Thermochemistry of carbonate-pyroxene equilibria

The enthalpies of drop solution of calcite, magnesite, dolomite, wollastonite and diopside have been measured in a lead borate solvent at 977 K in a Calvettype microcalorimeter. The carbonate calorimetry was done under flowing gas atmosphere. Both natural and synthetic samples were used. From these calorimetric data, the enthalpies of several reactions of carbonate with quartz were calculated. The enthalpies of these reactions (kJ/mol) at 298 K are: calcite+quartzwollastonite+CO₂, 92.3±1.0; magnesite+quartzenstatite+CO₂, 82.9±2.8; dolomite+quartzdiopside+CO₂, 163.0±1.9. These values generally are in agreement with those calculated from Robie et al., Helgeson et al., Berman and Holland and Powell. The enthalpy of dolomite-quartz reaction overlaps marginally with those from Berman and Holland and Powell. The enthalpy of formation of dolomite from magnesite and calcite (-11.1±2.5 kJ/mol) was also derived from the measured enthalpies, and this value is consistent with that from acid solution calorimetric measurements as shown by Navrotsky and Capobianco, but different from values in the earlier literature. These results support the premise that drop-solution of carbonates into molten lead borate results in a well-defined final state consisting of dissolved oxide and evolved CO₂. This was also confirmed by weight change experiments. Thus, oxide melt calorimetry is applicable to carbonates.     

A staurolite-talc assemblage in tourmaline-phlogopite-chlorite schist from northern Victoria Land,Antarctica, and its petrogenetic significance

Staurolite and corundum are found as inclusions in tourmaline in a talc-phlogopite-chlorite-albite chist near Mount Bernstein (71°37S, 163°07E), northern Victoria Land, Antarctica. These inclusions are interpreted as relics of a staurolite-talc-corundum-chlorite assemblage that was stable during an early stage in the metamorphic cycle and subsequently armored by tourmaline, probably during the middle stage. Pressures and temperatures during the middle stage are estimated to be 650–700°C and 5.5–6.4 kbar. The transition from the early to the middle stage represents a roughly isothermal decrease in pressure of 2–3 kbar. During a late retrograde stage (T=300–370°C, P=3–5 kbar), staurolite was partly replaced by a muscovitic aggregate containing clinozoisite, pumpellyite, and margarite.The staurolite is unusually Si-poor (26.77, 25.85 weight % SiO₂ or 7.275, 7.091 Si per formula unit for 46 oxygens anhydrous), Al-rich (58.00, 57.85% Al₂O₃, 18.579, 18.702 Al), low in divalent cations (Fe+Mg+Mn+Zn=3.301, 3.560) and magnesian (atomic Mg/(Mg+Fe)=0.42, 0.40). Ion microprobe analysis of the first grain indicates about 0.2% Li₂O (0.219 Li) is present. The following substitutions are proposed to explain the unusual chemistry of this staurolite (crystallographic site notation of Smith 1968, in bold letters): Al(Si)+Al(Al(3A,B))Si(Si)+Fe(Fe), Li(Fe)+Al(Al(3A,B))2 Fe(Fe), and 2 Al(Al(3A,B)) 3 Fe(Fe).According to a pressure-temperature diagram constructed by the method of Schreinemakers for the model system FeO-MgO-Al₂O₃-SiO₂ (H₂O in excess), the talc-staurolite assemblage should be stable only in quartz-free rocks at temperatures near 700° C and pressures of 8 kbar or more. The rarity of the staurolite-talc assemblage even in Mg-Al-rich rocks metamorphosed at the appropriate pressure-temperature conditions is attributed to the appearance of anthophyllite or, in Na₂O-bearing rocks, gedrite. Orthoamphibole-cordierite and orthoamphibolekyanite assemblages with chlorite or corundum are incompatible with staurolite-talc±albite. In rocks lacking corundum and formed at pressures above the stability limit of cordierite, staurolite-talc may be metastable relative to orthoamphibole-kyanite, while in corundum-bearing rocks, staurolite-talc may appear under certain conditions, possibly at higher water activities than the orthoamphibole-kyanite assemblage.     

Multi-stage metamorphic re-equilibration in eclogitic rocks from the Hercynian basement of NE Sardinia (Italy)

Summary Eclogitic rocks are hosted within gneisses and migmatites of the Hercynian basement of NE Sardinia. They are characterized by two compositional layers: garnet-pyroxene rich-layers and amphibole-plagioclase layers. The former contain structural, mineralogical and compositional relics of eclogite facies re-equilibration. Four stages of evolution have been identified: an eclogite stage, a granulite stage and a retrograde amphibolite to greenschist stage. A possible pre(?)-eclogite stage is documented by inclusions of euhedral tschermakitic amphibole + zoisite within the core of garnet. This early stage was followed by an increase in pressure under which the eclogite climax developed (T up to 700 °C, P =13-15 kbar), as documented by omphacite inclusions towards the rim of garnet.Characteristic mineral reactions after the eclogitic stage are: omphacite diopside + plagioclase (symplectite) and garnet orthopyroxene + plagioclase. These reactions testify the presence of a granulite stage during which the peak of metamorphism was reached (T up to 870'C, P 10 kbar). The orthopyroxene cummingtonite + quartz and garnet + diopside hornblende + plagioclase (kelyphite) transformations indicate extensive amphibolite retrogression (T = 550650 °C, P = 3-7 kbar). Finally, actinolite and chlorite developed (greenschist stage) at falling temperature and pressure (T = 300-400 °C, P < 2-3 kbar).

