Mixed valence of iron in minerals with cation clusters

The valence and distribution of iron in vivianite, lazulite, babingtonite, rockbridgeite, acmite, aegirine-augite, hedenbergite, and ilvaite were studied with optical and Mössbauer spectroscopy. Optically activated intervalence charge transfer between Fe²⁺ and Fe³⁺ in neighboring sites through common edges or faces is observed in all these minerals irrespective of the polymerization of the iron-oxygen polyhedra ranging from finite clusters to infinite structural units. However, a distinct decrease occurs in the energy of the corresponding optical absorption band with increasing number of Fe²⁺ and Fe³⁺ ions involved in the charge transfer process. Thermally activated electron delocalization between Fe²⁺ and Fe³⁺ occurs only if Fe²⁺ and Fe³⁺ occupy crystallographically equivalent or geometrically very similar neighboring sites which share common edges to form extended structural units such as the ribbon in ilvaite. If the Fe-O polyhedra form finite clusters of two, three, or four polyhedra (e.g., in vivianite, lazulite, and babingtonite, respectively) no thermally-activated mixed-valence states of iron are observed. In aegirine, extended regions of the M1 chain are statistically occupied by Fe²⁺ and Fe³⁺ giving rise to thermally-activated electron delocalization in addition to the intervalence band in the optical absorption spectrum. The intensity of the optical intervalence absorption has been measured in a number of systems: ? values range from 60 to 210.     

Titanian chondrodite and clinohumite in marbles from the Ötztal crystalline basement

Summary Marble lenses within the polymetamorphic Ötztal crystalline complex frequently contain pockets of clinohumite and chondrodite and their titanium-rich varieties. Chondrodites contain up to 9.1 wt% TiO₂ and clinohumites about half that amount. The maximum amounts of Ti in both minerals do not exeed values of 0.4 in the formula. XTi and X_F are correlated by a slope of –1, indicating the efficiency of the TiO₂Mg_–1F_–2 substitution at constant OH (Evans andTrommsdorff, 1983). Clinohumites sometimes contain lamellae which have nonstoichiometric cation ratios reflecting a composition between clinohumite and olivine. In many cases Ti-rich clinohumites and chondrodites coexist with Mg-ilmenite. Ti-rich clinohumites and chondrodites often break down to a symplectite of Ti-poor clinohumite (or olivine) and Mg-ilmenite. Parts of the marbles, which are barren of Mg-ilmenite contain F-rich clinohumites. The latter do not show any signs of breakdown features. We conclude therefore that fluorine stabilizes the humite group minerals to a wide range of metamorphic conditions. Ti-rich humite-group minerals are not stable till amphibolite facies conditions, and below F-rich humite-group minerals and olivine are the more stable phases in a H₂O-rich, SiO₂-poor carbonate system.

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Titanreiche Chondrodite und Klinohumite in Marmoren des Ötztalkristallins.

Zusammenfassung In Marmorlinsen des polymetamorphen Ötztalkristaliins kommen häufig titanarme und titanreiche Clinohumite und Chondrodite vor. Die höchsten Titan-Gehalte in Chondrodit betragen 9.1 Gew.-% TiO₂ während Clinohumite nur etwa die Hälfte dieses Wertes enthalten. Dies entspricht einem Maximalgehalt an Titan von 0.4 in den Formeln von Chondrodit und Clinohumit. Eine negative Korrelation zwischen X_Ti, und X_F mit der Steigung von –1 bestätigt die Wirksamkeit der Substitution TiO₂Mg_–1F_–2 bei konstantem OH (Evans undTrommsdorff, 1983). In Clinohumiten konnten nichtstöchiometrische Lamellen nachgewiesen werden, die chemisch zwischen Clinohumit und Olivin zusammengesetzt sind. Ti-reiche Clinohumite und Chondrodite koexistieren immer mit Mg-Ilmenit und wandeln sich häufig an ihren Rändern in einen Symplektit von Ti-ärmerem Clinohumit oder Olivin und Mg-Ilmenit um. In den Mg-Ilmenit freien Bereichen der Marmore kommen stets Ti-arme aber F-reiche Clinohumite vor, die niemals randliche Umwandlungserscheinungen zeigen. Die grobkörnigen (mm-großen) Humitminerale werden der variszischen Metamorphose in Amphibolitfazies zugeschrieben, während die Symplektite als Produkte der eoalpinen grünschieferfaziellen Überprägung angesehen werden. Wir schließen daraus, daß die Humitminerale durch Fluor in einem großen Bereich metamorpher Bedingungen stabilisiert werden, während Ti-reiche Humitminerale bei Bedingungen der Grünschieferfazies instabil werden und F-reiche Humitminerale und Olivin die stabilen Phasen in einem H₂O-reichen, SiO₂-armen Karbonatsystem sind.

