Experimental determination of the effects of pressure and temperature on the stoichiometry and phase relations of wüstite

When quenched metastable wüstite (Fe_.924O and Fe_.947O) is held at 300°C at pressures up to 200 kbar in a diamond anvil cell, a mixture of magnetite, metallic iron and wüstite is found. We interpret this to indicate that magnetite plus metallic iron constitute the stable phase assemblage at pressures and temperatures below this boundary is stoichiometric FeO ($\text{a}{}_0\text{= 4.332 ± 0.001}\text{A}\text{?}$) at pressures below 110 kbar at 300°C. However, just below the boundary in the pressure range 110 kbar to 200 kbar at 300°C, the residuál wüstite is non-stoichiometric ($\text{a}{}_0\text{< 4.332}\text{A}\text{?}$). Data collected at pressures and temperatures above the boundary indicate that non-stoichiometric wüstite (Fe_xO) plus metallic iron constitute the stable phase assemblage and that the value of x in Fe_xO increases as pressure is increased isothermally to 100 kbar and then decreases as pressure is increased above 100 kbar.     

Composition and pressure dependence of lattice thermal conductivity of (Mg,Fe)O solid solutions

We measured the lattice thermal conductivities of Fe_0.98O wüstite and iron-rich (Mg,Fe)O magnesiowüstite using the pulsed light heating thermoreflectance technique with a diamond anvil cell up to 61 GPa at 300 K. We found that the thermal conductivity of wüstite does not show a monotonic increase as a function of pressure, contrary to that of MgO periclase. Rocksalt (B1) to rhombohedral B1 transition is likely to induce an abnormal pressure response in the conductivity of wüstite. Our results also show that magnesiowüstite has a lower conductivity than that of MgO and FeO endmembers due to a strong iron impurity effect, which is well reproduced by a model considering phonon-impurity scattering in a binary solid solution.     

Über den Eisengehalt von Alumosilikaten aus Quarzknauern

Zusammenfassung Der Eisengehalt von Andalusiten und Disthenen aus Quarzknauern im Gebiet des Ötztaler—Stubaier Altkristallins wurde regional untersucht. Der Gehalt and Gesamteisen in primären Disthen liegt zwischen 0,17 und 0,22 Gew.% Fe₂O₃, während primäre Andalusite zwischen 0,26 und 1,93 Gew.% Fe₂O₃ schwanken. Dieser Unterschied in den Andalusiten wird auf ein wechselndes Angebot von Fe₂O₃ aus dem Nachbargestein der Knauern zurückgeführt.Ein Zusammenhang zwischen dem Eisengehalt der Andalusite und den verschiedenen Umwandlungsstadien Andalusit—Disthen konnte nicht nachgewiesen werden.

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On the iron content of alumosilicates in quartz nodules

Summary A determination of the regional distribution of the ironcontent of andalusites and kyanites in quartz-segregations of the Oetztal—Stubai crystalline complex gave values of 0.17–0.22% for the total iron in primary kyanite and 0.26–1.93% in andalusite. This difference is probably due to a variation in the Fe₂O₃-content in the country rocks of the quartz veins. No relationship between the iron-content in andalusite and the different stages of transformation from andalusite to kyanite could be established.

     

Chromian spinels in metamorphosed ultramafic rocks from Mangabal I and II complexes, Goiás, Brazil

Summary Chromian spinel occurs in feldspathic metaperidotites and feldspathic metaharzburgites, respectively, at Mangabal I and II mafic-ultramafic layered complexes, Brazil. Both complexes were metamorphosed (700-750°C and 6-7 Kbars) under variable P_{H 2}O conditions. Wherever P_{H 2}O = P_tot an almost complete metamorphic recrystallization occurred, but where P_{H 2}O < P_tot relict igneous cumulate textures are well preserved. Chromian spinel occurs as opaque grains included in cumulus olivine and as brown translucent crystals enclosed by intercumulus orthopyroxene, clinopyroxene, and plagioclase. Subsolidus reactions resulted in exsolution of opaque spinel into two phases: a Fe⁺²Fe ₂ ⁺³ -rich and a MgAl₂-rich one. Fe₂TiO₄-rich lamellae and patches may also occur. Coronas developed between olivine and plagioclase including orthopyroxene, pargasite and MgAl₂-rich green spinel. Whenever complete metamorphic reequilibration occurred (P_{H 2}O = Ptot) the brown and green spinels reacted with silicate phase to form clinochlore, leaving the Fe+2Fe ₂ ⁺³ -rich spinel phase, magnetite.

