Synthesis of Ca-tourmaline in the system CaO-MgO-Al2O3-SiO2-B2O3-H2O-HCl

Summary. ?Ca-tourmaline has been synthesized hydrothermally in the presence of Ca(OH)₂ and CaCl₂-bearing solutions of different concentration at T = 300–700 °C at a constant fluid pressure of 200 MPa in the system CaO-MgO-Al₂O₃-SiO₂-B₂O₃-H₂O-HCl. Synthesis of tourmaline was possible at 400 °C, but only above 500 °C considerable amounts of tourmaline formed. Electron microprobe analysis and X-ray powder data indicate that the synthetic tourmalines are essentially solid solutions between oxy-uvite, CaMg₃- Al₆(Si₆O₁₈)(BO₃)₃(OH)₃O, and oxy-Mg-foitite, □(MgAl₂)Al₆(Si₆O₁₈)(BO₃)₃(OH)₃O. The amount of Ca ranges from 0.36 to 0.88 Ca pfu and increases with synthesis temperature as well as with bulk Ca-concentration in the starting mixture. No hydroxy-uvite, CaMg₃(MgAl₅)(Si₆O₁₈)(BO₃)₃(OH)₃(OH), could be synthesized. All tourmalines have < 3 Mg and > 6 Al pfu. The Al/(Al + Mg)-ratio decreases from 0.80 to 0.70 with increasing Ca content. Al is coupled with Mg and Ca via the substitutions Al₂□Mg₋₂Ca₋₁ and AlMg₋₁H₋₁. No single phase tourmaline could be synthesized. Anorthite ( + quartz in most runs) has been found coexisting with tourmaline. Other phases are chlorite, tremolite, enstatite or cordierite. Between solid and fluid, Ca is strongly fractionated into tourmaline ( + anorthite). The concentration ratio D = Ca(fluid)/Ca(tur) increases from 0.20 at 500 °C up to 0.31 at 700 °C. For the assemblage turmaline + anorthite + quartz + chlorite or tremolite or cordierite, the relationship between Ca content in tourmaline and in fluid with temperature can be described by the equation (whereby T = temperature in °C, Ca(tur) = amount of Ca on the X-site in tourmaline, Ca( fluid) = concentration of Ca²⁺ in the fluid in mol/l). The investigations may serve as a first guideline to evaluate the possibility to use tourmaline as an indicator for the fluid composition.

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Zusammenfassung. ?Synthese von Ca-Turmelin im System CaO-MgO-Al ₂ O ₃ -SiO ₂ -B ₂ O ₃ -H ₂ O-HCl Im System CaO-MgO-Al₂O₃-SiO₂-B₂O₃-H₂O-HCl wurde Ca-Turmalin hydrothermal aus Ca(OH)₂ and CaCl₂-haltigen L?sungen bei T = 300–700 °C und einem konstanten Fluiddruck von 200 MPa synthetisiert. Die Synthese von Turmalin war m?glich ab 400 °C, aber nur oberhalb von 500 °C bildeten sich deutliche Mengen an Turmalin. Elektronenstrahl-Mikrosondenanalysen und R?ntgenpulveraufnahmen zeigen, da? Mischkristalle der Reihe Oxy-Uvit, CaMg₃Al₆(Si₆O₁₈)(BO₃)₃(OH)₃O, und Oxy-Mg-Foitit, □(MgAl₂)Al₆(Si₆O₁₈)(BO₃)₃(OH)₃O gebildet wurden. Der Anteil an Ca variiert zwischen 0.36 und 0.88 Ca pfu und nimmt mit zunehmender Synthesetemperatur und zunehmender Ca-Konzentration im System zu. Hydroxy-Uvit, CaMg₃(MgAl₅) (Si₆O₁₈)(BO₃)₃(OH)₃(OH), konnte nicht synthetisiert werden. Alle Turmaline haben < 3 Mg und > 6 Al pfu. Dabei nimmt das Al/(Al + Mg)- Verh?ltnis mit zunehmendem Ca-Gehalt von 0.80 auf 0.70 ab. Al ist gekoppelt mit Mg und Ca über die Substitutionen Al₂□Mg₋₂Ca₋₁ und AlMg₋₁H₋₁. Einphasiger Turmalin konnte nicht synthetisiert werden. Anorthit (+ Quarz in den meisten F?llen) koexistiert mit Turmalin. Andere Phasen sind Chlorit, Tremolit, Enstatit oder Cordierit. Ca zeigt eine deutliche Fraktionierung in den Festk?rpern Turmalin (+ Anorthit). Das Konzentrationsverh?ltnis D = Ca(fluid)/Ca(tur) nimmt von 0.20 bei 500 °C auf 0.31 bei 700 °C zu. Für die Paragenese Turmalin + Anorthit + Quarz mit Chlorit oder Tremolit oder Cordierit gilt folgende Beziehung zwischen Ca-Gehalt in Turmalin und Fluid und der Temperatur: (wobei T = Temperatur in °C, Ca(tur) = Anteil an Ca auf der X-Position in Turmalin, Ca(fluid) = Konzentration von Ca²⁺ im Fluid in mol/l). Die Untersuchungen dienen zur ersten Absch?tzung, ob Turmalin als Fluidindikator petrologisch nutzbar ist.

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Received July 24, 1998;/revised version accepted October 21, 1999     

Calciocarbonatite and magnesiocarbonatite rocks and magmas represented in the system CaO-MgO-CO2-H2O at 0.2 GPa

Summary ?The low-pressure eutectic for the coprecipitation of calcite, portlandite, and periclase/brucite (with H₂O-rich vapor) has served as a model for the existence and crystallization of carbonatite magmas. Attempts to determine conditions for the appearance of dolomite at this eutectic have been unsuccessful. We have discovered a second low-temperature eutectic for more magnesian liquids which excludes portlandite and includes dolomite (all results are vapor-saturated). Addition of Ca(OH)₂-Mg(OH)₂ to CaCO₃-MgCO₃ at 0.2 GPa depresses the liquidus to temperatures below the crest of the calcite-dolomite solvus; the vapor-saturated liquidus surface falls steeply, and the field boundary for liquids coexisting with calcite and periclase reaches a peritectic at 880 °C, where a narrow field for liquidus dolomite begins, extending down to the eutectic at 659 °C for the coprecipitation of calcite, dolomite and periclase (brucite should replace periclase at slightly higher pressures). The calcite liquidus is very large. The field boundary for coexistence of calcite and dolomite extends approximately in the direction from CaMg(CO₃)₂ towards Mg(OH)₂. The results illustrate conditions for the formation of mineral-specific cumulates from variable magma compositions. Hydrous (or sodic) carbonate-rich liquids with compositions from CaCO₃ to CaMg(CO₃)₂ will precipitate calcite-carbonatites first, followed by calcite-dolomite-carbonatites, with the prospect of precipitating dolomite-carbonatite alone through a limited temperature interval, and with periclase joining the assemblage in the closing stages. Periclase in the Fe-free system may represent the ubiquitous occurrence of magnetite in natural carbonatites. The restricted range for the precipitation of dolomite-carbonatites adds credibility to the evidence for primary magnesiocarbonatite (near-dolomite composition) magmas. Magnesiocarbonatite magmas can precipitate much calcite-carbonatite rock.

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Zusammenfassung ?Calciokarbonatitische und magnesiokarbonatitische Gesteine und Magmen im System CaO-MgO-CO ₂ -H ₂ O bei 0.2 GPa Das Niedrigdruck-Eutektikum der gemeinsamen Ausscheidung von Calcit, Portlandit und Periklas/Brucit (mit H₂O-reicher Fluidphase) diente als Modell um die Existenz und Kristallisation karbonatitischer Magmen zu erkl?ren. Versuche die Bedingungen des Auftretens von Dolomit an diesem Eutektikum zu bestimmen blieben bisher ergebnislos. Wir entdeckten ein zweites Niedrigtemperatur-Eutektikum für magnesiumreichere Schmelzen, das Portlandit ausschlie?t, aber Dolomit inkludiert (alle Ergebnisse bei Fluids?ttigung). Die Zugabe von Ca(OH)₂-Mg(OH)₂ zu CaCO₃-MgCO₃ bei 0.2 GPa senkt den Liquidus auf Temperaturen unter die Solvus-Schwelle von Calcit-Dolomit. Die fluidges?ttigte Liquidusfl?che verl?uft steil und die Grenzfl?che von Schmelze, die mit Calcit und Periklas koexistiert erreicht ein Peritektikum bei 880 °C. Dort ?ffnet sich ein schmales Feld für Liquidus-Dolomit, das bis zum Eutektikum bei 659 °C reicht, an dem Calcit, Dolomit und Periklas (Brucit sollte Periklas bei geringfügig h?heren Drucken ersetzen) gemeinsam ausgeschieden werden. Der Calcit- Liquidus ist sehr gro?. Die Linie an der Calcit und Dolomit koexistieren erstreckt sich ungef?hr von CaMg(CO₃)₂ zu Mg(OH)₂. Die Ergebnisse zeigen die Bildungsbedingungen für die Bildung mineralspezifischer Kumulate aus unterschiedlichen Magmenzusammensetzungen. Aus w?ssrigen (oder Na-reichen) karbonatreichen Schmelzen mit Zusammensetzungen zwischen CaCO₃ und CaMg(CO₃)₂ werden sich zuerst Calcitkarbonatite und dann Calcit-Dolomitkarbonatite ausscheiden, mit der M?glichkeit Dolomitkarbonatite über ein sehr eingeschr?nktes Temperaturintervall zu bilden und mit Periklas, der zu dieser Vergesellschaftung im Endstadium hinzukommt. Periklas im Fe-freien System k?nnte das weitverbreitete Analog zu Magnetit in natürlichen Karbonatiten sein. Der enge Bereich für die Ausscheidung von Dolomitkarbonatiten untermauert die Existenz prim?rer magnesiokarbonatitischer Magmen (nahe der Zusammensetzung von Dolomit). Magnesiokarbonatitische Magmen k?nnen daher entsprechende Mengen an calcitkarbonatitischen Gesteinen ausscheiden.