     

Polymetamorphose und Deckenbau der Strand-Halbinsel/SW-Norwegen

Zusammenfassung Die Metamorphite der Halbinsel Strand / SW-Norwegen gehören zu einem Deckensystem präkambrischer Gesteine, das während der kaledonischen Orogenese von NNW her auf den Baltischen Schild geschoben worden ist (Sigmond Kildal 1978). Eine hangende Deckeneinheit umfa\t Metagranite, Melagabbroide und Gneise. Ihr granulitfazieller Mineralbestand (Metamorphosealter 1,5 Milliarden Jahre) wurde wahrscheinlich vor 1,18 Milliarden Jahren grünschieferfaziell retrograd überprägt. Die Decke ist nur noch in kleinen Erosionsinseln vorhanden. Eine liegende Dekkeneinheit besteht aus metasedimentären Gesteinen. Sie weist Mineralbestände der höheren Amphibolitfazies auf, die ebenfalls grünschieferfaziell überprägt wurden. Die Al^VI-Gehalte der bei beiden metamorphen Prozessen gebildeten Amphibole deuten bei Anwendung eines Diagramms vonRaase (1974) an, da\ die retrograde Metamorphose hier bei höheren Drücken ablief als die ältere Metamorphose. Ein Gesamtgesteinsalter von 1,16 Milliarden Jahren scheint für diese grünschieferfazielle Metamorphose das gleiche orogene Ereignis anzuzeigen wie für die hangende Einheit. Produkt der schwachen kaledonischen Metamorphose (400 Millionen Jahre) ist Stilpnomelan, der auch im Grundgebirge des Baltischen Schildes auftritt.

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The Strand Peninsula, Stavanger district, Southwestern Norway, has become well known, when V. M.Goldschmidt (1920) published his hypothesis of regional metasomatism. All rocks of the Strand area were assumed to be situated in autochthonous position. The main point ofGoldschmidt's hypothesis was progarde metamorphism of argillaceous sediments and their transformation to albite schists and plagioclase gneisses by metasomatic solutions given off from intruded trondhjemitic magmas.However, in contrast toGoldschmidt's ideas, the granitoid sill of the Ormakam-Moldhesten area, Strand Peninsula, and its wall rocks, which played an important role inGoldschmidt's discussion, are now found to be parts of a polymetamorphous thrust unit.Granulite facies assemblages, mainly consisting of orthopyroxene +clinopyroxene+plagioclase+hastingsite±orthoclase and quartz, have been partially replaced by lowgrade assemblages. Probably, the high-grade metamorphism has an age of about 1.5 Ga (Andresen &Heier 1975) whereas the age of the greenschist facies event may be conform to an orogenic cycle at about 1.15 Ga (Sigmond Kildal 1978).A lower nappe, covering the Strand Peninsula for its most parts, was subject of a petrologic re-examination using the microscope and the microprobe analyser. Its contacts with the hanging nappe as well as those with the underlying gneissic basement are characterized by thrust planes and horizons of phyllonites and cataclasites inside of the nappe and by local brecciation in the uppermost zones of the basement.The rocks of the lower nappe have been formed a long with the upper amphibolite facies as indicated by the following mineral assemblage: andesine + hastingsite and Mg-hornblende + quartz +biotite.Obviously, an inverse order of temperature regimes is recognizable in the allochthonous units. Maximum temperature of the upper nappe reached 800C (Müller &Herbert 1984) whereas T_max of the lower nappe did not exceed 750C.Using a diagram ofRaase (1974) the Al^VI-contents of the primary hastingsitic hornblendes of the lower nappe rocks indicate pressures which range distinctly below 5 kbars, whereas the secondary pargasitic hornblendes were formed at pressures of about 5 kbars. Probably the thrusting happened before the formation of secondary hornblendes took place. The load pressure in the lower nappe (< 5 kbars) was distinctly increased when the upper nappe was thrusted upon the lower one. Consequently the Al^VI-contents of secondary hornblendes indicate increased pressure ( 5 kbars).In the gneisses of the lower nappe late fractures were filled by stilpnomelane, chlorite and quartz. Very probably this depends on thrust movements during the Caledonian orogeny.Verschure et al. (1980) found a similar stilpnomelane formation in adjacent terrains of the basement and proposed a weak Caledonian metamorphism of about 400 my.