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Mehrstufige metamorphe Reequilibration eklogitischer Gesteine aus dem hercynischen Basement NE Sardiniens (Italien)

Zusammenfassung Eklogitische Gesteine kommen in Gneisen und Migmatiten des hereynischen Basements in NE Sardinien vor. Sie sind durch einen modalen Zweitagenbau von einerseits Granat-Pyroxen andererseits Amphibol-Plagioklas charakterisiert. In ersteren sind Relikte einer strukturellen, mineralogischen und mineralchemischen Reequilibration unter eklogitfaziellen Bedingungen enthalten. Vier Entwicklungstadien sind unterscheidbar: ein Eklogit-, ein Granulit-, sowie ein retrogrades Amphibolit- und Grünschieferstadium. Ein mögliches prä(?)-eklogitisches Stadium ist durch die Einschlüsse von tschermakitischem Amphibol + Zoisit in Granatkernen angedeutet. Auf dieses Frühstadium folgte, dokumentiert durch Omphaziteinschlüsse im Granatrandbereich, Druckzunahme und es wurden eklogitfazielle Bedingungen (T bis zu 700 °C, P = 13-15 kbar) erreicht.Charakteristische Mineralreaktionen nach der Eklogitbildung sind Omphazit Diopsid + Plagioklas (Symplektite) und Granat Orthoyroxen + Plagioklas. Diese Reaktionen belegen das Vorliegen eines Granulitstadiums, während dem der Metamorphosehöhepunkt (T bis 870°C, P 10 kbar) erreicht wurde. Die Umwandlungen von Orthopyroxen Cummingtonit + Quarz und Granat + Diopsid Hornblende + Plagioklas (Kelyphit) belegen eine intensive retrograde amphibolitfazielle Überprägung (T = 550-650°C, P = 3-7 kbar). Aktinolith und Chlorit (Grünschieferstadium) bildeten sich bei weiter fallenden Temperaturen und Drucken (T = 300-400 °C, P < 2-3 kbar).

     

Temperature — composition relationships of authigenic micaceous minerals in the Los Azufres geothermal system

Smectite, illite, celadonite and chlorite are the major products of alteration of rhyolites and andesites, in the upper part of the Los Azufres geothermal system. Changes in mineral assemblages and composition of phases are observed as a function of depth and host rock lithology. Two different sequences characterize the rhyolites and the andesites from the surface to a depth of about 1500 m: kaolinitesmectite (±interlayered illite/smectite)illitemuscovite (rhyolites), and kaolinitesmectite (±interlayered illite/smectite)illite+celadoniteillite+chloritechlorite (andesites).Illite, and chlorite at depth, are largely dominant. Similar substitutions and correlations among chemical constituents characterize illites from rhyolites or andesites, but their compositions in the two host rock lithologies exhibit slight but significant differences, especially in their Fe and Mg contents which are the highest in illites from andesites. Illite exhibits progressive changes in composition with depth: a strong increase in the K content in the interlayer, together with an increase of the Fe content in the octahedral site. These changes correspond to a slight increase in the molar fraction of Fe-(Mg) celadonite end-members, and mostly to a dramatic decrease of pyrophyllite with increasing temperature.Temperature of the mineralogical and compositional changes was estimated from fluid inclusions studies, combined with other geothermometric approaches (chemical geothermometers and direct measurements). Variation of X-pyrophyllite with temperature is proposed as a geothermometer for different host rock lithologies. Transitions between the stability fields of illite±interstratified illite-smectite and illite+chlorite is around 200±30° C, and between illite+chlorite and chlorite around 290±20° C.     

The origin of fumarolitic andradite at Menoyre,France and Fant'Ale,Ethiopia

Recent discoveries of fumarolitic andradite in alkaline or peralkaline trachytes (Menoyre, Cantal, France, and Fant'Ale, Ethiopia) are interpreted genetically.The andradites were formed from the constituents of pyroxene, always calcic and iron-rich in these rocks. The elements Ca and Fe were fixed on the surface of fractures by late fumaroles of high oxidizing capacity.The following reaction can be established at Menoyre: hedenbergite+O₂andradite+hematite+cristobalite.In a hyperalkaline medium, which is the case for the trachyte of Fant'Ale, the reaction is: Hedenbergite+sodium metasilicate+O₂andradite+aegirinic pyroxene+cristobalite.     

Sapphirine/kornenipine-bearing rocks and crustal uplift history of the Limpopo belt,Southern Africa

Sapphirine/kornerupine-bearing rocks occur within the anorthosites of the Messina layered intrusion in the Limpopo mobile belt of Zimbabwe. The X_Mg range of the major minerals is as follows: cordierite (0.98-0.93); enstatite (0.97-0.86); chlorite (0.98-0.92); phlogopite (0.98-0.90); sapphirine (0.98-0.86); kornerupine (0.94-0.88); gedrite (0.96-0.85); spinel (0.92-0.78). There are four rock types, the constituent minerals of which have different values, which decrease in the above mineral order; other minerals are corundum, sillimanite and relict kyanite. We recognise twenty reactions without phlogopite and nine reactions involving phlogopite. The textural relations and the plots of the microprobe data of coexisting minerals in the MgO-Al₂O₃-SiO₂-(H₂O) system are consistent with the following sequence of main reactions: (1) enstatite+corundum cordierite+sapphirine; (4) sapphirine+sillimanite cordierite+corundum; (8) kornerupine+corundum cordierite+sapphirine; (13) kornerupine cordierite+sapphirine+enstatite; (15) enstatite+spinel chlorite+sapphirine; (18) cordierite+sapphirine chlorite+corundum; (20) sapphirine chlorite+corundum+spinel. The early reactions are shown by coarse-grained reaction intergrowths, kornerupine and gedrite breakdown is shown by finer-grained symplectites, and the latest reactions by very fine-grained products in micro-fractures. These selected reactions illustrate a remarkably steep trajectory from thePT peak close to 10 kbar and 800° C to the minimum observable at 3.5–4.5 kbar and 700° C as indicated by the pure MASH system. Very rapid uplift took place under nearly isothermal conditions. The protolith of this material was possibly sedimentary, derived from altered volcanic rocks. The bulk composition is close to the composition of kornerupine or to a mixture of alunite, chlorite and pyrophyllite. These texturally and mineralogically complex rocks contain a wealth of relevant data for documenting crustal uplift history.     