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Chromspinelle in metamorphen, ultramafischen Gesteinen der Mangabal I und II Komplexe, Goiás, Brasilien

Zusammenfassung Chromspinell kommt in feldspatführenden Metaperidotiten und Metaharzburgiten in den geschichteten mafisch-ultramafischen Komplexen in Mangabal I and II, Brasilien, vor. Beide Komplexe wurden unter variablem P_{H 2}O metamorphisiert (700–750°C, 6–7 Kbar). Während unter fluidreichen Bedingungen (P_{H 2}(O = P_tot) eine beinahe vollständige metamorphe Rekristallisation erfolgte, bleiben unter P_{H 2}O < P_tot reliktische magmatische Kumulustexturen erhalten. Chromspinell tritt in opaken körnern in Kumulus-Olivin und als braune, durchscheinende Körner, eingeschlossen in den Interkumulusmineralen Orthopyroxen, Klinopyroxen und Plagioklas, auf. Subsolidusreaktionen resultierten in der Entmischung von opakem Spinell in eine Fe²⁺ Fe ₂ ³⁺ -und eine MgAl₂-reiche Phase. Fe₂TiO₄-reiche Lamellen und Nester treten außerdem auf. Koronas zwischen Olivin und Plagioklas bestehen aus Orthopyroxen, Pargasit und grünem MgAl₂-reichem Spinell. Dort wo ein vollständige metamorphe Reequilibration (P_{H 2}O = P_tot) erfolgte, reagierte brauner und grüner Spinell mit Silikaten und bildete clinochlor, unter Zurücklassung von Fe²⁺Fe ₂ ³⁺ -reichem Spinell, dem Magnetit.

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With 8 Figures     

Thermal expansion and phase transitions in åkermanite and gehlenite

Thermal expansion has been measured by laboratory and synchrotron X-ray powder diffraction for end-member åkermanite (ak, Ca₂MgSi₂O₇) and gehlenite (ge, Ca₂Al₂SiO₇) in the range 20–1,500 K. In ak in the range 340–390 K, there is a negative linear thermal expansion in [001] direction. This is related to the phase transition from an incommensurate modulated structure (IC) to a normal one (N). The volumetric mean thermal expansion coefficients for ak and ge, obtained with a linear fit of the experimental data in the temperature range 298–1,400 K, are respectively 32.1×10^–6 and 28.3×10^–6 K^–1 . The variation of the c/a ratio with temperature, due to different thermal expansion along the crystallographic axes, can be related to the different behaviour of the tetrahedral layers in the N and IC phases. Analysis of the variation of the superstructure peaks intensity across the phase transition confirms the tricritical behaviour of the IC/N transition in ak.     

Sideronatrite: A mineral with a {Fe2(SO4)4(OH)2} guildite type chain?

Summary Recently several natural and artificial ferric iron sulphate crystal structures have been solved. Sideronatrite, Na₂Fe³⁺(SO₄)₂(OH)·3H₂O, does not provide good crystals for structural purposes. However if we examine crystallographic, chemical and physical data some useful information about the ...Fe–O–S... structural topology can be inferred. In fact this analysis strengthens the hypothesis that there is a {Fe ₂ ³⁺ (SO₄)₄(OH)₂} chain in sideronatrite like that found in guildite, Cu²⁺Fe³⁺(SO₄)₂(OH)·4H₂O.

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Sideronatrit: Ein Mineral mit einer {Fe₂(SO₄)₄(OH)₂}-Kette vom Typ Guildit?

Zusammenfassung Kürzlich wurden die Kristallstrukturen mehrerer natürlicher und künstlicher Ferrisulfate gelöst. Sideronatrit, Na₂Fe³⁺(SO₄)₂(OH)·3H₂O, liefert keine für die Strukturuntersuchung gut geeigneten Kristalle. Dennoch erhält man aus der Untersuchung der kristallographischen, chemischen und physikalischen Daten nützliche Information über die ...Fe–O–S...-Topologie der Struktur. Eine solche Analyse spricht für die Hypothese, daß der Sideronatrit eine {Fe ₂ ³⁺ (SO₄)₄(OH₂)}-Kette enthält, wie sie im Guildit, Cu²⁺Fe³⁺(SO₄)₂(OH)·4H₂O, gefunden wurde.