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Résumé Les roches métamorphiques de la presqu'Île de Strand (sud-ouest de la Norvège) appartiennent à un empilement de nappes formées de roches pré-cambriennes et charriées vers le SSE sur le bouclier baltique au cours de l'orogenèse calédonienne (Sigmond Kildal 1978).Une nappe supérieure comprend des métagranites, des mélagabbroÏdes et des gneiss. Leurs paragenèses, du facies des granulites (âge du métamorphisme: 1,5 Ga) ont été rétromorphosées dans le facies des schistes verts il y a probablement 1,18 Ga. Cette nappe ne subsiste qu'en petits fragments épargnés par l'érosion.Une nappe inférieure est composée de roches métasédimentaires. Ces roches présentent des paragenèses du faciès supérieur des amphibolites, également rétromorphosées dans le facies des schistes verts. L'application du diagramme de Raase (1974) aux teneurs en Al^VI des amphiboles formées lors des deux processus métamorphiques indique que la rétromorphose s'est déroulée à une pression supérieure à celle du métamorphisme ancien. Un âge de 1,16 Ga sur roche totale semble indiquer que le mÊme processus orogénique a servi de cadre à la rétromorphose en facies des schistes verts dans les deux nappes.Du stilpnomélane, présent tant dans la nappe inférieure que dans le bouclier baltique autochtone, témoigne d'un métamorphisme calédonien (400 Ma) de faible degré.

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Strand ( ) , NNW (Sigmond KILDAL, 1978). , . - 1,5 , 118 , . . . , . Al^VI , , RAASE (1974) , , . 1,6 , , , . (400 ) , .

     

Polymetamorphic relations in iron ores from the Iron Quadrangle,Brazil: The correlation of oxygen isotope variations with deformation history

This study deals with the oxygen isotope composition of hematite-rich ore bodies in the Iron Quadrangle, Brazil. The area studied can be divided into two different regions: a western (W) zone of greenschist facies assemblages and an eastern (E) zone of amphibolite facies with transitions into granulite facies assemblages.The ¹⁸O values of 136 quartz-iron oxide pairs have been determined and temperatures of formation have been calculated. The ¹⁸O values of quartz vary between +6 and 20 except one value near +23, whereas the iron oxides fall between –4 and +10, with nearly 80% of the iron oxide values between –0.5 and 4.0. The regional distribution of the ¹⁸O values is as follows: in the W-region 85% of the quartz are >12, whereas in the E-region only 46% fall in this range, In contrast to quartz the iron oxides do not show any regional differences.The variation of oxygen isotope fractionations between quartz and iron oxides is obviously related to the complex deformation history of the iron ores. Samples with a primary schistosity (S₁) only represent peak metamorphic conditions. In the E-region the (S₁) high temperatures >700° C seem to correspond to orogenic events in the Archaen basement 2,700 m.y. ago. In the W-region S₁-temperatures between 460° and 560° C seem to represent peak metamorphic conditions of the Proterozoic Minas metamorphism 2,000 m.y. ago. Iron ores which have been overprinted by later deformation events are selectively reset to lower isotopic temperatures. The more closely spaced the schistosity planes the larger the extent of a temperature lowering.The genetic processes associated with these hematite-rich ore bodies appear to be sedimentary-metamorphic rather than metasomatic processes. Furthermore, there is no evidence for secondary leaching by weathering solutions.     