The Al-Fe(III)epidote miscibility gap in a metamorphic profile through the penninic series of the Tauern window,Austria

The compositional variations in epidotes, Ca₂Al₂(Fe³⁺, Al)-Si₃O₁₂(OH), from a prograde Mesozoic rock series in the Eastern Alps, Austria, are systematically related to metamorphic grade and the oxidation state of the rock. With increasing metamorphic grade the average composition of the zoned epidotes shifts to Fe³⁺-poorer compositions reflecting not only the effect of temperature and total pressure but also the concomitant decrease of the oxidation state of the rocks. Oxidized hematite-bearing assemblages are: 90 mole % Al₂FeEp (greenschists) 70 mole % Al₂FeEp (garnet amphibolites) 58 mole % Al₂FeEp (eclogites); reduced sulfidebearing assemblages are: 42 mole % Al₂FeEp (greenschists) 24 mole % Al₂FeEp (garnet amphibolites) 23 mole % Al₂FeEp (eclogites).A similar compositional evolution of the epidotes as in the spatial sequence of the samples can be observed within the single zoned crystals, reflecting the temporal changes of temperature, total pressure and oxygen fugacity during the prograde crystallization. The Fe³⁺-contents of core and rim decrease with increasing metamorphic grade and decreasing oxidation state. Generally the zoned epidotes consist of a Fe³⁺-rich core (90 to 63 mole % Al₂FeEp) and a Fe³⁺-poorer rim (55 to 23 mole % Al₂FeEp). Core and rim of the epidote crystals are separated by a compositional gap the extension of which is independent of the bulk rock composition, the oxidation state, and the mineralogical composition of the assemblages but becomes smaller with increasing metamorphic grade: 7253 mole % Al₂FeEp (low grade greenschists, 400° C) 6355 mole % Al₂FeEp (higher grade greenschists, 500° C), and 6055 mole % Al₂FeEp (garnet amphibolites, 500–550° C). At the temperature conditions of the highest grade garnet amphibolites and eclogites (550° C) the compositional gap closes at a composition of 58 mole % Al₂FeEp.The data presented thus confirm clearly the existence of an asymmetric miscibility gap in the monoclinic Al-Fe(III)-epidote solid solution series, which, for the first time, has been assumed by Strens (1964, 1965).A model is proposed that describes the prograde compositional evolution of the epidotes studied through the competing mechanisms of growth and diffusional Al-Fe³⁺ exchange and their dependence on metamorphic grade and oxidation state.     

Osumilite-sapphirine-quartz granulites from Enderby Land Antarctica — Mineral assemblages and reactions

The pre-Cambrian granulites of Enderby Land Antarctica, contain coexisting spinel-quartz, sapphirine-quartz, hypersthene-sillimanite-quartz and osumilite on a regional extent. Osumilite is present in a variety of mineral assemblages, most of which are documented in granulites for the first time. The mineral assemblages, reactions and compositional zoning in minerals are discussed in terms of continuous and discontinuous reactions in response to changing conditions of metamorphism. The development of many of the mineral coronas can be explained by continuous rather than discontinuous reactions, due to the effects of Mg-Fe and (Mg,Fe)-2Al exchange equilibria with decreasing temperature. The highest P-T conditions of metamorphism (8–10 kb, 900 °–980 ° C, Ellis, in preparation) were beyond the stability limit of coexisting garnet-cordierite. Secondary cordierite has developed through a large number of mineral reactions in response to cooling of these granulites.A theoretical analysis of the phase relations involving osumilite in the chemical systems K₂O-MgO-Al₂O₃-SiO₂ and K₂O-MgO-FeO-Al₂O₃-SiO₂ is presented. In the pure Mg-system the lower temperature stability limit of Mg-osumilite is inferred to be defined with increasing pressure by the reactions OsCd+En+Kfeld+Qtz, OsSa+En+Kfeld+Qtz, OsSill+En+Kfeld+Qtz. In iron-bearing systems an important reaction involving osumilite is Os+GtCd+Hy+Kfeld+Qtz.At moderate temperatures and pressures, osumilite is limited to rocks which lie on the Mg-rich side of the Cd-Hy stable tie line on an AFM diagram. At higher pressures and temperatures osumilite occurs in a widerrange of rock compositions because of the stability of coexisting garnet and osumilite. Petrographic data, as well as chemographic relations indicate that for many common rock compositions, garnet, cordierite, hypersthene, sapphirine and sillimanite cannot coexist with both osumilite and K-feldspar.Published with the permission of the Director, Bureau of Mineral Resources     

High-density CO2−N2 inclusions in eclogite-facies metasediments of the Münchberg gneiss complex,SE Germany

The eclogite-facies metasedimentary rocks in the Münchberg gneiss complex (T=630±30° C/P17–24 kbar) locally contain CO₂–N₂-rich fluid inclusions of extremely low molar volumes (32 cm³/mol) in quartz. These fluid compositions are mainly found in rocks intercalated with calcsilicate bands. Densities were determined from low-temperature phase transitions like stable or metastable homogenization (L+VL), partial homogenization (S+L+VS+L) and the transition S+LL (L = liquid, V = vapour, S = solid). The high fluid densities are in agreement with eclogite-facies pressure and temperature and subsequent amphibolite facies. CO₂–N₂ inclusions were not observed in adjacent eclogites nor in non-calcareous metasediments. These rock types contain predominantly H₂O-rich inclusions correlating with amphibolite-facies conditions. The variation of fluid composition with lithological differences indicates local fluid gradients and speaks against a pervasive fluid flow during eclogite-facies metamorphism.     