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With 1 Figure

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Paper presented at the Sixth European Crystallographic Meeting. Barcelona, Spain 1980.     

Comparative study of the kinetics of the thermal decomposition of synthetic and natural siderite samples

The mechanism of the thermal decomposition of two siderites (a pure synthetic and a natural Mg-containing sample) has been determined from comparison of the results obtained from linear heating rate (TG) and constant rate thermal analysis (CRTA) experiments in high vacuum. The thermal decomposition of the synthetic siderite takes place approximately 200 K below the decomposition temperature of the natural sample. The mechanism and the product of the thermal decomposition are different for the siderite samples. In fact, an A₂ kinetic model describes the thermal decomposition of the synthetic siderite, whereas the thermal decomposition of the natural sample obeys an F₁ kinetic law. Decomposition products of the synthetic siderite are iron and magnetite, those of the natural siderite are wüstite and minor magnetite. Received: 22 July 1999 / Accepted: 12 February 2000     

A granulite facies kalsilite-leucite-hibonite association from Punalur,Southern India

Summary Kalsilite, leucite and hibonite occur together with spinel, corundum, sphene, perovskite, Ti-phlogopite and K-feldspar in a granulite facies gneiss in the Punalur district in Kerala, southern India. Kalsilite-leucite-perovskite-phlogopite and kalsilite-hibonite-spinelcorundum formed distinct, texturally equilibrated assemblages during the granulite facies metamorphism. Sphene occurs as coronas on perovskite suggesting the retrograde breakdown of the perovskite-leucite association; leucite is partially altered to symplectites of K-feldspar and kalsilite, while hibonite shows partial replacement by corundum and perovskite in spinel-rich domains. Unlike other terrestrial hibonites the majority of the Punalur hibonites contain no significant rare earths (REE < 0.01 atoms per 190), with a composition approximated by Ca_0.85Ti_0.9Mg_0.25Fe_0.25Ali_10.4O₁₉ although a few zoned hibonites have REE rich cores with REE > 0.6 atoms per 19 O. Garnet-hypersthene granulites from Punalur and garnet-charnockites from elsewhere in Kerala suggest metamorphism at 700–800°C and 3.5–6.5 kbars; consistent with experimentally determined stability limit of leucite of low a(H₂O). The metamorphic conditions recorded by the Punalur assemblages testify to relatively low pressure conditions for a granulite facies terrain but are by no means unique. The scarcity of potassium feldspathoid in the metamorphic record must therefore be attributed to the exceptional compositional requirements of extreme silica undersaturation combined with low Na/K ratios.

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Eine Kalsilit-Leucite-Hibonit Paragenese in Granulit Fazies von Punalur, Süd-Indien

Zusammenfassung Kalsilit, Leuzit, and Hibonit kommen zusammen mit Spinell, Korund, Titanit, Perovskit, Ti-Phlogopit and K-Feldspat in einem granulitfaziellen Gneiss des Punalur-Distriktes in Kerala, Süd-Indien vor. Kalsilit-Leuzit-Perovskit-Phologopit and Kalsilit-Hibonit-Spinell-Korund bildeten wdhrend der Granulit-Fazies-Metamorphose deutliche Paragenesen, die texturell im Gleichgewicht sind. Titanit kommt als Koronas aufPerovskit vor und dies weist auf den retrograden Zerfall der Perovskit-Leuzit Paragenese hin. Leuzit ist teilweise zu Symplektiten von K-Feldspat und Kalsilit umgewandelt, während Hibonit Verdrängung durch Korund und Perovskit in spinellreichen Domänen zeigt. Im Gegensatz zu anderen terrestrischen Hiboniten, führt die Mehrzahl der Hibonite von Punalur, mit einer ungefähren Zusammensetzung von Ca_0.85Ti_0.9Mg_0.58Fe_0.25Ali_10.4O₁₉, keine wesentlichen Seltenen-Erd-Gehalte (SEE < 0.01 Atome per 19 0). Trotzdem gibt es einige wenige zonierte Hibonite, deren Kerne reich an SEE sind mit ESEE > 0.6 Atome per 19 O. Granat-Hypersthen Granulite aus Punalur and Granat-Charnockite von anderen Teilen Kerala's weisen auf eine Metamorphose bei 700–800°C und 3.5–6.5 kbar hin; dies ist in guter Übereinstimmung mit der experimentell bestimmten Stabilitätsgrenze von Leuzit bei niederigen a(H₂O). Die metamorphen Bedingungen, die die Punalur-Paragenesen dokumentieren, zeigen relativ niedrige Druckbedingungen für ein Granulit-Fazies Terrain an; das ist aber keineswegs einmalig. Die Seltenheit von Kali-Feldspathoiden während der metamorphen Entwicklung muß deshalb auf die ungewöhnlichen Erfordernisse extremer Silizium-Untersättigung, zusammen mit niedrigen Na/K-Verhältnissen, zurückgehen.