<Superscript>57</Superscript>Fe Mössbauer spectroscopy,X-ray single-crystal diffractometry,and electronic structure calculations on natural alexandrite

Natural alexandrite Al₂BeO₄:Cr from Malyshevo near Terem Tschanka, Sverdlovsk, Ural, Russia, has been characterized by ⁵⁷Fe Mössbauer spectroscopy, electron microprobe, X-ray single-crystal diffractometry and by electronic structure calculations in order to determine oxidation state and location of iron. The sample contains 0.3 wt% of total iron oxide. The ⁵⁷Fe Mössbauer spectrum can be resolved into three doublets. Two of them with hyperfine parameters typical for octahedrally coordinated high-spin Fe³⁺ and Fe²⁺, respectively, are assigned to iron substituting for Al in the octahedral M2-site. The third doublet is attributed to Fe³⁺ in hematite. Electronic structure calculations in the local spin density approximation are in reasonable agreement with experimental data provided that expansion and/or distortion of the coordination octahedra are presumed upon iron substitution. The calculated hyperfine parameters of Fe³⁺ are almost identical for the M1 and M2 positions, but the calculated ligand-field splitting is by far too large for high-spin Fe³⁺ on M1.     

Unravelling the pre-Variscan evolution of the Habach terrane (Tauern Window, Austria) by U-Pb SHRIMP zircon data

The U-Pb SHRIMP age determinations of zircons from the Habach terrane (Tauern Window, Austria) reveal a complex evolution of this basement unit, which is exposed in the Penninic domain of the Alpine orogen. The oldest components are found in zircons of a metamorphosed granitoid clast, of a migmatitic leucosome, and of a meta-rhyolitic (Variscan) tuff which bear cores of Archean age. The U-Pb ages of discordant zircon cores of the same rocks range between 540 and 520 Ma. It is assumed that the latter zircons were originally also of Archean origin and suffered severe lead loss, whilst being incorporated into Early-Cambrian volcanic arc magmas. The provenance region of the Archean (2.64-2.06 Ga) zircons is assumed to be a terrane of Gondwana affinity: i.e., the West African craton (Hoggar Shield, Reguibat Shield). The Caledonian metamorphism left a pervasive structural imprint in amphibolite facies on rocks of the Habach terrane; it is postdated by discordant zircons of a migmatitic leucosome at <440 Ma (presumably ca. 420 Ma). Alpine and Variscan upper greenschist- to amphibolite-facies conditions caused partial lead loss in zircons of a muscovite gneiss ('white schist') only, where extensive fluid flow and brittle deformation due to its position near a nappe-sole thrust enhanced the grains' susceptibility to isotopic disturbance. The Habach terrane - an active continental margin with ensialic back-arc development - showed subduction-induced magmatic activity approx. between 550 and 507 Ma. Back-arc diorites and arc basalts were intruded by ultramafic sills and subsequently by small patches of mantle-dominated unaltered and (in the vicinity of a major tungsten deposit) altered granitoids. Fore-arc (shales) and back-arc (greywackes, cherts) basin sediments as well as arc and back-arc magmatites were not only nappe-stacked by the Caledonian compressional regime closing the presumably narrow oceanic back-arc basin and squeezing mafic to ultramafic cumulates out of high-level magma chambers (496-482 Ma). It also induced uplift and erosion of deeply rooted crystalline complexes and triggered the development of a successor basin filled with predominantly clastic greywacke-arkosic sediments. The study demonstrates that the basement rocks exposed in the Habach terrane might be the 'missing link' between similar units of the more westerly positioned External domain (i.e., Aar, Aiguilles Rouges, Mont Blanc) and the Austroalpine domain to the east (Oetztal, Silvretta).     