Crystallographic procedures in the study of experimental rocks: x-ray single-crystal structure refinement of C2/c clinopyroxene from lunar 74275 high-pressure experimental basalt

Summary The possibility of applying X-ray single crystal techniques to minerals pertaining to rocks experimentally crystallized in laboratory has been investigated as a new approach to precisely relate crystal-chemistry to pressure, temperature, fO₂, and composition of the magma from which the crystal formed.A clinopyroxene from the experimental lunar basalt (74275 composition) ofGreen et al. (1975) crystallized at 12 Kb and 1320 °C, was successfully refined to an R factor of 0.041. Its structure configuration turned out to be exceptional, expecially in relation to the record low Ca(M2) occupancy (0.57 atoms per formula unit henceforth a.f.u.), but comparable with the other lunar C2/c clinopyroxene previously studied with X-ray single crystal methodology: augite 12052 (Takeda 1972 a). Comparative analysis of the two lunar clinopyroxene structures revealed their common high temperature origin and the high-pressure imprint of the experimental specimen relative to the natural one.Both lunar samples differ radically from the studied terrestrial clinopyroxenes of C2/c diopside-like structure: the main difference of lunar clinopyroxenes with respect to terrestrial analogues is the high Ally (T) (Al^IV > 0.20 a.f.u.) in spite of low Ca(M2). Relative to the ideal diopside structure, Si⁴⁺ Al^IV and Ca Mg + Fe²⁺ substitutions in T and M2 sites, respectively, turned out to be not compatible with terrestrial clinopyroxenes.

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Kristallographische methoden zur untersuchung experimenteller gesteine: struktur verfeinerung von C₂/c klinopyroxen aus dem experimentellen hochdruck mond-basalt 74275

Zusammenfassung Die Anwendung von Einkristallverfahren auf Minerale aus experimentell hergestellten Gesteinen wurde untersucht; sie wird als ein neuer Weg zur quantitativen Korrelation der Kristallchemie mit Druck, Temperatur, fO₂ und der Zusammensetzung des Magmas, aus dem der Kristall gebildet wurde, gesehen.Die Struktur eines Klinopyroxens aus dem experimentellen Mond-Basalt (Zusammensetzung 74275) vonGreen et al. (1975), der bei 1320 °C kristallisierte, wurde mit Erfolg bis auf einen R-Faktor von 0.041 verfeinert. Es zeigte sich, daß seine Struktur-Konfiguration außergewöhnlich war, besonders im Hinblick auf die besonders niedrige Ca(M2) Besetzungsdichte (0.57 Atome pro Formeleinheit). Sie ist jedoch vergleichbar mit dem anderen lunaren C2/c Klinopyroxen der bisher mit Röntgen-Einkristallverfahren untersucht wurde, nämlich Augit 12052) (Takeda, 1972a). Vergleichsanalysen der beiden lunaren Klinopyroxen-Strukturen lassen ihre gemeinsame Hochtemperatur-Entstehung erkennen, sowie den — im Gegensatz zu der natürlichen Probe — deutlichen Einfluß hoher Drucke auf die experimentell hergestellte Probe.Beide lunare Proben unterscheiden sich deutlich von den untersuchten terrestrischen Klinopyroxenen mit Diopsid-artiger C2/c Struktur: der Hauptunterschied zwischen lunaren Klinopyroxenen und ihren terrestrischen Analogen ist der hohe Al^IV (T) (Al^IV > 0.20 a.f.u.) trotz niedrigem Ca(M2). Im Vergleich mit der idealen Diopsidstruktur zeigte sich daß, Si⁴⁺ Al^IV und Ca Mg + Fe²⁺ Substitutionen an T resp. M2 Plätzen nicht kompatibel mit terrestrischen Klinopyroxenen sind.

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With 4 Figures     

The complex antimony-lead/zinc deposit at Rujevac/Yugoslavia; its specific geochemical and mineralogical features

During the last years, several large complex antimony deposits (Sb-Pb/Zn-As association) have been discovered in Yugoslavia. One of these deposits is Rujevac in western Serbia. Genetically related to the Tertiary granodioritic magma, the mineral parageneses are characterized by some specific features. So, pyrite displays occasionally a zonal pattern of arsenic distribution: the marginal zones contain up to 6 wt% of As. Besides common galena, antimoniferous galena containing up to 10. 5% of Sb is known. Among lead sulphantimonides, some new species are indicated. The paragenetic sequence of the Pb-Sb-S minerals indicates that the fluctuations in the chemical potential of Sb₂S₃, influenced by the presence of lead and antimony in the ore-bearing hydrothermal solutions, and geochemistry of the deposit, were such that they resulted in formation of an order of deposition like stibnite lead sulphantimonides galena. This order of crystallization seems to be characteristic of some complex Sb-Pb-S ores.     