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With 6 figures     

Activity-composition relations of the magnesiowüstite solid solution series in equilibrium with metallic iron in the temperature range 1050–1400 K

The equilibrium $${\text{(1}} - y{\text{)Fe}}_{(s)} + \tfrac{{\text{1}}}{{\text{2}}}{\text{O}}_{{\text{2(g)}}} \rightleftarrows {\text{Fe}}_{{\text{1}} - y} {\text{O}}_{{\text{(}}s,{\text{ in MW)}}} $$ was studied by measuring oxygen potentials for a range of different magnesiowüstite compositions relative to those of the iron-wüstite system in an oxygen concentration cell involving yttria stabilized zirconia as the solid electrolyte. The temperature range covered was 1050 to 1400 K. Separate measurements of the mole fraction of trivalent iron in magnesiowüstite (x(Fe³⁺)) were made and the composition dependence ofx(Fe³⁺) was taken into account in calculations of the activity-composition relations of FeO, Fe_2/3O and MgO.     

Petrochemical evidence on the probable origin of ferriferous metasediments in western Bushmanland

The mineralized Proterozoic metasediments of Bushmanland are characterized by the presence of ferriferous rocks. This includes banded and unbanded iron formations and various types of gossans. These units are not laterally extensive and occur in different stratigraphic levels. The prevalent minerals in the ferriferous rocks are hematite, magnetite, quartz, garnet, muscovite, biotite and sillimanite, but less common occurrences of graphite, alunite, plumbojarosite, gahnite and dufrenite have been noted. The chemical variation (wt%) is extensive: total Fe₂O₃ (1.3–93.5), SiO₂ (4–93), Al₂O₃ (0.2–14.0), CaO (0.02–20.7), MnO (0.0–14.3), MgO (0.0–5.7), TiO₂ (0.0–4.4), Na₂O (0.0–2.0), K₂O (0.0–1.5) and P₂O₅ (0.1–7.0). The preliminary nature of the data set precludes, however, firm conclusions regarding stratigraphic control of the chemical composition. The trace-element contents (ppm) extend over several orders of magnitude: Zn (0–7,000), Ba (0–5,200), Cu (0–1,400), Pb (0–1,070) and Ni (6–540). Collectively, the data indicate that most of the ferriferous rocks represent highly metamorphosed sediments.     

Spherules with pure iron cores from Myanmar jadeitite: Type-I deep-sea spherules?

Here we report spherules in Myanmar jadeitite, a rock forming from jadeitic fluids within mantle-derived serpentinized rocks in subduction zones under high-pressure conditions (>1.0 GPa) and rather low temperatures of about 250-370 °C. The spherules have off-centre iron nuclei and dendritic wüstite cortexes, with tiny wüstite crystals perpendicular to the surface of iron core. Within the spherules are vesicles occupied by calcite, jadeite, albite? or mixtures of these phases, and the cortexes contain about 10 wt.% SiO₂ + Al₂O₃ + Na₂O filling materials within wüstite. The spherules are in direct contact with jadeite crystals. Contrasting patterns of some individual spherules are obvious between a front area with a crowd of hill-like prominences and a rear zone with one or more rings on the surface. Such surface features and internal textures suggest that they experienced movement at high temperature and then rapid cooling. Chemical compositions of the nuclei are homogenous and consist of nearly pure iron with minor Cr (<0.05 wt.%), Mn (<0.80 wt.%), and Ni (0.142-0.23 wt.%), and a trend of Ni decreasing and Cr increasing from core to cortex. Mn in the cortex (up to about 2.00 wt.%) is far more enriched than the nucleus. The bulk ratios (average) of δ⁵⁶Fe and δ⁵⁷Fe in the core and cortex are 0.51and 0.78, respectively. Such features suggest that there is a very low possibility of origin associated with volcanic explosive eruption, impact ejecta, chemical reduction or oxidation of iron on seafloor. Since biological reduction processes are not significant under high P/T condition in subduction zones, this origin is excluded. Considering their low Ni contents, it is more likely that they belong to the minor type-I deep-sea cosmic spherules/dusts of low isotope fractionation. This discovery shows that such spherules could remain stable under low-temperature and high-pressure conditions during recycling processes, and therefore could be found in rocks related to slab-derived sediments within subduction zones. This also suggests that subducted oceanic slab sediments contribute to the formation of jadeitite, coupled with dehydration of sediments and altered oceanic crust.     

