Partition of Ni between olivine and sulfide: equilibria with sulfide-oxide liquids

The partition of Ni between olivine and monosulfide-oxide liquid has been investigated at 1300–1395° C, =10^–8-9–10^–6.8, and =10^–2.0–10^–0.9, over the composition range 20–79 mol. % NiS. The product olivine compositions varied from Fo98 to Fo59 and from 0.06 to 3.11 wt% NiO. The metal/sulfur ratio of the sulfide-oxide liquid increases with increase in , decrease in , and increase in NiS content. The Ni/Fe exchange reaction has been perfectly reversed using natural olivine and pure forsterite as starting materials. The FeO and NiO contents of olivine from runs equilibrated at the same and form isobaric distributions with NiS content, which, to a first approximation, are dependent at constant temperature and total pressure on a variable term, –0.5 log ( / ). The Ni/Fe distribution coefficient (K _D3) exhibits only a weak decrease from 35 to 29 with increase in from the IW buffer to close to the FMQ buffer. At values higher than FMQ, the sulfide-oxide liquid has the approximate composition (Ni,Fe)₃±_xS₂K _D358. The present K _D3 vs O/(S+O) data define a trend which extrapolates to K _D320 at 10 wt% oxygen in the sulfide-oxide liquid. The compositions of olivine and Ni-Cu sulfides associated with early-magmatic basic rocks and komatiites are consistent, at 1400° C, with a value of -log ( / ) of about 7.7, which is equivalent to 0.0 wt% oxygen in the hypothesized immiscible sulfide-oxide liquid. Therefore, K _D3 would not be reduced significantly from the 30 to 35 range for sulfide-oxide liquids with low oxygen contents.     

The pressure and temperature stability limits of lawsonite: implications for H2O recycling in subduction zones

The stability relations of lawsonite, CaAl₂Si₂O₇(OH)₂H₂O, have been investigated at pressures of 6 to 14 GPa and temperatures of 740 to 1150°C in a multi-anvil apparatus. Experiments used the bulk composition lawsonite+H₂O to determine the maximum stability of lawsonite. Lawsonite is stable on its own bulk composition to a pressure of 13.5 GPa at 800°C, and between 6.5 and 12 GPa at 1000°C. Its composition does not change with pressure or temperature. All lawsonite reactions have grossular, vapour and two other phases in the system Al₂O₃-SiO₂-H₂O (ASH) on their high-temperature side. A Schreinemakers analysis of the ASH phases was used to relate the reactions to each other. At the lowest pressures studied lawsonite breaks down to grossular+kyanite+coesite+vapour in a reaction passing through 980°C at 6 GPa and 1070°C at 9 GPa. Above 9 GPa the reactions coesite=stishovite and kyanite+vapour=topaz-OH are crossed. The maximum thermal stability of lawsonite is at 1080°C, at 9.4 GPa. At higher pressures the lawsonite breakdown reactions have negative slopes. The reaction lawsonite=grossular+topaz-OH+stishovite+vapour passes through 1070°C at 10 GPa and 1010°C at 12 GPa. At 14 GPa, 740–840°C, lawsonite is unstable relative to the assemblage grossular+diaspore+vapour+a hydrous phase with an Al:Si ratio of 1:1. Oxide totals in electron microprobe analyses suggest that the composition of this phase is AlSiO₃(OH). Two experiments on the bulk composition lawsonite+pyrope [Mg₃Al₂Si₃O₁₂] show that at 10 GPa the reaction lawsonite=Gr-Py_ss+topaz-OH+stishovite+vapour is displaced down temperature from the end-member reaction by 200°C for a garnet composition of Gr₂₀Py₈₀. Calculations suggest similar temperature displacements for reaction between lawsonite and Gr-Py-Alm garnets of compositions likely to occur in high-pressure eclogites. Temperatures in subduction zones remain relatively low to considerable depth, and therefore slab P-T paths can be within the stability field of lawsonite from the conditions of its crystallisation in blueschists and eclogites, up to pressures of at least 10 GPa. Lawsonite contains 11.5 wt% H₂O, which when released may trigger partial melting of the slab or mantle, or be incorporated in hydrous phases such as the aluminosilicates synthesised here. These phases may then transport H₂O to an even greater depth in the mantle.     