Untersuchungen über die Petrographie kulmischer Kieselschiefer

Zusammenfassung Profile von kulmischen Kieselschiefern des hessischen Hinterlandes wurden optisch, röntgenographisch, chemisch, spektralanalytisch und differential-thermoanalytisch untersucht. Die nicht-lyditischen Bestandteile wurden besonders berlicksichtigt.Als Vergleichsmaterial dienten kulmische Kieselschiefer aus dem Harz, sowie tertiäre (Monterey), silurische und algonkische Kieselschiefer. Es wurde festgestellt, daß in der Kulmstufe II–III (dunkle und bunte Lydite) im hessischen Hinterland und im Harz zahlreiche, gering mächtige Tuffhorizonte auftreten; ihre Häufigkeit nimmt nach obenhin zu. Die bunten Lydite führen tuffitische Bänke, deren Grundmasse ursprünglich kalkig war. Die bisher nur aus dem Harz bekannten, kieseligen Tuffe des Kulms (Typ Lerbacher Adinole) Bind auch im hessischen Hinterland verbreitet.Met Röntgen- und DTA-Aufnahmen wurde zu zeigen versucht, daß die Kieselsäure seit der Entstehung des Sediments folgende Phasenumwandlungen erfahren hat:Opal Cristobalit mikrokristalliner Quarz (Chalzedon, Quarzin), und daß in paläozoischen Kieselsedimenten noch amorphe oder stark fehlgeordnete Kieselsäure vorhanden sein kann.Die Entstehung der kulmischen Kieselschiefer wird diskutiert.     

Petrographisehe Untersuehung der Gleesite des Laacher Seegebietes

In the present publication the hauyn-gleesites (in earlier publications called hauynsanidinites) and the other rocks, which belong genetically to the hauyn-gleesites, as hauynfree gleesites, hornblende-rich alkaligabbros, hornblendites, Laacher hauyntrachytes and hauynlatites, are described. All these different products can only be found in form of fragments in the trachyttuffs around the Laacher See (Germany).The microscopical analysis of the Laacher trachytes and hauynlatites demonstrates, that the magma has been strongly influenced by assimilation. This is characteristically demonstrated by the strong oscillation of the anorthit-content of the plagioclases in each fragment.The primary rocks, which are metamorphosed by the alkalisyenitic respectively alkalitrachytic magma, are the differentiationsproducts of an alkaligabbroic magma, hornblendites, hornblende-rich alkaligabbros and possibly monzonites. The crystallisations sequence of these rocks is: biotite hornblendite augite. The same sequence can be seen in the hauyn-free and the hauyn-bearing gleesites.The relative high content of titanite in the gleesites is remarcably. The source of the TiO₂, which is necessary for the formation of titanite, lies in the magnetites of the alkaligabbroic rocks. In the basic rocks the magnetit contains nearly 17 % Ti0₂. In the magnetite of the hauyn-free gleesites there is only 11 % and in the hauyn-gleesites, which are found in the latest phase of metamorphic transformation, is only 8–9% Ti0₂. The same content of 8–9% TiO₂ is found in the magnetites of the white trachyttuffs around the Laacher See. The glas in all these rock-fragments was formed by the heat during the eruption of the tuffs, possibly under the influence of alkali-rich gases.     

Simulation of primary phase relations and mineral compositions in the Partridge River intrusion,Duluth Complex,Minnesota: implications for the parent magma composition

In order to describe the composition and crystallinity of the initial (parental) magma of the Partridge River intrusion of the Keweenawan Duluth Complex, and thereby understand the mode of emplacement and solidification of the intrusion, we have applied a numerical simulation technique called geochemical thermometry (Frenkel et al. 1988). The parental magma was a low-alumina, high-Ti-P olivine tholeiite similar to typical Keweenawan low-alumina, high-Ti-P basalts associated with the Duluth Complex and from the nearby Portage Lake area of the Lake Superior region. The parental magma was emplaced as a crystal-liquid suspension, followed by chilling of an evolved, leading edge ferrodioritic liquid in the basal zone of the intrusion. The conditions of emplacement at the present crustal location were 1,150°C, 2 kbar, and f _{O 2} slightly above the wustite-magnetite (WM) buffer. The main differentiation process after emplacement was the sorting and redistribution of plagioclase and olivine crystals on a local scale accompanied by less efficient convection and minor settling of olivine. Calculated crystallization sequence for the parental magma is olivine+plagioclase (1,240°C)olivine+plagioclase+magnetite (1,146°C, WM+0.5)olivine+plagioclase+magnetite+augite (1,140°C, WM+0.5). The calculated compositions of the cumulus olivine and plagioclase in equilibrium with the parent magma at 1,150°C are Fo_66.7±1.1 and An_64.5±2.5, respectively, and are similar to the estimated average composition of primary olivine (Fo_69.1±2.8) and the average composition of plagioclase core (An_66.3±2.8) measured in drill core samples through the intrusion (Chalokwu and Grant 1987).     

Wittite with Se-rich Cosalite and Bismuthinite from Nevskoe Tin Deposit (Magadan District,Russia)