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Received July 20, 1998;/revised version accepted August 18, 1999     

Phase relations in the MgO–P2O5–H2O system and the stability of phosphoellenbergerite: petrological implications

The polymorphic relations for Mg₃(PO₄)₂ and Mg₂PO₄OH have been determined by reversed experiments in the temperature-pressure (T-P) range 500–1100 °C, 2–30 kbar. The phase transition between the low-pressure phase farringtonite and Mg₃(PO₄)₂-II, the Mg analogue of sarcopside, is very pressure dependent and was tightly bracketed between 625 °C, 7 kbar and 850 °C, 9 kbar. The high-temperature, high-pressure polymorph, Mg₃(PO₄)₂-III, is stable above 1050 °C at 10 kbar and above 900 °C at 30 kbar. The low-pressure stability of farringtonite is in keeping with its occurrence in meteorites. The presence of iron stabilizes the sarcopside-type phase towards lower P. From the five Mg₂PO₄OH polymorphs only althausite, holtedahlite, β-Mg₂PO₄OH (the hydroxyl analogue of wagnerite) and ɛ-Mg₂PO₄OH were encountered. Relatively speaking, holtedahlite is the low-temperature phase (<600 °C), ɛ-Mg₂PO₄OH the high-temperature, low-pressure phase and β-Mg₂PO₄OH the high-temperature, high-pressure phase, with an intervening stability field for althausite which extends from about 3 kbar at 500 °C to about 12 kbar at 800 °C. Althausite and holtedahlite are to be expected in F-free natural systems under most geological conditions; however, wagnerite is the most common Mg-phosphate mineral, implying that fluorine has a major effect in stabilizing the wagnerite structure. Coexisting althausite and holtedahlite from Modum, S. Norway, show that minor fluorine is strongly partitioned into althausite (K_D ^F/OH≈ 4) and that holtedahlite may incorporate up to 4 wt% SiO₂. Synthetic phosphoellenbergerite has a composition close to (Mg_0.9□_0.1)₂Mg₁₂P₈O₃₈H_8.4. It is a high-pressure phase, which breaks down to Mg₂PO₄OH + Mg₃(PO₄)₂ + H₂O below 8.5 kbar at 650 °C, 22.5 kbar at 900 °C and 30 kbar at 975 °C. The stability field of the phosphate end-member of the ellenbergerite series extends therefore to much lower P and higher T than that of the silicate end-members (stable above 27 kbar and below ca. 725 °C). Thus the Si/P ratio of intermediate members of the series has a great barometric potential, especially in the Si-buffering assemblage with clinochlore + talc + kyanite + rutile + H₂O. Application to zoned ellenbergerite crystals included in the Dora-Maira pyrope megablasts, western Alps, reveals that growth zoning is preserved at T as high as 700–725 °C. However, the record of attainment of the highest T and/or of decreasing P through P-rich rims (1 to 2 Si pfu) is only possible in the presence of an additional phosphate phase (OH-bearing or even OH-dominant wagnerite in these rocks), otherwise the trace amounts of P in the system remain sequestered in the core of Si-rich crystals (5 to 8 Si pfu) and can no longer react. Received: 7 April 1995 / Accepted: 12 November 1997     

Phase relations and chemistry of Ti-rich K-richterite-bearing mantle assemblages: an experimental study to 8.0 GPa in a Ti-KNCMASH system

Experiments have been conducted in a peralkaline Ti-KNCMASH system representative of MARID-type bulk compositions to delimit the stability field of K-richterite in a Ti-rich hydrous mantle assemblage, to assess the compositional variation of amphibole and coexisting phases as a function of P and T, and to characterise the composition of partial melts derived from the hydrous assemblage. K-richterite is stable in experiments from 0.5 to 8.0 GPa coexisting with phlogopite, clinopyroxene and a Ti-phase (titanite, rutile or rutile + perovskite). At 8.0 GPa, garnet appears as an additional phase. The upper T stability limit of K-richterite is 1200–1250 °C at 4.0 GPa and 1300–1400 °C at 8.0 GPa. In the presence of phlogopite, K-richterite shows a systematic increase in K with increasing P to 1.03 pfu (per formula unit) at 8.0 GPa/1100 °C. In the absence of phlogopite, K-richterite attains a maximum of 1.14 K pfu at 8.0 GPa/1200 °C. Titanium in both amphibole and mica decreases continuously towards high P with a nearly constant partitioning while Ti in clinopyroxene remains more or less constant. In all experiments below 6.0 GPa ΣSi + Al in K-richterite is less than 8.0 when normalised to 23 oxygens+stoichiometric OH. Rutiles in the Ti-KNCMASH system are characterised by minor Al and Mg contents that show a systematic variation in concentration with P(T) and the coexisting assemblage. Partial melts produced in the Ti-KNCMASH system are extremely peralkaline [(K₂O+Na₂O)/Al₂O₃ = 1.7–3.7], Si-poor (40–45 wt% SiO₂), and Ti-rich (5.6–9.2 wt% TiO₂) and are very similar to certain Ti-rich lamproite glasses. At 4.0 GPa, the solidus is thought to coincide with the K-richterite-out reaction, the first melt is saturated in a phlogopite-rutile-lherzolite assemblage. Both phlogopite and rutile disappear ca. 150 °C above the solidus. At 8.0 GPa, the solidus must be located at T≤1400 ^°C. At this temperature, a melt is in equilibrium with a garnet- rutile-lherzolite assemblage. As opposed to 4.0 GPa, phlogopite does not buffer the melt composition at 8.0 GPa. The experimental results suggest that partial melting of MARID-type assemblages at pressures ≥4.0 GPa can generate Si-poor and partly ultrapotassic melts similar in composition to that of olivine lamproites. Received: 23 December 1996 / Accepted: 20 March 1997     

Glass-bearing inclusions in Nakhla(SNC meteorite) augite: heterogeneouslytrapped phases

Summary Nakhla augite and olivine grains commonly contain glass-bearing inclusions. In contrast to olivines, augites host only one type of multiphase inclusions which consists of euhedral to subhedral augite, Ti-magnetite and pigeonite plus silica-rich glass and a bubble. No fractures surround these inclusions, making it likely that they are of a pristine composition. Heating experiments with a final temperature of 1150 °C were done for the first time with Nakhla augite inclusions. During heating the glass melted and crystals inside the inclusions were dissolved in the melt whereby its chemical composition changed. The quenched glass is poorer in SiO₂ and Al₂O₃ and richer in CaO, FeO and MgO compared to unheated inclusion glass. Our in situ analyses allowed us to estimate the initial composition of a liquid co-existing with Nakhla augite at 1150 °C and 1 atm pressure. Several features of Nakhla, such as the high Fe/Mg ratio of the augite, which is out of equilibrium with the glass, the highly variable alkali content and the Na/K ratio of the glasses are incompatible with the standard model that states that SNC meteorites are all igneous rocks formed from basaltic magmas. Our results on re-melted glasses suggest a more complex and possibly non-magmatic genesis of Nakhla. Both types of glass-bearing inclusions (those hosted by augite or olivine) could represent heterogeneously trapped mineral + glass inclusions. Those hosted by augites mimic at least in part parental melt inclusions. However, the quenched glass is out of equilibrium with the host with respect to the Fe/Mg ratio and has too much compositional variation to be representative of a parental melt.

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Zusammenfassung Glasführende Einschlüsse im Augit von Nakhla (SNC-Meteorit): Heterogeneingeschlossene Phasen Augite und Olivine im Achondriten Nakhla enthalten h?ufig glasführende Einschlüsse. Im Gegensatz zu den Olivinen enthalten die Augite nur einen Typ Multiphasen-Einschlu?, welcher aus idiomorphem bis subidiomorphem Augit, Ti-Magnetit, Pigeonit und einem SiO₂-reichen Glas mit Blase besteht. Diese Einschlüsse sind nicht von Sprüngen umgeben, was es wahrscheinlich macht, dass sie ihre ursprüngliche Zusammensetzung unver?ndert erhalten haben. Erstmals wurden Schmelz-Experimente mit Endtemperaturen von 1150 °C an Nakhla Augiten durchgeführt. In diesen Experimenten schmolz das Glas der Einschlüsse, l?ste die koexistierenden kristallinen Phasen auf und ?nderte dabei seine chemische Zusammensetzung. Das durch Abschrecken dieser Schmelze erzeugte Glas ist ?rmer an SiO₂ und Al₂O₃ und reicher an CaO, FeO und MgO als das ursprüngliche Einschlu?glas. Diese in situ-Analyse erlaubt eine Absch?tzung der ursprünglichen Zusammensetzung einer Schmelze im Gleichgewicht mit Nakhla Augit bei 1150 °C und 1 atm Druck. Einige Eigenschaften von Nakhla, wie das hohe Fe/Mg-Verh?ltnis des Augites, welches nicht im Gleichgewicht mit dem Glas ist, die variablen Alkali-Gehalte und die Na/K-Verh?ltnisse im Glas sind inkompatibel mit dem Standard-Modell für die SNC-Meteorite, welches diese als magmatische Gesteine basaltischer Herkunft sieht. Unsere Ergebnisse weisen auf eine komplexe, m?glicherweise nicht-magmatische Entstehung von Nakhla hin. Sowohl die glasführenden Einschlüsse im Olivin als auch jene im Augit von Nakhla k?nnten Produkte eines heterogenen Aufsammelns von Mineral plus Glas sein. Die Einschlüsse im Augit imitieren zumindest zum Teil Schmelzeinschlüsse. Allerdings sind sie mit ihrem Fe/Mg – Verh?ltnis nicht im Gleichgewicht mit dem Augit und sind auch in ihrer Zusammensetzung zu inhomogen, um für ein m?gliches Mutter-Magma repr?sentativ zu sein.