The crystal structure of 2O brittle mica: Anandite

Summary Anandite has an approximate formula of Ba(Fe³⁺, Fe²⁺)₃[Si₂(Fe³⁺, Fe²⁺, Si)₂O_10–x(OH)_x] (S, Cl) (OH), withx=0–1, and belongs to the 2 O brittle mica group. It is orthorhombic; space groupPnmn;a=5.468(9) Å,b=9.489(18)Å,c=19.963(11) Å;Z=4.The structure was determined from 3dim. Weissenberg-data, starting with an approximate structure in the pseudo space groupCcmm. Least squares refinement resulted inR=0.061 for 409 photometric intensities, andR=0.131 for all 853 observedhkl-reflexions.The iron of the tetrahedral layer is concentrated in one of the two crystallographically different kinds of tetrahedra. The basal oxygen rings of the tetrahedral layer form approximate hexagons and have not the ditrigonal configuration of the common micas. This peculiarity is considered to be a consequence of the size and charge of the barium ion. The role of OH in the common micas is played partly by S^2– and Cl^– in anandite.

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Die Kristallstruktur des 2 O Sprödglimmers Anandit

Zusammenfassung Anandit hat die ungefähre Formel Ba(Fe³⁺, Fe²⁺)₃[Si₂(Fe³⁺, Fe²⁺, Si)₂O_10–x(OH)_x] (S, Cl) (OH) mitx=0–1 und gehört zur 2O Sprödglimmergruppe. Er ist rhombisch; RaumgruppePnmn; a=5,468(9) Å,b=9,489(18) Å,c=19,963(11) Å;Z=4.Die Struktur wurde aus Weissenberg-Daten bestimmt, wobei mit einer approximativen Struktur in der PseudoraumpruppeCcmm begonnen wurde. Die Verfeinerung nach der Methode der kleinsten Quadrate führte für 409 photometrierte Reflexe aufR=0,061 und für alle 853 beobachtetenhkl-Reflexe aufR=0,131.Der Eisengehalt der Tetraederschicht ist in einer der beiden kristallographisch verschiedenen Tetraederarten konzentriert. Die basalen Sauerstoffringe der Tetraederschicht bilden annäherungsweise Sechsecke und haben nicht die ditrigonale Konfiguration der gewöhnlichen Glimmer. In Anandit spielen S^2– und Cl^– teilweise die Rolle der Hydroxylgruppen in den gewöhnlichen Glimmern.

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With 4 Figures     

Texture development and elastic stresses in magnesiowűstite at high pressure

Cubic magnesiowűstite has been deformed in a diamond anvil cell at room temperature. We present results for (Mg_0.4Fe_0.6)O, (Mg_0.25Fe_0.75)O, and (Mg_0.1Fe_0.9)O up to 37, 16, and 18 GPa, respectively. The diffraction images, obtained with the radial diffraction technique, are analyzed using both single peak intensities and a Rietveld method. For all samples, we observe a [100] fiber texture but the texture strength decreases with increasing iron content. This texture pattern is consistent with {110}〈1-10〉 slip. The images were also analyzed for stress, elastic strains, and elastic anisotropy. In general, the stress measured in magnesiowűstite samples is lower than previously measured on MgO. The elastic anisotropy deduced from the X-ray measurements shows a broad agreement with models based on measurements with other techniques.     