Wasserstandserhöhungen in der Deutschen Bucht infolge von Schwingungen und Schwallerscheinungen und deren Bedeutung bei der Sturmflut vom 16./17. Februar 1962

Zusammenfassung Nach den Erfahrungen im Windstau- und Sturmflutwarndienst des Deutschen Hydrographischen Instituts müssen bei Wasserstands- oder Sturmflutvorausberechnungen, außer einer statistisch ermittelten Beziehung Windfeld-Windstau, der statische Luftdruck, die Böigkeit des Windes sowie die Inhomogenität des Windfeldes berücksichtigt werden. Der noch verbleibende Reststau wird untersucht, soweit er dem Betrage nach größer als 30 cm ist.Es lassen sich nachweisen: 1. Fortschreitende Wellen, die mit Luftdruckschwankungen in Resonanz stehen, 2. Querschwingungen der Nordsee, 3. Schwallerscheinungen in der Deutschen Bucht, die mit den an der englischen Küste bekannten external surges in Beziehung gesetzt werden. Es wird dargestellt, wie diese wellenförmigen Wasserstandserhöhungen bei der Vorhersage berücksichtigt werden können. Zum Schluß wird eine Aufgliederung der bei der Sturmflut vom 16./17. Februar 1962 gemessenen Wasserstandserhöhungen auf die oben dargelegte Weise gegeben.

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Elevations of water level in the German Bight due to oscillations and surges and their importance to the storm surge of 16/17th February 1962

Summary According to the experiences made by the Storm Surge Warning Service of Deutsches Hydrographisches Institut in predicting water level and storm surges, it is necessary to consider not only the relation wind field — wind effect, calculated by statistical means, but also the squally character of the wind, the static atmospheric pressure, and the inhomogeneity of the wind field. The still remaining residual wind effect is analysed, as far as its value exceeds 30 cm.The following phenomena have been verified: 1. Progressive waves caused by atmospheric pressure variations (resonance case), 2. Transverse oscillations of the North Sea, 3. Surges in the German Bight that may be related to the external surges, a well known phenomenon on the British coasts. It is discussed how these wave-shaped elevations of the water level can be considered in predicting storm surges. Finally, the different elevations of the water level, measured during the storm surge of 16th to 17th February, 1962, are analysed with the aid of the afore mentioned method.

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Elévations du niveau de la mer dues aux oscillations et aux ondes de tempêtes et leur importance à l'inondation du 16^e et du 17^e février 1962 dans la Deutsche Bucht

Résumé Suivant les expériences que le Service d'Avertissement des Marées de Tempêtes au Deutsches Hydrographisches Institut a faites à l'occasion de la prévision des ondes de tempêtes, il s'est montré nécessaire de tenir compte non seulement de la relation entre le champ du vent et l'effet du vent calculée à l'aide des moyens statistiques mais qu' il faut aussi bien considérer le vent à rafales, la pression atmosphérique statique et l'inhomogénéité du champ du vent. L'effet résiduel du vent qui pourtant reste, est analysé en tant que sa valeur s'élève à plus de 30 centimètres.Les phénomènes suivants ont été vérifiés: 1⁰ «Ondes progressives» causées par des variations de la pression atmosphérique (cas de résonance), 2⁰ «Oscillations transversales» de la mer du Nord, 3⁰ «Houles» dans la Deutsche Bucht qui peuvent être associées aux houles externes (external surges), phénomènes bien connus sur les côtes britanniques. On discute de quelle manière on pourrait tenir compte de ces élévations ondulatoires du niveau de la mer dans la prévision des ondes de tempêtes. Enfin, les élévations diverses du niveau de la mer, mesurées à l'occasion de l'inondation du 16^e et du 17^e février 1962, sont analysées à l'aide de la méthode décrite ci-dessus.

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Ein Vortrag wurde am 11. Oktober 1962 auf der Meteorologentagung in Hamburg gehalten.     