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Received April 10, 2000; revised version accepted October 19, 2000     

P-T paths and tectonic evolution of shear zones separating high-grade terrains from cratons: examples from Kola Peninsula (Russia) and Limpopo Region (South Africa)

Summary ?The petrology and P-T evolution of mica schists from two regional scale tectonic (shear) zones that separate high grade terrains (“mobile belts”) from cratons are described. These are the 2.4–1.9 Ga Tanaelv Belt, a suture zone that separates the Lapland granulite complex from the Karelian craton (Kola Peninsula–Fennoscandia), and the 2.69 Ga Hout River Shear Zone that separates the > 2.9 Ga Kaapvaal craton from the 2.69 Ga South Marginal Zone of the Limpopo high-grade terrain (South Africa). Two metamorphic zones are identified in strongly deformed mica schists from the 1.9 Ga Korva Tundra Group of the Tanaelv belt: (1) a chlorite-staurolite zone tectonically overlaying gneisses of the Karelian craton, and (2) a kyanite-biotite zone tectonically underlying garnet amphibolites of the Tanaelv Belt, which are in tectonic contact with the Lapland granulite complex. The prograde reaction Chl+St+Ms ↠ Ky+Bt+Qtz+H₂O clearly defines a boundary between zones (1) and (2). Rotated garnet porphyroblasts from zone (1) contain numerous inclusions (Otz, Chl, Ms), and show clear Mg/Fe chemical zoning, suggesting garnet growth during prograde metamorphism. The metamorphic peak, T = 650°C and P = 7.5 kbar, is recorded in the kyanite-biotite zone and characterized by unzoned snowball garnet. In many samples of mica schists euhedral garnet porphyroblasts of the retrograde stage are completely devoid of mineral inclusions while N _Mg decreases from core to rim, indicating a decrease in P-T from 650°C, 7.5 kbar to 530°C, 5 kbar. The Hout River Shear Zone (South Africa) shows metamorphic zonation from greenschists through epidote amphibolites to garnet amphibolites. Rare strongly deformed mica schists (Chl+Grt+Pl+Ms+Bt+Qtz) occur as thin layers among epidote-amphibolites only. Garnet porphyroblasts in the schists are similar to that of the Tanaelv Belt recording a prograde P-T path with peak conditions of T = 600°C and P∼ 5.5 kbar. The retrograde stage is documented by the continuous reaction Prp+2Ms+Phl ↠ 6Qtz+3East recording a minimum T = 520°C and P ∼ 3.3 kbar. Similar narrow clock-wise P-T loops recorded in mica schists from both studied shear zones suggest similarities in the geodynamic history of both shear zones under consideration.

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Zusammenfassung ?P-T Pfade und tektonische Entwicklung von Scherzonen, die hochgradige Terranes von Kratonen trennen: Zwei Beispiele von der Halbinsel Kola (Russland) und der Limpopo-Region (Südafrika) Die Petrologie und P-T Entwicklung von Glimmerschiefern aus zwei regionalen tektonischen Scherzonen, die hochgradige Terranes (“mobile belts”) von Kratonen trennen, werden beschrieben. Diese sind der 2.4−1.9 Ga Tanaev Belt, eine Suturzone, die die Lappland Granulite vom karelischen Pluton (Halbinsel Kola - Fennoskandien) trennt, sowie die 2.69 Ga Hout River Shear Zone, die den > 2.9 Ga Kaapvaal Kraton von der 2.69 Ga South Marginal Zone des hochgradigen Limpopo Terranes (Südafrika) trennt. Zwei metamorphe Zonen sind in stark deformierten Glimmerschiefern der 1.9 Ga Korva Tundra Group zu unterscheiden: (1) eine Chlorit-Staurolith-Zone, die den Gneisen des karelischen Kratons auflagert, und (2) eine Kyanit-Biotit-Zone, die die Granatamphibolite des Tanaev Belt unterlagert und in tektonischem Kontakt mit dem Lappland Granulitkomplex steht. Die prograde Reaktion Chl+St+Ms ↠ Ky+Bt+Qtz+H₂O trennt die beiden Zonen. Rotierte Granatporphyroblasten aus der Zone (1) enthalten zahlreiche Einschlüsse (Qtz, Chl, Ms) und zeigen eine Mg/Fe Zonierung, die Granatwachstum w?hrend des prograden Metamorphosestadiums nahelegen. Der Metamorphoseh?hepunkt (650°C, 7.5 kbar) wurde in der Kyanit-Biotit-Zone erreicht und ist durch nicht zonierte Schneeballgranate charakterisiert. In vielen Glimmerschieferproben sind die euhedralen Granatporphyroblasten des retrograden Stadiums vollkommen einschlu?frei und N _Mg nimmt vom Kern zum Rand hin ab. Das zeigt eine Abnahme der P-T Bedingungen von 650°C, 7.5 kbar auf 530°C, 5 kbar an. Die Hout River Shear Zone in Südafrika zeigt eine metamorphe Zonierung von Grünschiefern, über Epidotamphibolite zu Granatamphiboliten. Selten kommen stark deformierte Glimmerschiefer (Chl+Grt+Pl+Ms+Bt+Qtz) als dünne Lagen zwischen den Epidotamphiboliten vor. Die Granatporphyroblasten sind ?hnlich wie die aus dem Tanaev Belt und belegen eine prograde P-T Entwicklung mit Peak-Bedingungen von 600°C und ≈ 5.5 kbar. Das retrograde Stadium ist durch die kontinuierliche Reaktion Prp+2Ms+Phl ↠ 6Qtz+3East mit minimal 530°C und ≈ 3.3 kbar dokumentiert. Die sehr ?hnlichen P-T Pfade der Glimmerschiefer belegen ?hnlichkeiten in der geodynamischen Geschichte der beiden bearbeiteten Scherzonen.

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Received January 29, 1999;/revised version accepted August 10, 1999     

Mg-Fe partitioning between silicate spinel and magnesiowüstite at high pressure: experimental determination and calculation of phase relations in the system Mg2SiO4-Fe2SiO4

 Mg-Fe partitioning experiments between (Mg,Fe)₂SiO₄ spinel and (Mg,Fe)O magnesiowüstite were carried out at pressures of 17–21.3 GPa at temperatures of 1400 and 1600 °C, using a multi-anvil apparatus, in order to determine interaction parameters of spinel and magnesiowüstite solid solutions and also to constrain the equilibrium boundaries of the postspinel transition in the Fe-rich side in the system Mg₂SiO₄-Fe₂SiO₄. The obtained values of the interaction parameters were 3.4 ± 1.5 and 13.9 ± 1.4 kJ mol⁻¹, respectively, for spinel and magnesiowüstite solid solutions at 19 GPa and 1600 °C. The partitioning data in the system Mg₂SiO₄-Fe₂SiO₄ at 1400 and 1600 °C showed that the transition boundary between spinel and the mixture of magnesiowüstite and stishovite has a negative dP/dT slope. Using the above interaction parameters and available thermodynamic data of the Mg₂SiO₄ and Fe₂SiO₄ end members, the transition boundaries of spinel to the mixture of magnesiowüstite and stishovite were calculated. Within the uncertainties of the data used, the calculated boundaries are in good agreement with the boundaries at 1400 and 1600 °C experimentally determined in this study. The dissociation boundary of Fe₂SiO₄ spinel to wüstite and stishovite, calculated from the thermodynamic data, has a negative slope of −1.5 ± 0.6 MPa K⁻¹. Received: 18 February 1998 / Revised, accepted: 18 October 1999     

Base metal – platinum-group element sulfidesfrom the Urals and the Eastern Alps:characterization and significance formineral systematics