Heterogene Gleichgewichte in der Wolframitgruppe

Zusammenfassung Im System Fe–Mn–W–O wurden die heterogenen Gleichgewichte bei 1000°C ausgehend von allen binären und ternären Randsystemen untersucht. Im System Fe–Mn–W wurde die intermetallische Verbindung Mn₅Fe_2,7W_2,3 gefunden. Im System Fe–Mn–O gibt es keine ternären Verbindungen, in den anderen Dreistoffsystemen nur FeWO₄, Fe₂WO₆ und MnWO₄. Mn₂WO₆ ließ sich bis pO₂=100 atm nicht darstellen. Quaternäre Verbindungen fehlen völlig. ZnWO₄ und NiWO₄ sind gegen FeO und MnO nicht stabil und reagieren zu FeWO₄ und MnWO₄ plus ZnO und NiO. Hydrothermal konnte bei pH₂O=2000 atm vollständige Mischbarkeit von FeWO₄ und MnWO₄ bis 160°C herab nachgewiesen werden. Die früher (Schröcke, 1960) durch Festkörperreaktionen festgestellte asymmetrische Mischungslücke im System FeWO₄–NiWO₄ konnte korrigiert werden,T _kj =525°C,x _kr =0.15 FeWO₄. FeWO₄–ZnWO₄ und MnWO₄–ZnWO₄ sind bis mindestens 414°C, MnWO₄ und NiWO₄ bis mindestens 454°C herab vollständig mischbar.

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Heterogeneous equilibria in the Wolframite group

Summary In the system Fe–Mn–W–O solid state equilibria at 1000°C were determined beginning with all binary and ternary bordering systems. In the system Fe–Mn–W the ternary phase Mn₅Fe_2.7W_2.3 was found. In the system Fe–Mn–O there does not exist any ternary phase. In the other systems only FeWO₄, Fe₂WO₆ and MnWO₄ exist. Mn₄WO₆ could not be synthesized up to 100 atm partial pressure of oxygen. Quaternary phases do not exist. ZnWO₄ and NiWO₄ are not stable in coexistence with FeO and MnO oxides. Reaction products are always FeWO₄ or MnWO₄ with ZnO or NiO. Hydrothermal studies at pH₂O=2000 atm showed complete solid solution in the system FeWO₄–MnWO₄ down to 160°C.Schröcke (1960) found an asymmetrical miscibility gap in the system FeWO₄–NiWO₄ by means of solid state reactions. Now this miscibility gap has been corrected: Critical temperature 525°C, critical composition 0,15 FeWO₄. Complete miscibility exists in the systems FeWO₄–ZnWO₄ and MnWO₄–ZnWO₄ down to at least 414°C, in the system MnWO₄–NiWO₄ down to at least 454°C.

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Mit 6 Abbildungen     

Titanian andradite in a metapyroxenite layer from the Malenco ultramafics (Italy): implications for Ti-mobility and low oxygen fugacity

Ti-andradite (melanite) has been found in a metapyroxenite layer in the upper part of the Malenco ultramafics(Italy), coexisting with clinochlore, diopside and magnetite. Field observations, as well as major and trace elementbulk-rock composition, strongly suggest a cumulate origin for the layer. Textural relationships indicate thatTi-andradite formed during two different metamorphic stages. Under peak metamorphic conditions (400–450°C, 5±2 kbar)Ti-andradite grew in an assemblage of diopside, clinochlore, magnetite and rare ilmenite and perovskite. Later, retrograde brittle deformationinduced formation of veins containing the paragenesis Ti-andradite, vesuvianite, diopside, chlinochlore, magnetite and accessory perovskite.The Ti-andradite varies considerably in TiO₂ (0.11–9.62 wt%), Fe₂O₃(14.3–30.5 wt%), Al₂O₃ (0.65–3.90 wt%), Cr₂O₃(>0.18–0.98 wt%) and SiO₂ (32.1–36.1 wt%); this is mostly, but not entirely, due to distinct zoning.Ti-andradite contains 0.32 to 0.66 wt% H₂O as determined by infrared spectroscopy and 0.83 to 1.76 wt% FeO. The CaO shows almost no variation (34.1±0.7 wt%) and Ca completely fills the dodecahedral site. Single crystal site refinements indicate that no tetrahedral Ti or Fe replaces Si. Titanium incorporation is attributed to similar degrees of substitution along the exchange vectors Ti³⁺ Fe³⁺, Ti⁴⁺ Al^IV Al _-1 ^VI Si_-1 and (Fe²⁺, Mn²⁺, Mg²⁺)Ti⁴⁺ 2Fe _-1 ³⁺ . The presence of mixed valence states of both Fe and Ti suggests a low oxygen fugacity during crystallization of Ti-andradite. Mass balance calculations indicate an isochemical origin of the first generation of Ti-andradite in the clinopyroxenite layer. Its occurrence is restricted to antigorite-free mineral assemblages containing clinochlore of 0.95X _Al>1.1. The hydrothermal crystallization of Ti-rich andradite in veins demonstrates Ti mobility in aqueous fluids under moderate P-T conditions. The zonation patterns indicate disequilibrium conditions during vein crystallization. As no fluorine-, carbonate- and phosphate-bearing minerals were found, OH^- is most probably the ligand complexing Ti.     