Summary A second confirmed occurrence of wittite, one of the four known Pb-Bi-Se-sulfosalts, has been found in the Nevskoe tin deposit (Eastern Siberia). Microprobe analyses of wittite show pronounced variation of Se content (from 9.5 to 16.5 wt. %), due to S --> Se substitution; Pb and Bi contents vary from 29 and 43%, up to 34 and 46%, respectively. Minor elements are also present: Sb up to 1.5%, Ag up to 1.3 %, and Cu (0 to 0.2%). Comparison of microprobe data of wittite from Nevskoe and Falun, on the one hand, and cannizzarite from different deposits on the other hand, indicate that Ag is incorporated in the wittite/cannizzarite structure through the substitution 2 Pb -> Bi + Ag. Conversely, Ag substraction gives a constant Bi/(Bi + Pb) atomic ratio, independent of the Se/(Se+"S) ratio, and close to 55.1%. Se-rich wittite is compositionally very close to proudite and weibullite. X-ray powder and electron microdiffraction patterns are given; the incommensurate structure agrees with the 7H/12Q match along , like in wittite from Falun. Nevskoe wittite is close to Pb₈Bi₁₀(S, Se)₂₃, but the 7H/12Q match requires the formula Pb_11.61Bi_14.26S₃₃, with about 3% of the Pb atoms in the Q layer replaced by Bi atoms and vacancies (p). Taking into account all microprobe data, the general formula developed is: Pb_{11.61–2x0.13}Ag_x(Bi_14.26+x-ySb_y)(S_1–zSe_z)₃₃ with x and y 0.86 at., and z 0.45. At Nevskoe, associated bismuthinite contains from 5 to 12% Se, with minor Sb, Pb and Cu. Se-rich cosalite contains from 4 to 8% Se, with Sb from 2.7 to 5.3%, and minor Ag and Cu. Wittite in contact with cosalite clearly shows a relative Se-enrichment, that could be due to the pseudo-hexagonal sub-lattice of this incommensurate structure, very similar to the Bi₂(Se, Te, S)3 sheet in the tetradymite series. According to microprobe data, there is a continuous change from Se-free cannizzarite to Se-rich wittite. Therefore, the validity of wittite as a specific mineral species appears questionable, and more accurate crystallographic studies on this incommensurate series are necessary.

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Wittite avec Cosalite et Bismuthinite Séléniferes du Gisement d'Etain de Hevskoe (District de Magadan, Russie)

Resume Une seconde occurrence de wittite, l'un des quatre sulfosels de Pb-Bi-Se cormus, a été trouvée daps le gisement d'étain de Nevskoe (Sibérie Orientale). Son analyse á la microsonde électronique montre une forte variation de la teneur en sélénium (de 9,5 á 16,5%), qui se substitue au soufre; les teneurs en Pb et Bi varient de 29 à 43 et 34 á 46%, respectivement. On note la présence de Sb (, 1,5%), Ag ( 1,3%) et Cu (< 0,2%). La comparaison des analyses de wittite de Nevskoe et Falun, et de cannizzarite de différents gisements, montre que Bans cette série l'argent est incorporé suivant la substitution 2 Pb Bi + Ag. Après soustraction de Ag, le rapport atornique Bi/(Bi + Pb) corrigé apparaït constant, proche de 55,1%, et indépendant du rapport Se/(S + Se). La wittite la plus riche en Se est chimiquement très proche de la proudite et de la weibullite. Son diagramme de poudre aux rayons X ainsi que son étude en microdiffraction électronique sont présentés; la structure, de type incommensurable, s'accorde aver un ajustement selon le rapport 7H/12Q suivant , comme dans la wittite de Falun. La formule de la wittite de Nevskoe est proche de Pb₈Bi₁₀(S, Se)₂₃, mais l'ajustement 7H/12Q demande la formule Pb_11.61Bi_14.26S₃₃, avec environ 3% des sites à Pb du feuillet Q remplacés par des atomes de Bi et des sites vacants (). La prise en compte de l'ensemble des analyses conduit á la formule développée générale: Pb_11.61-2x0.13Ag_x(Bi_14,26+x–ySb_y)-(S_{1 –z}Se_z)₃₃ avec x et y 0,86 at., et z 0,45. A Nevskoe, la bismuthinite associée contient de 5 à 12% Se, avec Sb, Pb et Cu mineurs. La cosalite contient de 4 a 8% Se, 2,7 á 5,3% Sb, avec Ag et Cu mineurs. Lá où wittite et cosalite sont en contact étroit, la wittite montre clairement un enrichissement relatif en Se, qui pourrait etre du au sousréseau pseudo-hexagonal de cette structure incommensurable, très proche du feuillet Bi₂(Se, Te, S)3 présent dans la série de la tétradymite. Les analyses à la microsonde indiquant une continuité chimique de la cannizzarite sans Se à la wittite 1a plus riche en Se, la validité de la wittite en tant qu'espéce spécifique apparaït discutable. Mais le caractère incommensurable de cette série demande une etude cristallographique plus détaillée.

     

Clinopyroxenes from plagioclase peridotites (Zabargad Island,Red Sea) and comparison between high- and low-pressure mantle clinopyroxenes

Summary A detailed crystal-chemical study of clinopyroxenes from the peridotite-pyroxenite association from Zabargad Island (Red Sea) has been carried out to decline the intercrystalline relationships in mantle-derived clinopyroxenes equilibrated at low pressure conditions (plagioclase facies:Pl-Cpx).Pl-Cpx typically show larger cell volume (>437 °A3) compared with those from spinel and garnet-spinel peridotite nodules (Sp-Cpx). The larger cell volume is mainly achieved through higher Mgm, and louver Al^VI occupancies, which strongly increase the M l volume. Concurrently, overcharging on the O3 oxygens due te, the high Ca_M2 ( 0.828 atoms per formula unit, a.f.u.) and low Na_M2 (< 0.037 a.f.u.) occupancies requires lengthening of T-0 distances and increase of the T volume. Consequently: i) for the saine M 1 volume,Pl-Cpx have larger cell volume compared withSp-Cpx; ii) for a given trivalent cations (R³⁺) content in M1, Al^IV is higher inPl-Cpx than inSp-Cpx. Plots of cell volume vs Ml volume and of M1-O2 vs T-O_nbr bond lengths are a simple way to illustrate the complex intracrystalline relationships which control (Ca Na)_M2, (Si Al^IV)_T and (Mg R³⁺)_M1 substitutions, and thus permit sensitive qualitative discrimination of the pressure regimes of equilibration of mantle clinopyroxenes.