Summary ?A mineralogical classification of sulfides containing base metals (BM) and platinum group elements (PGE) is proposed based on BM-PGE ratios. Group A comprises BM sulfides carrying PGE as trace or minor elements (e.g., pentlandite). Group B is characterized by BM/PGE > 1 comprising kharaelakhite and some poorly defined minerals (thiospinels and monosulfides) which are described in detail. In group C, all sulfides with BM/PGE < 1 are summarized, comprising PGE-rich thiospinel, minerals related to the thiospinel group (e.g. xingzhongite, konderite, inaglyite), and the Pd-Pt±Ni sulfides. A number of BM-PGE sulfides are described from podiform chromite occurrences in ultramafic portions of ophiolite complexes in the southern Urals (Kempirsai, Kazakhstan) and the Eastern Alps (Kraubath, Austria). Copper- and (Ir, Rh, Pt)-rich thiospinel (general formula AB₂S₄, with A = Cu, Ni, Fe and B = Ir, Rh, Pt) is present in complex assemblages in Kraubath, usually intergrown with laurite, Pt-Fe alloy and Rh sulfide. These thiospinels are commonly associated with lamellae and inclusions of Ni-and/or Fe-rich (Ir, Rh) sulfide showing either monosulfide or BM-rich thiospinel stoichiometry. In massive chromitite from Kempirsai, (Ni,Cu,Fe,Ir,Rh,Os) sulfides are intergrown with laurite-erlichmanite, Ir-Os alloy, and rarely, PGE sulfarsenides (e.g. irarsite), and usually have monosulfide (BM,PGE)S compositions. A small number of grains have (BM+PGE)/S matching PGE-rich thiospinel (cuproiridsite) and BM-rich thiospinel (Ni,Cu,Fe)_1.5(Ir,Rh)_1.5S₄. In the occurrences studied, monosulfides exhibit sulfur-deficient stoichiometries (e.g., (BM,PGE)_1−xS) and are characterized by BM/PGE ranging from 0.8 to 2.2. Although anisotropic in reflected light, their reflectance spectra (Y% = 33–38) differ only slightly from those of isotropic cuproiridsite and cuprorhodsite (Y% = 36–38). At least three groups of monosulfides can be distinguished on chemical grounds using literature data: monosulfides dominated by Ni and Ir (“iridian millerite”) with BM/PGE ranging from 1.6 to 5.9, monosulfides dominated by Fe and Rh (“rhodian pyrrhotite”) with BM/PGE ranging from 1.6 to 7.1, and monosulfides dominated by Cu, Ir or Rh (“xingzhongite”-type) with BM/PGE ranging from 0.6 to 1.1. While the first two types presumably crystallize in a hexagonal NiAs structure and exhibit extensive solid solution between each other, xingzhongite is cubic (BM-rich thiospinel?) and usually poor in Ni and Fe. Monosulfides and thiospinel may form from PGE-rich base metal sulfide liquids after cooling and equilibration in chromite-precipitating magmatic systems.

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Zusammenfassung ?Buntmetall-PGE-Sulfide aus dem Ural und den Ostalpen: Charakterisierung und Bedeutung für die Mineral-Systematik In diesem Beitrag wird eine Einteilung von Sulfiden mit bedeutenden Konzentrationen von Buntmetallen (BM) und Platingruppenelementen (PGE) aufgrund ihrer BM/PGE-Verh?ltnisse vorgestellt. Gruppe A enth?lt Buntmetallsulfide mit Spuren- oder Nebenelementgehalten von PGE (z.B. Pentlandit). Sulfide der Gruppe B sind charakterisiert durch BM/PGE-Verh?ltnisse > 1, z.B. Kharaelakhit sowie einige schlecht definierte Minerale (Thiospinelle und Monosulfide), die im folgenden n?her beschrieben werden. In Gruppe C werden alle Sulfide mit BM/PGE < 1 zusammengefasst, wie z.B. PGE-reiche Thiospinelle, einige mit Thiospinell verwandte Minerale (z.B. Xingzhongit, Konderit, Inaglyit), sowie die Pd-Pt±Ni Sulfide. Verschiedene BM-PGE Sulfide treten als Einschlüsse in ophiolitischen podiformen Chromiten im Südural (Kempirsai, Kasachstan) und in den Ostalpen (Kraubath, ?sterreich) auf. In Kraubath sind Cu- und (Ir, Rh, Pt)-reiche Thiospinelle (generelle Formel AB₂S₄, mit A = Cu, Ni, Fe und B = Ir, Rh, Pt) in Verwachsung mit Laurit, Pt-Fe Legierungen und Rh-Sulfiden recht h?ufig. Soche Thiospinelle sind manchmal mit Lamellen und winzigen Einschlüssen eines Ni- und/oder Fe-reichen (Ir, Rh)-Sulfids assoziiert, das st?chiometrisch entweder einem Monosulfid oder einem BM-reichen Thiospinell entspricht. In massiven Chromititen von Kempirsai sind (Ni, Cu, Fe, Ir, Rh, Os)-Monosulfide mit Laurit-Erlichmanit, Ir-Os Legierungen und selten PGE-Sulfarseniden (Irarsit) vergesellschaftet. Die (BM+PGE)/S Verh?ltnisse einiger K?rner entsprechen denen von PGE-reichem Thiospinell (Cuproiridsit) bzw. BM-reichem Thiospinell [(Ni,Cu,Fe)_1.5(Ir,Rh)_1.5S₄]. In den meisten F?llen weisen die Monosulfide leichte Schwefeldefizite auf [z.B. (BM,PGE)_1−xS] und sind charakterisiert durch BM/PGE Verh?ltnisse von 0.8 bis 2.2. Obwohl sie im Auflicht, soweit erkennbar, schwach anisotrop sind, differieren ihre Reflexionsspektren (Y% = 33–38) nur schwach von isotropem Cuproiridsit und Cuprorhodsit (Y% = 36–38). Zumindest drei chemische Gruppen von Monosulfiden konnten anhand einer Literaturrecherche identifiziert werden: Ni- und Ir-dominierte Monosulfide (“Iridium-Millerit”) haben BM/PGE Verh?ltnisse von 1.6 bis 5.9; Fe- und Rh-dominierte Monosulfide (“Rhodium-Magnetkies”) haben BM/PGE Verh?ltnisse von 1.6 bis 7.1; Cu-, Ir oder Rh-dominierte Minerale vom “Xingzhongit-Type” habben BM/PGE-Verh?ltnisse von 0.6 bis 1.1. Die ersten beiden Typen kristallisieren wahrscheinlich in einer hexagonalen NiAs-Struktur und weisen weitgehende Mischbarkeiten miteinander auf. Xingzhongit dagegen ist kubisch (BM-reicher Thiospinell?) und hat general niedrige Ni- und Fe-Gehalte BM-PGE-Monosulfide und Thiospinelle bilden sich wahrscheinlich aus kleinen PGE- und BM-reichen Sulfidschmelztropfen bei der Abkühlung und ?quilibrierung von Chromit.

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Received June 17, 1998;/Revised version accepted July 1, 1999     

Multiple phase transitions of leonite-type compounds: optical, calorimetric, and X-ray data

Summary Low-temperature phase transitions of leonite-type compounds, K₂Me²⁺(SO₄)₂ · 4H₂O (Me = Mg, Mn, Fe), are investigated by temperature dependent measurements of single-crystal X-ray reflection intensities and lattice parameters. The transition temperatures and the progress of the transitions are determined by birefringence data and differential scanning calorimetry. The cause for the phase transitions of leonite-type compounds is a dynamic disorder of sulphate groups at room temperature (C2/m), that freezes in to an ordered structure (I2/a) at −4(1) °C in leonite, K₂Mg(SO₄)₂ · 4H₂O. At −153(1) °C the crystal structure switches to another ordered phase (P2₁/a). The Mn analogue shows the same succession with transition temperatures at −68(1) °C and −104(1) °C. The disordered room temperature structure of the isotypic mineral mereiterite, K₂Fe(SO₄)₂ · 4H₂O, transforms directly to the ordered P2₁/a structure at 3(2) °C. Analysis of X-ray intensities and of excess birefringence reveals that the displacive I2/a ⇔ P2₁/a phase transition of leonite and Mn-leonite is first order. According to Landau theory the C2/m ⇔ I2/a (leonite, Mn-leonite) and C2/m ⇔ P2₁/a (mereiterite) order-disorder transitions are almost tricritical. Received March 7, 2001; revised version accepted June 27, 2001     

Batiferrite, Ba[Ti2Fe10]O19, a new ferrimagnetic magnetoplumbite-type mineral from the Quaternary volcanic rocks of the western Eifel area, Germany