Das Bodenwasser und die Vertikalzirkulation des Mittelländischen Meeres

Zusammenfassung Der Beitrag stellt eine Fortsetzung der 1960 in dieser Zeitschrift Jahrgang 13, Heft 3 erschienenen Abhandlung (Wüst [1960]) dar und führt die Studien über die mittelmeerische Tiefenzirkulation in bezug auf die Ausbreitungs- und Vermischungsvorgänge im Bodenwasser (bei Wassertiefen von mehr als 1500 m) fort. Nach einem detaillierten Nachweis über das Quellenmaterial, das 234 Stationen (von 11 Forschungsschiffen) umfaßt, wedden weitere Belege zur Frage der Formung des Nordbalearischen und des Adriatischen Bodenwassers gebracht und die Verbreitung dieser beiden Wasserarten auf Grund neuer Karten der potentiellen Bodentemperatur und des Bodensalzgehaltes in den beiden mittelmeerischen Großbecken verfolgt. Durch ein schematisches dreigeteiltes Blockdiagramm (Tafel 5) wird die Vertikalzirkulation und Salzgehaltsverteilung des Mittelmeeres im Winter in ihrem Zusammenwirken zonaler und meridionaler Komponenten veranschaulicht. In einem Nachtrag (zum 1. Beitrag 1960) wird eine weitere Kernschichtkarte des Levantinischen Zwischenwassers auf grund der Armauer Hansen-Stationen Mai–Juni 1931 vorgelegt.

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The bottom water and the vertical circulation of the Mediterranean Sea

Summary The present paper is a continuation of the first article published in vol. 13, page 105 of this journal (Wüst [1960]). It continues the studies of the deep circulation in the Mediterranean Sea with regard to distribution and mixing in the bottom water (at depths of 1500 m and more). A detailed verification of the observational material comprising 234 stations (of 11 research vessels) is presented and some further proofs concerning the formation of the North-balearic and the Adriatic bottom water are given. Besides, basing on new charts of the potential bottom temperature and bottom salinity, the distribution of the aforementioned two water types in the two large mediterranean basins is discussed. A schematical diagram consisting of three four-edged columns (Tafel 5), shows clearly the vertical circulation and salinity distribution in the Mediterranean Sea and the combined action of their zonal and meridional components during the winter months. As a supplement to the 1960-paper in this journal, another chart is added showing the core layers of the Levantine intermediate water based on the Armauer Hansen-stations from May and June 1931.

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Les eaux du fond et la circulation verticale de la mer Méditerranée

Résumé L'article actuel fait suite au premier travail, paru dans le volume13, page 105 de ce journal (Wüst [1960]). Il continue les recherches de la circulation mediterranéenne par rapport aux processus de distribution et de mélange des eaux du fond (à 1500 mètres de profondeur et plus). Le matériel d'observation comprenant 234 stations (exécutées par 11 bâtiments de recherche) est soumis à une vérification détaillée; d'autres preuves sont apportées concernant la formation des eaux du fond dans la région septentrionale du bassin baléarique et dans la mer Adriatique. Partant de nouvelles cartes de la température potentielle et de la salinité des eaux du fond on poursuit, en même temps, les études de la distribution des deux types d'eaux rencontrés dans les deux grands bassins de la Méditerranée mentionnés ci-dessus. Un diagramme schématique se composant de trois colonnes quadrangulaires (Tafel 5) montre nettement la circulation verticale et la distribution de la salinité méditerranéenne ainsi que l'action combinée de leurs composantes régionales et méridionales pendant les mois d'hiver. Dans un supplément au premier travail (Wüst [1960]) une autre carte est ajoutée représentant les couches de noyaux des eaux intermédiaires levantines basant sur les stations de l'«Armauer Hansen» en mois de mai et de juin 1931.

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Hierzu Tafeln 2–5 im Anhang

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Herrn Professor Dr. Günter Dietrich zum 50. Geburtstag gewidmet.     

Kaledonische Intrusivgesteine des Stavanger-Gebietes

An empirical approach has been taken to develop a geothermometer based on plagioclase-magmatic liquid equilibrium. Compositions of coexisting plagioclase and liquid (glass) obtained by electron microprobe analysis of quenched samples from equilibrium melting experiments of natural granitic rocks at water pressures of 0.5 and 1.0 kilobars have been used along with data from the equilibrium experiments of Bowen (1913, 1915), Prince (1943) and Yoder et al. (1957) to calibrate this geothermometer. Applications of this geothermometer to natural occurrences demonstrate that it can provide useful information on temperature of equilibration of coexisting plagioclase and liquid in rocks ranging in composition from basalt to rhyolite. The plagioclase geothermometer is in good general agreement with other geothermometers wherever these are applicable. Where temperatures are known from other sources it can be used to predict the equilibrium compositions of plagioclase in magmas as well as to provide a rough estimate of water pressure.