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Klinopyroxene aus Plagioklas-Peridotiten der Insel Zabargad (Rotes Meer) und Verqleich zwischen Hoch- und Tiefdruck-Klinopyroxenen des Mantels

Zusammenfassung Klinopyroxene aus der Peridotit-Pyroxenit-Assoziation der Insel Zabargad (Rotes Meer) wurden eingehend kristallchemisch untersucht, um die inter-kristallinen Bezie-hungen in aus dem Mantel stammenden Klinopyroxenen zu definieren, die unter niedrigem Druck (Plagioklas-Fazies,PI-Cpx) equilibriert wurden.PI-Cpx zeigen typisch ein größeres Zellvolumen (>437 ų) im Vergleich zu jenen aus Knollen von Spinell- und Granat-Spinell-Peridotiten (Sp-Cpx). Das größere Zellvolumen wird hauptsächlich durch größere Mg_M1- und kleinere Al^VI-Besetzungen erreicht, welche das M1-Volumen stark erhöhen. Gleichlaufend verlangt ein Ladungsüberschuß an den O3-Sauerstoffen durch hohe Ca_M2-Besetzungen (> 0,828 Atome pro Formeleinheit) und niedrige Na_M2-Besetzungen ( 0,037 Atome pro Formeleinheit) eine Verlängerung der T-O-Abstände und ein Anwachsen des T-Volumens. Folglich haben für das gleiche M1-Volumen diePl-Cpx ein größeres Zellvolumen gegenüber denSp-Cpx, und ferner ist für einen gegebenen Gehalt an dreiwertigen Kationen (R³⁺) auf M1 das Al^IV inPI-Cpx höher als inSp-Cpx. Diagramme von Zellvolumen gegen Volumen von M1, sowie von M1-O2 gegen T-O_nbr sind ein einfaches Mittel, um die komplexen interkristallinen Beziehungen aufzuzeigen, welche die Substitutionen (Ca Na)_M2, (Si AI_IV)_T und (Mg R³⁺)_M1 beherrschen, sie erlauben eine empfindliche qualitative Unterscheidung der Druckverhältnisse bei der Equilibrierung von Klinopyroxenen aus dem Mantel.

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With 6 Figures     

1Tc-Strontiohilgardit (Ca,Sr)2[B5O8(OH)2Cl] und seine Stellung in der Hilgarditgruppe X2/II[B5O8(OH)2Cl]

Zusammenfassung 1Tc-Strontiohilgardit (Ca, Sr)₂ [B₅O₈(OH)₂,Cl] mit Ca : Sr etwa 1 : 1 ist ein neues Mineral der Hilgarditgruppe. Fundpunkt: Reyersbausen (9° 59,7 E, 51° 36,6 N), Grube Königshall-Hindenburg, Flöz Staßfurt in sylvinitischer Ausbildung.Konstanten : triklin-pedial,a ₀=6,38 Å,b ₀=6,480 Å,c ₀=6,608 Å, =75,4°,=61,2°, =60,5°; tafelige-gestreckte Links- und Re chtskristalle, farblos, wasserunlöslich, piezoelektrisch. Härte 5–7, Dichte 2,99 g cm^–3;n =1,638,n =1,639,n =1,670; 2V =19°.Neue Daten für die Hilgarditgruppe : 2 M (Cc)-Calciumhilgardit (=Hilgardit) =4 Ca₂[B₅O₃(OH)₂Cl], Raumgruppe Cc.3Tc-Calciumhilgardit (=Parahilgardit) = 3 Ca₂[B₅O₃(OH)₂Cl]; trinklin-pedial, ₀=6,31 Å,b =6,484 Å,c ₀=17,50 Å; =84,0°,=79,6°, =60,9°.Die Polymorphiebeziehungen sind geometrisch deutbar durch eine spezielle Art der Polytropie (Stapelung von Links- und Rechtskristallen im Elementarbereich).     

Gypsum as a precursor to pyrrhotite in metamorphic rocks

During low-grade regional metamorphism, pyrrhotite can form from gypsum by the reaction: CaSO₄·2H₂O+Fe _sol. ²⁺ +2C_org.FeS+Ca _sol. ²⁺ +2H₂O+2CO₂. This reaction takes place in the anchizone, below 350°C and might be initiated by the thermal dehydration of gypsum (200°C) and aided by the generation of gaseous hydrocarbons. Evidence for the reaction is the occurrence in dolomitic layers in the Ballachulish Slate, East Larroch quarry, Argyll of lath and swallow-tail shaped quartz+dolomite+pyrrhotite pseudomorphs after gypsum. Quartz+pyrrhotite bodies in slate represent replaced and deformed (mainly flattened) crystals, concretions and possible veinlets of gypsum. Pyrite porphyroblast growth, after the peak of metamorphism and under relatively high fS₂ conditions, failed to destroy some early pyrrhotite because it is encapsulated in quartz. Pyrite-silicate reactions and hydrothermal exhalations have been suggested previously to account for pyrrhotite-enriched horizons in regionally metamorphosed rocks. Replacement of gypsum by pyrrhotite is an additional explanation for pyrrhotite-enriched horizons, especially in dolomitic and graphitic lithologies.     