Summary Batiferrite, ideally Ba[Ti₂Fe₁₀]O₁₉, was found in the Quaternary volcanic rocks near üdersdorf, Graulai, and Altburg, western Eifel area, Germany. The new mineral typically occurs as euhedral platy grains in cavities of melilite- and leucite-nephelinite basalts. Associated minerals are hematite, magnetite, titanite, g?tzenite, clinopyroxene, nepheline, and biotite. It exhibits a hexagonal tabular habit flattened on {0001}, diameter 0.5–1 mm, thickness 20–125 μm, and {10&1macr;3}, {10&1macr;0} as observable forms. The mineral is opaque, of black color with submetallic lustre, and shows a ferrimagnetic behavior. VHN₅₀ is 793 with a range of 710–841 from ten indentations. The quantitative reflectance measurements of R_o/R_e on oriented grains in air and oil immersion, respectively, are [%]: for 470 nm 22.1/20.1 and 8.4/7.1, for 546 nm 21.0/19.4 and 7.8/6.6, for 589 nm 20.2/18.8 and 7.4/6.3, and for 650 nm 19.3/18.3 and 6.8/5.9. The bireflectance is distinct (air) to weak (oil), and parallel (0001) a moderate anisotropy with straight extinction can be observed. Typical microprobe analyses give [wt%] K₂O 0.28–0.33, Na₂O 0.17–0.20, SrO 0.46–0.55, BaO 11.80–12.17, MgO 1.27–1.47, Al₂O₃ 0.31–0.33, TiO₂ 13.11–13.63, MnO 2.38–2.57, Fe₂O₃ 61.36–63.12, FeO 5.49–5.86 (Fe³⁺/Fe²⁺ calculated for charge compensation), which is equivalent to (Ba_0.84Na_0.06K_0.06Sr_0.05)_1.01(Fe_8.48 ³⁺Fe_0.86 ²⁺Ti_1.82Mg_0.37Mn_0.37Al_0.06)_11.96O₁₉ as the average composition based on 19 oxygen atoms. Batiferrite is a magnetoplumbite-type mineral with hexagonal symmetry, space group P6 ₃ /mmc (no. 194), a = 5.909(1) ?, c = 23.369(4) ?, V = 706.6(2) ?³, Z = 2, and a calculated density of 5.016 gcm⁻³. The structure was refined to R1 = 0.031 for 278 unique reflections with F_o ² > 4σ (F_o ²) and R1 = 0.079 for all 452 unique observations using single crystal X-ray data. The strongest reflections of the X-ray powder diffraction pattern are [d _obs, I/I_o, (hkl)]: 2.631, 100, (114); 2.799, 80, (107); 1.478, 70, (220); 2.429, 60, (203); 1.672, 50, (217). The new mineral is comparable to the other Ba containing magnetoplumbite-type minerals haggertyite and hawthorneite, the iron content, however, is much higher and in the range of magnetoplumbite. The large cation site (A) is dominated by Ba, and four of the five remaining crystallographic cation sites in the structure are dominated by Fe (M1, 2, 3, 5), the octahedrally coordinated M4-site is dominated by Ti. No oxygen vacancy on the O3-site like in plumboferrite can be observed. Batiferrite is named for its main chemical composition and the relationship to the M-type hexaferrites (polytype 5H).

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Zusammenfassung Batiferrit, ein neues ferrimagnetisches Mineral des Magnetoplumbit-Typs aus den quart?ren Vulkaniten der West-Eifel, Deutschland Das neue Mineral Batiferrite, mit der Idealformel Ba[Ti₂Fe₁₀]O₁₉, wurde an drei Fundpunkten in den Quart?ren Vulkangesteinen der westlichen Eifel, Deutschland, in der N?he von üdersdorf, Graulai und Altburg gefunden. Das neue Mineral tritt typischerweise bl?ttchenf?rmig in kleinen Hohlr?umen von Melilith- und Leucit-Nephelininit Basalten auf. Vergesellschaftete Minerale sind H?matit, Magnetit, Titanit, G?tzenit, Klinopyroxen, Nephelin und Biotit. Der Habitus ist hexagonal tafelig nach {0001}, mit einem Durchmesser von 0.5–1 mm und einer Dicke von 20–125 μm, zus?tzlich k?nnen die Formen {10&1macr;3} und {10&1macr;0} beobachtet werden. Das Mineral ist opak, hat eine schwarze Farbe mit einem leicht metallischen Glanz, und ist ferromagnetisch. Die H?rte VHN₅₀ ist 793 mit einem Bereich von 710–841 aus 10 Eindruckbestimmungen. Die quantitativen Reflexionsmessungen von R_o/R_e an orientierten K?rnern in Luft beziehungsweise ?limmersion, ergaben [%]: für 470 nm 22.1/20.1 und 8.4/7.1, für 546 nm 21.0/19.4 und 7.8/6.6, für 589 nm 20.2/18.8 und 7.4/6.3, und für 650 nm 19.3/18.3 und 6.8/5.9. Die Bireflexion ist deutlich (Luft) bis schwach (?l) und parallel (0001) kann eine mittlere Anisotropie mit gerader Ausl?schung beobachtet werden. Eine typische Mikrosondenanalyse ergibt [wt%] K₂O 0.28–0.33, Na₂O 0.17–0.20, SrO 0.46–0.55, BaO 11.80–12.17, MgO 1.27–1.47, Al₂O₃ 0.31–0.33, TiO₂ 13.11–13.63, MnO 2.38–2.57, Fe₂O₃ 61.36–63.12, FeO 5.49–5.86 (Fe³⁺/Fe²⁺ berechnet zum Ladungsausgleich), die mittlere chemische Formel auf der Basis von 19 Sauerstoffatomen lautet (Ba_0.84Na_0.06K_0.06Sr_0.05)_1.01 (Fe_8.48 ³⁺Fe_0.86 ²⁺Ti_1.82Mg_0.37Mn_0.37Al_0.06)_11.96O ₁₉. Batiferrit ist ein Mineral der Magnetoplumbitgruppe, hat hexagonale Symmetrie mit der Raumgruppe P6₃/mmc (Nr. 194), a = 5.909(1) ?, c = 23.369(4) ?, V = 706.6(2) ?³, Z = 2, und einer berechneten Dichte von 5.016 gcm⁻³. Die Struktur wurde aus Einkristall-R?ntgendaten bis zu einem R1-Wert von 0.031 für 278 F_o ² > 4σ(F_o ²), und einem R1-Wert von 0.079 für alle 452 F_o ² verfeinert. Die st?rksten Beugungsreflexe der Pulver-R?ntgendaten sind [d_obs, I/I_o, (hkl)]: 2.631, 100, (114); 2.799, 80, (107); 1.478, 70, (220); 2.429, 60, (203); 1.672, 50, (217). Das neue Mineral weist deutliche ?hnlichkeiten zu den anderen beiden Ba-reichen Mineralen Haggertyit und Hawthorneit der Magnetoplumbit-Gruppe auf, jedoch ist der Eisengehalt wesentlich h?her und im Bereich des Minerals Magnetoplumbit. Der gro?e Kationenplatz (A) ist von Barium dominiert, vier (M1, 2, 3, 5) der restlichen fünf kristallographischen Kationenpl?tze in der Struktur sind fast ausschlie?lich mit Fe, die oktaedrisch koordinierte M4-Position ist überwiegend mit Ti besetzt. An der O3-Position konnte kein Sauerstoffdefizit wie in Plumboferrit festgestellt werden. Batiferrit ist nach seiner chemischen Beschaffenheit und nach seiner Zugeh?hrigkeit zu den M-Typ Hexaferriten (Polytyp 5H) benannt.

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Received December 14, 1999; accepted March 2, 2000     

Crystal chemical properties of synthetic lazulite–scorzalite solid-solution series

Members of the lazulite–scorzalite (MgAl₂- (PO₄)₂(OH)₂-FeAl₂(PO₄)₂(OH)₂) solid-solution series were synthesized in compositional steps of 12.5?mol% at T?=?485?°C and P?=?0.3?GPa under hydrothermal conditions and controlled oxygen fugacities of the Ni/NiO-buffer. X-ray powder diffraction and ⁵⁷Fe-Mössbauer studies show that under these conditions a complete solid-solution series is formed which is characterized by the substitution of Mg²⁺ and Fe²⁺ on the octahedral Me ²⁺ site. The ⁵⁷Fe-Mössbauer spectra which reveal the presence of both ferrous and ferric iron and the compositional data were interpreted in terms of a defect model with a distribution of the ferric ions over both the Me ²⁺ and the Al³⁺ positions and vacancies on the Me ²⁺ site. The ⁵⁷Fe-Mössbauer parameters of the synthetic compounds correspond to those of natural lazulites except for the total absorption ratio of the ferric iron A(Fe³⁺)/(A(Fe³⁺)+A(Fe²⁺)), which is significantly higher in natural lazulites of the same composition. The total absorption ratio of the ferric iron increases from 4% in pure scorzalite to 15% in a Mg-rich solid-solution with x _Fe ?=?12(1)%     

Högbomite in migmatitic paragneiss in the Betroka shear belt, Vohidava area, Precambrian of southern Madagascar

Summary ?The Betroka sinistral shear belt is a major geotectonic unit in the Precambrian of southern Madagascar. It consists of migmatitic paragneiss commonly interlayered with phlogopite-bearing diopsidite, phlogopite-humite-diopside-spinel marble, sillimanite-garnet quartzite and syn-tectonic S-type leucogranite. H?gbomite occurs sporadically in the migmatitic paragneiss in patches of magnetite with hercynite, and at the border of magnetite where it is in contact with hercynite, rare ilmenite, rutile and cordierite, which contains a network of chlorite, pyrophyllite and rare corundum/diaspore. X_Mg = Mg/(Mg + Fe) decreases as follows: Crd > Bt > Chl > H?g > Hc. The textural relations suggest the following h?gbomite-participating reactions: Ti-bearing hercynite ↠ hercynite + h?gbomite (intergrown/exsolution lamellae) ilmenite + cordierite ↠ hercynite + h?gbomite + rutile + chlorite/pyrophyllite   h?gbomite ↠ hercynite + ilmenite + corundum The chemical composition of h?gbomite varies substantially from grain to grain in individual samples and from sample to sample, this variation being highly dependent on the associated minerals. There is a weak zoning from core to rim in individual grains intergrown with hercynite and also in grains at the margin of hercynite, but this zoning is overprinted by zones formed at grain rims depending on the surrounding phases. In contact with hercynite, h?gbomite has FeO (total Fe as FeO) 27.1–28.5 wt.%, and MgO 4.5–5.8 wt.%, and in contact with magnetite FeO 24.9–26.5 wt.%, and MgO 6.0–8.5 wt.% and the core contents are within these values. TiO₂7.5–4.0 wt.% and Al₂O₃62.0–59.0 wt.% show zonations with increase from core to rim. Estimated P-T conditions are 6.0 ± 1.0 kbar and 700 ± 100 °C reached during a peak metamorphic stage of the Pan-African orogeny. However, the presence of diaspore with exsolved hercynite-magnetite indicates extreme retrograde metamorphism in the decompressional central part of this shear belt of southern Madagascar.