Multi-stage metasomatism of diamondiferous eclogite xenoliths from the Udachnaya kimberlite pipe,Yakutia, Siberia

The primary garnet (pyrope-almandine)-omphacite (Cpx 1, 6.5–7 wt% Na₂O)-sulfide (Fe-Ni-Co mss) assemblage of the two diamondiferous eclogite xenoliths studied (U33/1 and UX/1) experienced two mantle metasomatic events. The metasomatic event I is recorded by the formation of platy phlogopite (~ 10 wt% K₂O), prior to incorporation of the xenoliths in the kimberlite. The bulk of the metasomatic alteration, consisting of spongy-textured clinopyroxene (Cpx 2A, 1–3 wt% Na₂O), coarser-grained clinopyroxene (Cpx 2B, 2–5 wt% Na₂O), pargasitic amphibole (~ 0.8 wt% K₂O; 3–3.5 wt% Na₂O), kelyphite (Cpx 3, mostly <1 wt% Na₂O; and zoned Mg-Fe-Al spinel), sodalite, calcite, K-feldspar, djerfisherite (K_5.95Na_0.02Fe_18.72Ni_2.36Co_0.01Cu_4.08S₂₆Cl ) and a small amount of K-Ca-Fe-Mg glass, is ascribed to the metasomatic event II that occurred also in the upper mantle, but after the xenoliths were incorporated in the kimberlite. A pervasive chloritic alteration (mainly clinochlore + magnetite) that overprints earlier assemblages probably took place in the upper crustal environment. The diamonds are invariably associated with secondary clinopyroxene and chlorite, but the diamonds formed before the entrainment of the xenoliths in the Udachnaya kimberlite.Editorial Responsibility: T.L. Grove     

A thermodynamic model of Fe–Cr spinels

A new thermodynamic model for multi-component spinel solid solutions has been developed which takes into account thermodynamic consequences of cation mixing in spinel sublattices. It has been applied to the evaluation of thermodynamic functions of cation mixing and thermodynamic properties of Fe₃O₄–FeCr₂O₄ spinels using intracrystalline cation distribution in magnetite, lattice parameters and activity-composition relations of magnetite–chromite solid solutions. According to the model, cation distribution in binary spinels, (Fe_1-x²⁺ Fe_x³⁺)[Fe_x²⁺Fe_2-2y-x³⁺Cr_2y]O₄, and their thermodynamic properties depend strongly on Fe²⁺–Cr³⁺ cation mixing. Mixing of Fe²⁺–Fe³⁺ and Fe³⁺–Cr³⁺ can be accepted as ideal. If Fe²⁺, Fe³⁺ and Cr are denoted as 1, 3 and 4 respectively, the equation of cation distribution is –RT ln(x²/((1–x)(2–2y–x)))= G₁₃^* + (1–2x)W₁₃+y(W₁₄–W₁₃–W₃₄) where G₁₃^* is the difference between the Gibbs energy of inverse and normal magnetite, W_ij is a Margules parameter of cation mixing and G₁₃^*, J/mol =–23,000+13.4 T, W₁₄=36 kJ/mol, W₁₃=W₃₄=0. The positive nonconfigurational Gibbs energy of mixing is the main reason for changing activity–composition relations with temperature. According to the model, the solvus in Fe₃O₄–FeCr₂O₄ spinel has a critical temperature close to 500°C, which is consistent with mineralogical data.     

Characterization of vivianite from Catavi,Llallagua Bolivia

Summary Vivianite from Catavi Mine, Llallagua, Bolivia, has a near ideal composition with traces of Mg, Zn and Mn. Total rare-earth elements are < 1,gmg/g. Mössbauer spectroscopy shows Fe^III/(Fe^II + Fe^III) is approximately 0.04.a = 10.030Å,b = 13.434Å,c = 4.714Å, = 102.73dg. The middle-infrared powder spectrum shows H₂O-related bands at 3490, 3290, 3130 cm^–1 (stretch), 1618 cm^–1 (bend), 825 cm^–1 (rock), and at 665 cm^–1 a possible M-OH₂ twist. P0₄ bands occur at 1045-940 cm^–1 (stretch) and 570-450 cm^–1 (bend). Corresponding laser Raman microprobe bands occur at 1051 (ms), 986 (m), 948 (vs), 867 (mw), 828 (w), 568, 532, 453 (m), 442 (mw). Weak Raman bands at about 342, 303, 270 (w), 235 (ms), 227 (sh, ms), 196 (ms), 187 (sh, m), 162 (mw), and 126 (m) may arise from lattice vibrations. Differential thermal responses include a major endotherm from 115–235°C with a shoulder at 170°C and a maximum at 210°C resulting from loss of structural water combined with oxidation of Fe²⁺, and two small exotherms with maxima at 605 and 780°C related to structural transformations.