Multifactorial control of sedimentation patterns in an ocean marginal basin: the Lusitanian Basin (Portugal) during the Kimmeridgian and Tithonian

The Mesozoic Lusitanian Basin developed as a part of the North Atlantic rift system. Tectonic rifting activity was rejuvenated during the Upper Jurassic, leading to intensive differentiation of facies development. Kimmeridgian and Lower Tithonian calcareous and siliciclastic sediments represent basinal and slope, shallow marine, and terrestrial environments. The lithostratigraphic arrangement of facies units is demonstrated. Sediment character, distribution and thicknesses are mainly controlled by synsedimentary faulting, with a partial overprint by uprise of salt diapirs. Eustatic sea level fluctuations, exogenic and biogenic factors resulted in additional control on facies development.Comparing bathymetric development of major basin sections and simplified plotting on a common time scale is a simple tool to unravel the multifactorial control of sedimentation and to test the validity of some biostratigraphic markers.During the Kimmeridgian, paleogeography was mainly determined by intensive subsidence of the basin center, by a large linear uplift zone m the north, and by a high amount of clastic influx. At the end of the stage and during the Tithonian, overall subsidence slowed down and inner basin uplifts arose further south. Degree of clastic input was variable. Thus shallow water carbonates were episodically widespread throughout the basin and mixed calcareous-clastic sequences were common. Sheltering and trapping effects resulted in local facies variations. Towards the Cretaceous the basin sanded up from northern, eastern and, particularly, northwestern directions.

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Zusammenfassung Das mesozoische Lusitanische Becken entstand als Teil des nordatlantischen Riftsystems. Während des Oberjuras lebte die tektonische Aktivität erneut auf und führte zu einer intensiven Differenzierung der faziellen Entwicklung. Die Kalke und Siliziklastika des Kimmeridge und Unteren Tithons, deren lithostratigraphische Beziehungen dargestellt werden, repräsentieren Becken-, Hang- und Flachwasserablagerungen sowie terrestrische Sedimente.Synsedimentäre Tektonik bestimmte überwiegend die Ausbildung, Verteilung und Mächtigkeiten der Sedimente. Halokinese, eustatische Meeresspiegelschwankungen, exogene und biogene Faktoren kontrollierten die Faziesverteilung zusätzlich. Ein Vergleich der bathymetrischen Entwicklung aller grö\eren Beckenprofile und Standardisierung auf eine gemeinsame Zeitachse erlauben, die überlagerung der einzelnen Kontrollfaktoren zu entschlüsseln sowie den Wert einiger biostratigraphischer Bezugshorizonte zu testen.Während des Kimmeridge wurde die Paläogeographie vor allem durch starke Subsidenz des Beckenzentrums sowie durch eine gro\e lineare Hebungszone im Norden und durch hohe klastische Zufuhr bestimmt. Am Ende des Kimmeridge und während des Tithons verlangsamte sich die Subsidenz. Anhebung innerer Beckenteile und schwankende Zufuhr von Klastika bewirkten die episodische Ausbreitung von Flachwasserkarbonaten und die verbreitete Entwicklung gemischt kalkig-klastischer Serien. Abschirmungs- und Abfangeffekte erlaubten kleinräumige Faziesvariationen. Zur Kreide hin verlandete das Becken durch klastische Zufüllung aus nördlicher, östlicher und vor allem nordwestlicher Richtung.

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Resumo Durante o Mesozóico, a Bacia Lusitânica desenvolveu-se como parte do sistema »rift« do Atlântico do Norte. A actividade tectónica, tipo »rifting« renasceu durante o Jurásico Superior, causando uma diferenciaÇÃo intensa no desenvolvimento de fácies. Os sedimentos calcários e siliciclásticos do Kimeridgiano e Titoniano inferior representam ambientes do mar mais ou menos profundo (fundo de bacia, declive, lagoa, delta) e ambientes continentais. O quadro litoestratigráfico das unidades de fácies é elaborado.O carácter, a distribuiÇÃo e a espessura dos sedimentos sÃo sobretudo controlados pela actividade tectónica sinsedimentária. Movimentos halokinéticos, fluctuaÇÕes eustáticas do nível do mar, e factores exogénicos e biológicos resultaram num controle adicional do desenvolvimento de fácies.Uma medida simples para destrinÇar os factores diferentes da sedimentaÇÃo e para testar o valor de alguns »markers« bioestratigráficos é comparar o desenvolvimento batimÊtrico dos coites principais da bacia e estandardizá-los num comum eixo temporal.Durante o Kimeridgiano, a paleogeografia foi dominada pela subsidÊncia intensa do centro da bacia, por um grande levantamento estreito no Norte, e por um grau elevado de introduÇÃo de clásticos. No fim do estágio e durante o Titoniano, a subsidÊncia geral diminuiu-se e novos levantamentos surgiram mais no Sul. O grau de introduÇÃo de clásticos foi variável. Por consequÊncia, calcários de agua pouco profunda alargaram-se por vezes sobre grandes partes da bacia e sequÊncias mistas de calcários e clásticos foram comum.No fim do Jurásico o mar desapareceu por causa de enchimento da bacia por clásticos de proveniÊncia norte, este, e partialmente noroeste.

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The authigenic zeolites of the Aritayn Volcaniclastic Formation, north-east Jordan

In the Aritayn Volcaniclastic Formation, the formation of zeolites is associated with the transformation of sideromelane into palagonite by reaction with percolating water in an open hydrological system. Three vertical zones are described, characterised by fresh sideromelane at the top (zone 1), palagonite-smectite in the middle (zone 2), and zeolites at the bottom (zone 3). Within zone 3, a phillipsite-chabazite sub-zone overlies a faujasite — phillipsite sub-zone. The paragenetic sequence (fresh sideromelane palagonite smectites (saponite montmorillonite) faujasite phillipsite chabazite natrolite calcite) resembles those described in the literature, except for the early formation of smectites in the Jordanian occurrences. Faujasite is more abundant in these zeolitic tuffs than at any other locality in the world that has yet been described, and the tuffs are considered to have excellent potential for beneficiation.