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Zusammenfassung ?H?gbomit in migmatitischem Paragneis von Vohidava in der Betroka Scherzone im südlichen Pr?kambrium von Madagaskar Die sinistrale Betroka Scherzone ist eine ausgepr?gte tektonische Einheit des Pr?kambriums in Süd Madagaskar. Sie besteht aus migmatitischem Paragneis, in dem Phlogopit-führender Diopsidit, Phlogopit-Humit-Diopsid-Spinell-Marmor, Sillimanit-Granat-Quarzit und syntektonischer S-Typ Granit eingelagert sind. Im migmatitischen Paragneis kommen sporadisch H?gbomit/Hercynit Nester im Magnetit vor und am Magnetitrand findet sich H?gbomit im Kontakt mit Hercynit und Cordierit, der mit einem Netzwerk aus Chlorit/Pyrophyllit gefüllt ist, sowie sporadisch mit Korund/Diaspor, Ilmenit und Rutil. X_Mg = Mg/(Mg + Fe) nimmt in folgender Reihung ab: Crd > Bt > Chl > H?g > Hc. Aus den texturellen Beziehungen werden folgende H?gbomit-partizipierende Reaktionen abgeleitet: Ti-führender Hercynit ↠ Hercynit + H?gbomit (verwachsen/Entmischungslamellen)   H?gbomit ↠ Hercynit + Ilmenit + Korund Die chemische Zusammensetzung von H?gbomit variiert betr?chtlich von Korn zu Korn in einer Probe und von Probe zu Probe; wobei die Variation von den Kontaktmineralen abh?ngt. H?gbomit im Hercynit hat eine schwache Zonierung von Kern zum Rand. Im H?gbomit am Hercynitrand ist die Kern-Rand-Zonierung durch die von den Kontaktmineralen abh?ngige Randzusammensetzung überpr?gt. Im Kontakt zum Hercynit hat H?gbomit 27,1–28,5 Gew.% FeO (total Fe als FeO) und 4,5–5,8 Gew.% MgO und im Kontakt zu Magnetit 24,9–26,5 Gew.% FeO und 6,0–8,5 Gew.% MgO, die Kernzusammensetzung liegt zwischen den beiden Randwerten. TiO₂nimmt vom Kern zu den R?ndern von 7,5 bis 4,0 Gew.% ab und Al₂O₃von 62,0 bis 59,0 Gew.%. Die P-T Bedingungen des Metamorphose-Peaks w?hrend der Pan-Afrikanischen Orogenese erreichten 6,0 ± 1,0 Kbar und 700 ± 100 °C. Die sp?te Bildung von Diaspor und die Hercynit-Magnetit-Entmischung weisen auf eine tiefgreifende retrograde Metamorphose im Dekompressions-Zentralbereich der Betroka-Scherzone im südlichen Madagaskar hin.

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Received January 15, 1999;/revised version accepted July 6, 1999     

Phase relations in the system fayalite–magnetite at high pressures and temperatures

The phase relations in the Fe₂SiO₄–Fe₃O₄ binary system have been determined between 900 and 1200 °C and from 2.0 to 9.0 GPa. At low to moderate pressures magnetite can accommodate significant Si, reaching X_Fe2SiO₄=0.1 and 0.2 at 3.0 and 5.0 GPa respectively, with temperature having only a secondary influence. At pressures below 3.5 GPa at 900 °C and 2.6 GPa at 1100 °C magnetite-rich spinel coexists with pure fayalite. This assemblage becomes unstable at higher pressures with respect to three intermediate phases that are spinelloid polytypes isostructural to spinelloids II, III and V in the Ni-aluminosilicate system. The phase relations between the spinelloid phases are complex. At pressures above ≈8.0 GPa at 1100 °C, the spinelloid phases give way to a complete spinel solid solution between Fe₃O₄ and Fe₂SiO₄. The presence of small amounts of Fe³⁺ stabilises the spinel structure to lower pressures compared to the Fe₂SiO₄ end member. This means that the fayalite–γ-spinel transition is generally unsuitable as a pressure calibration point for experimental apparatuses. The molar volumes of the spinel solid solutions vary nearly linearly with composition, having a small negative deviation from ideal behaviour described by W_v=−0.15(6) cm³. Extrapolation yields V°₍₂₉₈₎ = 41.981(14) cm³ for the Fe₂SiO₄-spinel end member. The cell parameters and molar volumes of the three spinelloid polytypes vary systematically with composition. Cation disorder is an important factor in stabilising the spinelloid polytypes. Each polytype exhibits a particular solid solution range that is directly influenced by the interplay between its structure and the cation distributions that are energetically favourable. In the FeO–FeO_1.5–SiO₂ ternary system Fe₇SiO₁₀ (“iscorite”) coexists with the spinelloid phases at intermediate pressures on the SiO₂-poor, or Fe³⁺-poor side of the Fe₂SiO₄–Fe₃O₄ join. On the SiO₂ and Fe³⁺-rich side of the join, orthopyroxene or high-P clinopyroxene coexists with the spinelloids and spinel solid solutions. The assemblage pyroxene+spinel+SiO₂ is stable over a wide range of bulk composition. The stability of spinelloid III is of particular petrologic interest since this phase has the same structure as (Mg,Fe)₂SiO₄–wadsleyite, indicating that Fe³⁺ can be easily incorporated in this important phase in the Earth's transition zone, in addition to silicate spinel. This has important implications for the redox state of the Earth's transition zone and for the depth at which the olivine to spinel transition occurs in the mantle, potentially leading to a shift in the “410 km” seismic discontinuity to shallower depths depending on the prevailing redox state. In addition, a coupled tetrahedral substitution of Fe³⁺+OH for Si+O could provide a further mechanism for the incorporation of H₂O in wadsleyite. Received: 10 January 2000 / Accepted: 12 May 2000     

Paleostress-tensor analysis of late deformation events in the Odenwald Crystalline Complex and comparison with other units of the Mid-German Crystalline Rise, Germany

Summary Geometric data of fault planes and fault plane lineations, together with the observed sense of shear on the slip planes, were used to calculate paleostress tensors and fields responsible for the post metamorphic peak D3 and D4 deformation events in the four Odenwald units sensu Krohe (1991). The paleostress fields were calculated using the method of Will and Powell (1991). As inferred from the paleostress analysis, the D3 strike-slip deformation west of the Otzberg fault zone was caused by a, ± N-S directed, compressional regional stress field, with shallowly plunging σ₁ axes and σ₃ directions that plunge at shallow to moderate angles to the E or W; the calculated mean orientations are: σ₁ 06 → 350, σ₂ 77 → 234 and σ₃ 12 → 085. The B?llsteiner Odenwald east of the Otzberg fault zone was not affected by this stress field. This implies that the Bergstr?sser and B?llsteiner Odenwald were spatially separated and formed independent crustal blocks during D3. The D4 faulting event is recognised in all areas investigated, even though most prominently in units III and IV, and juxtaposed the Bergstr?sser and B?llsteiner Odenwald. This faulting episode was caused by a paleostress field with a steeply westerly plunging σ₁ axis and a shallowly southsoutheasterly plunging σ₃ axis. The orientations of the principal stresses are: σ₁ 52 → 270, σ₂ 38 → 085 and σ₃ 06 → 174. With continued deformation from D3 to D4, there was a progressive change in the orientation of the stress field indicating a change from a N-S compressional to extensional stress field, accompanied by the progressive development of strike-slip faults and late normal faults. Paleostress field orientations in the Pfalz Forest, SW of the Odenwald, determined by Fl?ttmann and Oncken (1992) are very similar to those obtained for the Odenwald region and indicate a regionally consistent stress pattern in the southwestern part of the Mid-German Crystalline Rise (MGCR) during strike-slip and normal faulting deformations.

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Zusammenfassung Paleostress-Tensor Analyse sp?ter Deformationsereignisse im Odenwald-Kristallin und ein Vergleich mit anderen Einheiten der Mitteldeutschen Kristallinzone, Deutschland Für die vier Odenwald-Einheiten im Sinne von Krohe (1991) wurden Pal?ostressfelder für die Blattverschiebungs- und Abschiebungsereignisse D3 und D4 mit der Methode von Will und Powell (1991) berechnet. Die Analyse ergibt, da? das regionale Spannungsfeld, das westlich der Otzberg-Zone im Bergstr?sser Odenwald zum D3-Ereignis führte, ein ± N-S gerichtetes kompressives Stresssfeld war. Die σ₁-Achse f?llt flach nach N bzw. S ein, die σ₃-Achse mit kleinen bis moderaten Winkeln nach E bzw. W; die berechneten Orientierungen der Hauptspannungsrichtungen sind: σ₁ 08 → 350, σ₂ 77 → 234 and σ₃ 12 → 085. Der B?llsteiner Odenwald, ?stlich der Otzberg-Zone, wurde von diesem Spannungsfeld nicht erfa?t. Dies impliziert, da? Bergstr?sser und B?llsteiner Odenwald w?hrend des D3-Ereignisses voneinander getrennt waren und separate Krusteneinheiten darstellten. Auswirkungen der D4-Deformation k?nnen im gesamten Untersuchungsgebiet erkannt werden, am st?rksten jedoch in den Einheiten III und IV. Dieses Ereignis wurde von einem Pal?ostressfeld mit einer steil nach W einfallenden σ₁- und einer flach nach SSE einfallenden σ₃-Achse verursacht und führte zum Zusammenschlu? von Bergstr?sser und B?llsteiner Odenwald. Die berechneten Orientierungen der Hauptspannungsrichtungen sind: σ₁ 52 → 270, σ₂ 38 → 085 und σ₃ 06 → 174. Die Rotation der Hauptspannungsrichtungen war mit einer ?nderung von einem kompressionalen N-S gerichteten (D3) hin zu einem extensionalen (D4) Stressfeld verbunden. Die erzielten Ergebnisse sind sehr ?hnlich mit Resultaten, die Fl?ttmann und Oncken (1992) im Pf?lzer Wald ermittelten. Dies weist auf ein regional übereinstimmendes Spannungsfeld im SW-Teil der Mitteldeutschen Kristallinzone hin.

