang anhaltenden hydrothermalen Veränderung des Ventersdorp Contact Reef interpretiert. Das ältere Alter ist etwas jünger als die Intrusion des Bushveld Komplex (2060–2054 Ma) und die Vredefort Katastrophe (2020 Ma) - zwei gut dokumentierte Ereignisse, die das Witwatersrand Becken erfaßten. Das jüngere Alter könnte mit der eburnischen Orogenese entlang des Westrandes des Kaapvaal Kratons in Zusammenhang stehen, während der es zu Fluid Migration und hydrothermaler Aktivität quer über den Kontinent vom Griqualand Becken bis in das Witwatersrand Becken kam. Die neuen K-Ar Alter bestätigen somit, daß die Zeitspanne von 2.0–1.9 Ga wesentlich für die Alteration und möglicherweise auch für die Mobilisierung von Gold im Witwatersrand Becken war.

     

40Ar-39Ar dating of high pressure metamorphic micas from the Gran Paradiso area (Western Alps): Evidence against the blocking temperature concept

The⁴⁰Ar-³⁹Ar method has been applied to high pressure (HP) white micas from the Gran Paradiso crystalline massif and from the overthrust Schistes Lustrés of its western slope. Preliminary petrographic and microanalytical investigation of the phengite micas showed that their celadonite-content decreases with time (from Si_3.65 to Si_3.05), and that less foliated samples are the most suitable for the metastable persistence of the high celadonite-content of the early HP stage during subsequent metamorphic evolution.Such samples were investigated together with one where mica is a pure retrogressive product. Two groups of plateau-ages have been found: (a) 60 to 75 Ma on HP phengites and early paragonites of unretrograded HP parageneses, thus dating the early HP metamorphic stage; (b) 38–40 Ma on HP phengites (most often in slightly retrograded HP parageneses) and on the purely retrogressive mica. For the HP phengites in (b), this age is considered to reflect the end of Ar readjustement during the later lowerP and/or higherT metamorphic stage, and not their crystallization.This disparity in plateau-ages for micas sampled within the same area shows that under the sameP-T conditions some systems were open while others remained closed. This can be closely related to the mineralogical behaviour: chemically active systems are isotopically active, whereby the reverse is not necessarily true. Thus, although temperature exceeded by far the usually assumed sealing-temperature of white micas, many systems have remained unaffected during the late Eocene event. Therefore, temperature cannot be the determining parameter for the opening of a system. Chemical reactivity, starting mineralogy and, primarily, pervasive deformation and the related fluid behaviour appear to be the effective controls.This implies that thermally activated diffusion processes (volume diffusion...) cannot be geologically significant. Consequently, the blocking temperature concept which rests on the opposite assumption now appears questionable. The fact that a mica does not necessarily behave as open above its blocking temperature necessitates at least a clear distinction between opening- and sealing-temperatures.     

Dehydration and diffusion of radiogenic argon in micas

There is a close analogy between dehydration and loss of argon curves obtained by laboratory heating of muscovite (figs. 2 and 3). Potassium atoms lie in potential cleavage planes of the muscovite. When K⁴⁰ atoms disintegrate the resulting argon atoms are driven into the mica structure by recoil, except those whose paths make a small angle with the cleavage plane. These remain in the "unstable zone" and may escape from the muscovite. This introduces an element of uncertainty in K/A absolute age figures from mica. -- F. E. Ingerson.     

Structures of micas synthesized at high pressures and temperatures

Thermal karst, exposed in mine shafts, has been significantly developed in the commercial stratum of oil shales. Geochemical investigations in this karst have for the first time established the secondary changes in the kerogen of the oil shales, namely, an anomalous content of bituminoid A + C, the presence of processes of aromatization, the significant amount of hydrocarbon compounds and humic acids, and changes in the elemental composition of the residual organic matter (in particular, an increase in the C/H ratio). The secondary changes suggest that a favorable geochemical and thermobaric environment existed in the thermal karst for intense bitumen formation. The results obtained are of interest in the study of the kerogen of oil shales as a possible parental source for oil and gas. —Authors.     

Lithium in the interlayer space of synthetic trioctahedral micas

This paper gives several new and strong arguments in favour of the possibility of fixation of anhydrous lithium in the interlayer space of trioctahedral potassium micas. From the chemical viewpoint Li⁺ can replace K⁺, but is located out of the alkaline cation site; it enters pseudo-octahedral cavities limited by the triangular bases of two aluminous tetrahedra of two consecutive sheets. The solubility limit of Li⁺ in the interlayer is a function of the Al^IV content of the mica. It is given by the relation (Li/Li + K)_max = 2[(Al/Si + Al)^IV]². In both micas investigated — phlogopite, KMg₃(Si₃Al)O₁₀(OH)₂, and eastonite, K(Mg_2.5Al_1.5)(Si_2.5Al_1.5)O₁₀(OH)₂ — there is a remarkable agreement between the calculated values of the solubility limits and those measured by exchange reactions with hydrothermal solutions, at 600°C, 2 kbar. In high-Al micas, the interlayer Li content can be very important, with about one-third of K⁺ replaced by Li⁺.

The fixation of Li⁺ according to this model provokes a strong flattening of the interlayer (strong decrease of the reticular distance d₀₀₅) and a slight increase of the reticular distance d₀₆₀. Infra-red (IR) absorption spectrometry shows that vacant K⁺ sites are created when Li⁺ enters the interlayer; one observes low-frequency OH stretching bands attributed to OH dipoles lying towards these empty sites. Fixation of Li⁺ does not provoke any modification of the IR spectra in the region 1200-300 cm⁻¹, indicating that Li⁺ is really out of the sheet. For both cell dimensions and IR spectra, a comparison is made with “ordinary” lepidolites, having Li⁺ in the octahedral sheet; it provides a guide for the distinction between the two species of Li-bearing micas.     

Volatile contents of phlogopite micas from South African kimberlite

Phlogopite micas from nodules in South African kimberlites were analyzed for major elements with the electron microprobe and for volatile contents by high temperature mass spectrometry. The micas are from primary- (deformed) and secondary- (undeformed) textured grains in perodotite xenoliths, glimmerites, MARID (mica-amphibole-rutile-ilmenite-diopside) suite nodules and a mica megacryst. The major element and volatile contents of micas exhibiting these modes of occurrence overlap to a greater extent than indicated in previous studies. Concentrations of volatile species occupying structurally defined crystallographic sites (H₂O, F, Cl) are greater for many of the micas than predicted on the basis of the mica formula, particularly for the glimmerite and MARID suite samples. A correlation exists between micas with tetrahedral and octahedral cation deficiencies and those with excess H₂O, F and Cl. Substitution of H⁺ for tetrahedral and possibly octahedral cations may be responsible for the excess H₂O in these micas. Except for one sample, the major element and volatile data for the peridotite, glimmerite and MARID suite micas indicate that they crystallized at oxygen fugacities below the quartz-fayalite-magnetite buffer. F and K₂O are in the correct proportion in the micas to provide the source for these elements in alkali basalts, but not in mid-ocean ridge basalts. Kaersutite amphibole is a more likely source of potassium and fluorine in mid-ocean ridge basalts.