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Charakterisierung des Vivianits von Catavi, Llallagua, Bolivien

Zusammenfassung Vivianit von der Catavi Mine, Llallagua, Bolivien zeigt annähernd ideale Zusammensetzung mit Spuren von Mg, Zn und Mn. Der gesamte Gehalt an seltenen EvolElementen ist < 1 ppm. Die Mössbauer Spektroskopie liefert ein Fe³⁺/(Fe²⁺ + Fe³⁺) Verhältnis von ungefähr 0.04.a = 10.030,b = 13.434,c = 4.714 Å, = 102.73°. Das Infrarot-Pulverspektrum zeigt dem H₂0 zuzuordnende Banden bei 3490, 3290, 3130 cm^–1 (Streckschwingungen), 1618 cm^–1 (Deformationsschwingung), 825 cm^–1 (Schaukelschwingung) und eine mögliche M-OH₂ Torsionsschwingung bei 665 cm^–1. PO₄ Banden liegen bei 1045-940 cm^–1 (Streckschwingung) und 570-450 cm^–1 (Deformations-schwingung). Entsprechende Banden der Laser Raman Mikrosonde liegen bei 1051 (mst), 986 (m), 948 (sst) 867 (mschw), 828 (schw), 568, 532, 453 (m), 442 (mschw). Raman Banden bei etwa 342, 303, 270 (schw), 235 (mst), 227 (Schulter, mst), 196 (mst), 187 (Schulter, m), 162 (mschw) und 126 (m) können auf Gitterschwingungen zurückgeführt werden. Differential-thermoanalytische Untersuchungen zeigen einen endothermen Bereich von 115–235°C mit einer Schulter bei 170 und einem Maximum bei 210°C, was auf den Verlust von strukturellem Wasser, das an eine Oxidation des Fe²⁺ gebunden ist, zurückzuführen ist; zwei auf strukturelle Transformationen zurückzuführende exotherme Maxima liegen bei 605 und 780°C.

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With 4 Figures     

How Cr<Superscript>3+</Superscript> and Fe<Superscript>3+</Superscript> affect Mg–Al order–disorder transformation at high temperature in natural spinels

Three natural Mg(Al_2-yCr_y)O₄ spinels (y 0.07–0.16), highly ordered in terms of Mg–Al, and one Mg(Al_2–yFe³⁺_y)O₄ spinel (y0.08), highly ordered also in terms of Fe³⁺, were studied by means of X-ray single-crystal diffraction. All samples were heated in situ from 25 to 1000 °C in order to follow both thermal expansion and evolution of the structural state of spinel with temperature. Thermal expansion was monitored by means of the variation of cell edge a with temperature, and found to be well represented throughout the temperature range by a regression line a = a₀ (1+T), slightly different at lower and higher temperatures. Thermal expansion coefficient ₁, referring to the lower temperature range (i.e. during pure thermal expansion), was slightly lower than ₂, calculated only over the highest temperatures. The trend showed different slopes for individual crystals. Structural evolution with temperature was studied by means of the variation of oxygen positional parameter u, which is strongly influenced by intersite cation exchange and thus closely correlated with inversion parameter x. In particular, in the three Cr samples, in which Cr resides only in the octahedral site, u parameter variations and hence the order–disorder process, started at about 700 °C. Instead, in the Fe³⁺ sample, this process was triggered at lower temperatures, starting at 550 °C with Fe³⁺–Mg exchange followed at higher temperatures by that of Mg–Al. Cr contents in the Cr samples affected the occupancy of Al in the tetrahedral site at the highest temperatures. In both Mg–Al–Cr and Mg–Al–Fe³⁺ compositions, if CrFe³⁺, parameter u reached the same value only when the Mg–Al exchange was dominant, i.e. at the highest temperatures, but not before. Cation distribution at each temperature was obtained by the bond-length model, applying thermal expansion to pure bond lengths. This method is applied here to complex compositions for the first time.