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Received July 8, 1999; revised version accepted March 28, 2000     

Elasticity of the pyrope (Mg3Al2Si3O12)-majorite (MgSiO3) garnets solid solution

Dense isotropic polycrystalline specimens of majorite-rich garnets (Py₁₀₀, Py₆₂Mj₃₈, Py₅₀Mj₅₀, Py₂₁Mj₇₉ and Mj₁₀₀) along the pyrope (Mg₃Al₂Si₃O₁₂ = Py₁₀₀)-majorite (MgSiO₃ = Mj₁₀₀) join were fabricated in a 2000-ton uniaxial split-sphere anvil apparatus (USSA-2000) at pressures from 10 to 18.5 GPa and temperatures from 1200 to 1850 °C, within their stability fields in runs of 2–4-h duration, using hot-pressing techniques developed by Gwanmesia et al. (1993). These specimens are single-phased, fine-grained (≤5 mm), free of microcracks, and have bulk densities greater than 99% of the corresponding single-crystal X-ray density. Elastic compressional (P) and shear (S) wave velocities were determined at room pressure and temperature for these polycrystalline garnet specimens by phase comparison ultrasonic interferometry. For Mj₁₀₀, the P and S wave velocities are within 1% of the Hashin-Shtrikman averages calculated from the single crystal elastic moduli measured by Brillouin spectroscopy. Both the elastic bulk modulus (K) and the shear modulus (G) decrease continuously with increasing majorite content from pyrope garnet (Py₁₀₀) to pure majorite garnet (Mj₁₀₀). The compositional dependence of K and G are given by K = 172.3 (40) − 0.085X, and G = 91.6 (10) − 0.038X, where X = mol% majorite), respectively, indicating that substitution of Si for Mg and Al decreases both K and G by about 5% along the solid solution series. Received: 25 March 1999 / Accepted: 12 July 1999     

The crystal structure of arsentsumebite, Pb2Cu[(As, S)O4]2(OH)

Summary The crystal structure of arsentsumebite, ideally, Pb₂Cu[(As, S)O₄]₂(OH), monoclinic, space group P2₁/m, a = 7.804(8), b = 5.890(6), c = 8.964(8) ?, β = 112.29(6)°, V = 381.2 ?³, Z = 2, d_calc. = 6.481 has been refined to R = 0.053 for 898 unique reflections with I> 2σ(I). Arsentsumebite belongs to the brackebuschite group of lead minerals with the general formula Pb₂ Me(XO₄)₂(Z) where Me = Cu²⁺, Mn²⁺, Zn²⁺, Fe²⁺, Fe³⁺; X = S, Cr, V, As, P; Z = OH, H₂O. Members of this group include tsumebite, Pb₂Cu(SO₄)(PO₄)(OH), vauquelinite, Pb₂Cu(CrO₄)(PO₄)(OH), brackebuschite, Pb₂ (Mn, Fe)(VO₄)₂(OH), arsenbracke buschite, Pb₂(Fe, Zn)(AsO₄)₂(OH, H₂O), fornacite, Pb₂Cu(AsO₄)(CrO₄)(OH), and feinglosite, Pb₂(Zn, Fe)[(As, S)O₄]₂(H₂O). Arsentsumebite and all other group members contain M = M–T chains where M = M means edge-sharing between MO₆ octahedra and M–T represents corner sharing between octahedra and XO₄ tetrahedra. A structural relationship exists to tsumcorite, Pb(Zn, Fe)₂(AsO₄)₂ (OH, H₂O)₂ and tsumcorite-group minerals Me(1)Me(2)₂(XO₄)₂(OH, H₂O)₂. Received June 24, 2000; revised version accepted February 8, 2001     

Structural-metamorphic evolution of the Southern Yenisey Range of Eastern Siberia: implications for the emplacement of the Kanskiy granulite Complex

Summary ?The Southern Yenisey Range of Eastern Siberia consists of the granulite facies Kanskiy Complex bordered in the west by the lower-grade Yeniseyskiy and Yukseevskiy Complexes. Three deformational events were recognized in each of the three complexes along the Yenisey River cross-section: a D1 fabric forming event, a D2 shear and folding event, and a D3 shear event. Thrust kinematics across the Southern Yenisey Range suggest that during the D2 event the Kanskiy Complex was thrusted along a regional ductile shear zone onto the lower-grade complexes. This resulted in shearing and folding as well as the development of a dynamic metamorphic zonation. In the low-grade greenstone belt part of the cross section (Yukseevskiy complex) D2 shearing is associated with peak prograde (T ∼ 660 °C and P ∼ 5.8 kbar) metamorphism. The retrograde P-T path of the Yukseevskiy Complex coincides with minimum T of the near-isobaric cooling P-T paths for the adjacent granulites of the Kanskiy Complex (Perchuk et al., 1989). The metamorphism can therefore be attributed to deformation and heat transfer caused by exhumation of the Kanskiy Complex in the time period 2000–1800 Ma which also defines the most significant tectono-thermal event in the Southern Yenisey Range. The tectono-metamorphic pattern and evolution of the low- to high-grade metamorphic complexes of the Southern Yenisey Range is very similar to that described for the ∼ 2600 Ma Limpopo Complex of Southern Africa and the ∼ 1900 Ma Lapland Complex of the Kola Peninsula. Similar geodynamic processes were therefore possibly responsible for the formation of these high-grade terrains suggesting that their formation is linked to a general geodynamic model.

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Zusammenfassung ?Strukturelle und metamorphe Entwicklung des südlichen Jenissei-Gebirges in Ost-Sibirien: Bedeutung für die Platznahme des Kanskiy Granulit-Komplexes Das südliche Jenissei-Gebirge in Ost-Sibirien besteht aus dem granulit-faziellen Kanskiy Komplex, der im Westen durch die niedrig-gradigen Jenisseiski und Jukseevski-Komplexe begrenzt wird. Drei Deformations-Phasen k?nnen in jedem der drei Komplexe l?ngs eines Profiles am Jenissei-Fluss beobachtet werden: Eine Phase, die zur Entwicklung des D1 Gefüges führte, eine Phase D2 mit Scher- und Faltvorg?ngen und eine D3 Scher-Phase. Die Kinematik von überschiebungen über das südliche Jenissei-Gebirge deuten an, dass w?hrend der D2-Phase der Kanskiy-Komplex l?ngs einer regionalen duktilen Scherzone auf die niedriggradigeren Komplexe überschoben wurde. Dies führte zu Scherung und Faltung, sowie zur Entwicklung einer dynamischen metamorphen Zonierung. In dem niedriggradigen Grünsteingürtel innerhalb des Profils (Jukseevski-Komplex) ist D2-Scherung mit dem H?hepunkt der prograden Metamorphose (T ≈ 660 °C und P ≈ 5,8 kbar) zusammengefallen. Der retrograde P-T-Pfad des Jukseevski-Komplexes f?llt mit der Minimum-Temperatur der fast isobaren Abkühlung der P-T-Pfade für die benachbarten Granulite des Kanskiy-Komplexes zusammen (Perchuk et al., 1989). Die Metamorphose kann deshalb auf Deformation und W?rmefluss zurückgeführt werden, die durch die Freilegung des Kanskiy-Komplexes zwischen 2.00 und 1.80 Ma verursacht wurde; letztere f?llt auch mit der wichtigsten tektono-thermalen Phase im südlichen Jenissei-Gebirge zusammen. Das tektono-metamorphe Muster und die Entwicklung von niedrig- zu hochgradigen metamorphen Komplexen des südlichen Jenissei-Gebirges ?hnelt in vielf?ltiger Weise dem ungef?hr 2.600 Ma alten Limpopo-Komplex im südlichen Afrika und dem 1.900 Ma alten Lappland-Komplex der Kola-Halbinsel. ?hnliche geodynamische Prozesse waren deshalb m?glicherweise für die Entstehung dieser hochgradig metamorphen Terrains verantwortlich; dies wiederum weist darauf hin, dass ihre Entstehung einem allgemeinen geodynamischen Modell entspricht.

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Received April 27, 1999;/revised version accepted July 14, 1999     

Stability range and decomposition of potassic richterite and phlogopite end members at 5–15 GPa

Summary The phase relations of K-richterite, KNaCaMg₅Si₈O₂₂(OH)₂, and phlogopite, K₃Mg₆ Al₂Si₆O₂₀(OH)₂, have been investigated at pressures of 5–15 GPa and temperatures of 1000–1500 °C. K-richterite is stable to about 1450 °C at 9–10 GPa, where the dp/dT-slope of the decomposition curve changes from positive to negative. At 1000 °C the alkali-rich, low-Al amphibole is stable to more than 14 GPa. Phlogopite has a more limited stability range with a maximum thermal stability limit of 1350 °C at 4–5 GPa and a pressure stability limit of 9–10 GPa at 1000 °C. The high-pressure decomposition reactions for both of the phases produce relatively small amounts of highly alkaline water-dominated fluids, in combination with mineral assemblages that are relatively close to the decomposing hydrous phase in bulk composition. In contrast, the incongruent melting of K-richterite and phlogopite in the 1–3 GPa range involves a larger proportion of hydrous silicate melts. The K-richterite breakdown produces high-Ca pyroxene and orthoenstatite or clinoenstatite at all pressures above 4 GPa. At higher pressures additional phases are: wadeite-structured K₂Si^VISi^IV ₃O₉ at 10 GPa and 1500 °C, wadeite-structured K₂Si^VISi^IV ₃O₉ and phase X at 15 GPa and 1500 °C, and stishovite at 15 GPa and 1100 °C. The solid breakdown phases of phlogopite are dominated by pyrope and forsterite. At 9–10 GPa and 1100–1400 °C phase X is an additional phase, partly accompanied by clinoenstatite close to the decomposition curve. Phase X has variable composition. In the KCMSH-system (K₂CaMg₅Si₈O₂₂(OH)₂) investigated by Inoue et al. (1998) and in the KMASH-system investigated in this report the compositions are approximately K₄Mg₈Si₈O₂₅(OH)₂ and K_3.7Mg_7.4Al_0.6Si_8.0O₂₅(OH)₂, respectively. Observations from natural compositions and from the phlogopite-diopside system indicate that phlogopite-clinopyroxene assemblages are stable along common geothermal gradients (including subduction zones) to 8–9 GPa and are replaced by K-richterite at higher pressures. The stability relations of the pure end member phases of K-richterite and phlogopite are consistent with these observations, suggesting that K-richterite may be stable into the mantle transition zone, at least along colder slab geotherms. The breakdown of moderate proportions of K-richterite in peridotite in the upper part of the transition zone may be accompanied by the formation of the potassic and hydrous phase X. Additional hydrogen released by this breakdown may dissolve in wadsleyite. Therefore, very small amounts of hydrous fluids may be released during such a decomposition. Received April 10, 2000; revised version accepted November 6, 2000     

The low-pressure stability of phase A,Mg7Si2O8(OH)6

 Phase A, Mg₇Si₂O₈(OH)₆, is a dense hydrous magnesium silicate whose importance as a host of H₂O in the Earth’s mantle is a subject of debate. We have investigated the low-pressure stability of phase A in experiments on the reaction phase A=brucite+forsterite. Experiments were conducted in piston-cylinder and multi-anvil apparatus, using mixtures of synthetic phase A, brucite and forsterite. The reaction was bracketed between 2.60 and 2.75 GPa at 500° C, between 3.25 and 3.48 GPa at 600° C and between 3.75 and 3.95 GPa at 650^° C. These pressures are much lower than observed in the synthesis experiments of Yamamoto and Akimoto (1977). At 750^° C the stability field of brucite + chondrodite was entered. The enthalpy of formation and entropy of phase A at 1 bar (10⁵ Pa), 298 K, were derived from the experimental brackets on the reaction phase A=brucite+forsterite using a modified version of the thermodynamic dataset THERMOCALC of Holland and Powell (1990), which includes a new equation of state of H₂O derived from the molecular dynamics simulations of Brodholt and Wood (1993). The data for phase A are: ΔH ^o _f =−7126±8 kJ mol^-1, S ^o=351 J K^-1 mol^-1. Incorporating these data into THERMOCALC allows the positions of other reactions involving phase A to be calculated, for example the reaction phase A + enstatite=forsterite+vapour, which limits the stability of phase A in equilibrium with enstatite. The calculated position of this reaction (753° C at 7 GPa to 937° C at 10 GPa) is in excellent agreement with the experimental brackets of Luth (1995) between 7 and 10 GPa, supporting the choice of equation of state of H₂O used in THERMOCALC. Comparison of our results with calculated P-T paths of subducting slabs (Peacock et al. 1994) suggests that, in the system MgO–SiO₂–H₂O, phase A could crystallise in compositions with Mg/Si>2 at pressures as low as 3 GPa. In less Mg rich compositions phase A could crystallise at pressures above approximately 6 GPa. Received: 3 July 1995/Accepted: 14 December 1995     

Phase relations of calc-silicate assemblagesin the Auerbach marble, OdenwaldCrystalline Complex, Germany

Summary In the Odenwald Crystalline Complex, calc-silicate rocks are concentrated at the margins of the marble layer of Auerbach. They were presumably formed by metasomatic exchange between the calcite marble and the neighbouring granodioritic and quartz-dioritic intrusives. The investigated samples contain the characteristic mineral assemblages: garnet + clinopyroxene + epidote/clinozoisite + calcite + quartz ± titanite (1) and wollastonite + clinopyroxene + garnet + calcite ± quartz ± epidote/clinozoisite ± titanite (2). Microprobe analyses revealed the following compositional ranges: garnet grs_40–98adr_2–55alm_<5.5sps_<5.5pyp_<1; clinopyroxene di_46–88hed_9–47joh_0–5cats_0–6; epidote/clinozoisite ps_20–80. Different phase diagrams were calculated in the system CaO-MgO-Al₂O₃-TiO₂-SiO₂-CO₂-H₂O (CMATSCH) to decipher the P-T-X_CO2 parameters of metamorphism: isobaric T-X_CO2 sections and a P-T projection with mixed volatiles. The phase diagrams illustrate that the observed assemblages can only form in the presence of an H₂O-rich volatile phase. The assemblages are stable over a large range of temperatures, from 580 °C to < 400 °C (at 4 kbar) and at X_CO2 values of less than 0.055 (at 4 kbar). Higher temperatures can be inferred from reaction textures which indicate that garnet + plagioclase (T > 580 °C, at 4 kbar) and wollastonite + plagioclase (T > 660 °C, at 4 kbar) coexisted during an early metamorphic stage. A minimum pressure of 3.5 kbar can be inferred for the early high-temperature stage. Furthermore, on the basis of the calculated phase diagrams, combined with modal abundances in thin sections, it is possible to evaluate fluid behaviour; in the investigated specimens, infiltration of fluids from an external reservoir occurred. A minimum fluid:rock ratio of 3.6:1 can be estimated.

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Zusammenfassung Phasenbeziehungen in Kalksilikat-Paragenesen des Marmorzuges von Auerbach, Odenwald-Kristallin-Komplex, Deutschland Im kristallinen Odenwald konzentrieren sich kalksilikatische Gesteine in den Randbereichen des Marmorzuges von Auerbach. Die kalksilikatischen Partien wurden vermutlich duch metasomatischen Austausch zwischen dem Calcit-Marmor und benachbarten Granodioriten und Quarzdioriten gebildet. Die untersuchten Proben enthalten die charakteristischen Mineralparagenesen: Granat + Klinopyroxen + Epidot/Klinozoisit + Calcit + Quarz + Titanit (1) und Wollastonit + Klinopyroxen + Granat + Calcit ± Quarz ± Epidot/Klinozoisit ± Titanit (2). Mikrosondenanalysen ergaben folgendes Zusammensetzungsspektrum: Granat grs_40–98adr_2–55alm_<5.5sps_<5.5pyp_<1; Klinopyroxen di_46–88hed_9–47joh_0–5cats_0–6s; Epidot/Klinozoisit ps_20–80. Verschiedene Phasendiagramme wurden für das Modellsystem CaO-MgO-Al₂O₃-TiO₂-SiO₂-CO₂-H₂O (CMATSCH) berechnet, um die P-T-X_CO2-Parameter der Metamorphose einzugrenzen: Isobare T-X_CO2-Schnitte und eine P-T-Projektion mit einer Fluid-Mischphase. Die Phasendiagramme verdeutlichen, da? die beobachteten Paragenesen nur in Anwesenheit eines H₂O-reichen Fluids gebildet werden k?nnen. Die Paragenesen sind über einen gro?en Temperaturbereich hinweg stabil, von 580 °C bis < 400 °C (bei 4 kbar) und bei X_CO2-Gehalten von < 0.055 (bei 4 kbar). Ursprünglich h?here Temperaturen k?nnen anhand von Reaktions-Texturen rekonstruiert werden, die zeigen, da? Granat + Plagioklas (T > 580 °C, bei 4 kbar) und Wollastonit + Plagioklas (T > 660 °C, bei 4 kbar) w?hrend eines früheren Metamorphosestadiums koexistierten. Ein Minimaldruck von 3.5 kbar kann für dieses frühe Hochtemperatur-Stadium abgeleitet werden. Mit Hilfe der berechneten Phasendiagramme, in Kombination mit beobachteten Modalgehalten, ist es m?glich, das Verhalten der fluiden Phase abzusch?tzen. Die untersuchten Gesteine implizieren Fluidinfiltration, wobei ein minimales Verh?ltnis Fluid:Gestein von 3.6:1 abgesch?tzt werden kann.

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Received July 29, 1999; accepted March 28, 2000