Koritnigit,Zn[H2O|HOAsO3], ein neues Mineral aus Tsumeb,Südwestafrika

Zusammenfassung Das neue Mineral Koritnigit ist ein wasserhaltiges Zinkhydrogenarsenat der Formel Zn[H₂O|HOAsO₃]. Die chemische Analyse (Elektronenmikrosonde und T.G.A.) ergab: As₂O₅ 51,75%, ZnO 35,97% und H₂O 12,3%, Summe 100,0%. Die HOAsO₃-Ionen wurden IR-spektroskopisch nachgewiesen. Koritnigit ist löslich in kalter, verdünnter HCl und HNO₃.Die Gitterkonstanten sind:a ₀=7,948(2),b ₀=15,829(5),c ₀=6,668(2) Å, =90,86(2), =96,56(2), =90,05(2)^o,V=833,2(4)ų,V=8. Die Raumgruppe ist . Die stärksten Linien des Pulverdiagramms sind: 7,90(10) (020,100), 3,83(7) ( ), 3,16(9) ( ) 2,926(4) (150), 2,679(4) ( ), 2,461(6) ( ), 2,186(5) ( ), 1,969(4) (400), 1,649(3) (004).Koritnigit ist wasserklar bis durchscheinend weiß. Idiomorphe Kristalle sind nicht bekannt. Die Spaltbarkeit nach {010} ist ausgezeichnet und auf {010} sind Spaltspuren nach [001] und nach [100] erkennbar. Härte 2.G=3,54 g·cm^–3,D _x =3,56 g·cm^–3. Koritnigit ist optisch zweiachsig positiv, 2V70(5)^o. Die Werte der Lichtbrechung sind:n =1,632(5),n =1,652(3) undn =1,693(3).Koritnigit wurde auf der 31. Sohle der Tsumeb-Mine, Südwestafrika gefunden. Er kommt als Sekundärmineral in Paragenese mit Cu-Adamin, Stranskiit und drei weiteren, vorerst nicht identifizierten mineralen in Zersetzungshohlräumen von Tennantit vor.

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Koritnigite, Zn[H₂O|HOAsO₃], a new mineral from Tsumeb, South West Africa

Summary The new mineral koritnigite is a hydrated zinc hydrogen arsenate with the formula Zn[H₂O|HOAsO₃]. Chemical analysis (electron microprobe and t.g.a.) gave: As₂O₅ 51.75%, ZnO 35.97%, and H₂O 12.3%, total 100.0%. The HOAsO₃ ions were determined by IR spectroscopy. Koritnigite is soluble in cold diluted HCl and HNO₃. The unit cell dimensions are:a ₀=7.948(2),b ₀=15.829(5),c ₀=6.668(2)Å, =90.86(2), =96.56(2), =90.05(2)^o,V=833.2(4) ų,Z=8. The space group is . The strongest lines of the powder pattern are: 7.90(10) (020, 100), 3.83(7) ( ), 3.16(9) ( ), 2.926(4) (150), 2.679(4) ( ), 2.461(6) ( ), 2.186(5) ( ), 1.969(4)(400), 1.649(3) (004).

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Mit 2 Abbildungen

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Herrn Univ. Prof. Dr.H. Meixner zum 70. Geburtstag gewidmet.     

Nickenichite,a new arsenate from the Eifel,Germany

Summary Nickenichite is a new mineral found close to the village of Nickenich at the Nickenicher Sattel, Eifel, Germany. The chemical composition is Na_xCa_yCu_z(Mg, Fe, Al)₃(AsO₄)3, x 0.8, y 0.4, 0.4 and was derived by means of electron microprobe analyses and by a crystal structure investigation. The latter was determined from single-crystal X-ray data:a = 11.882(4)Å,b = 12.760(4)Å,c = 6.647(2)Å, = 112.81(2)°, space group C2/c,Z = 4;R = 0.053 andR _w = 0.033 from 984 observed data and 102 free variables. Nickenichite is structurally related to the minerals o'danielite and johillerite. The two crystallographically different octahedrally coordinated cation positionsMe = (Mg, Fe, Al) have averageMe-O distances of 2.108 Å and 2.056 Å, octahedra share edges to form zig-zag chains in ; the chains are interconnected by AsO₄ tetrahedra. In addition the compound is characterized by partially occupied Na^[4+4], Ca^[6+2] and Cu^[4] positions.

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Nickenichit, ein neues Arsenat aus der Eifel, Deutschland

Zusammenfassung Nickenichit ist ein neues Mineral, das nahe dem Ort Nickenich, am Nickenicher Sattel, Eifel, Deutschland, gefunden wurde. Die chemische Formel ist Na_xCa_yCu_z, (Mg, Fe, Al)₃(AsO₄)₃, x 0,8, y 0,4, z 0,4 und wurde mittels Elektronenstrahl-Mikrosondenanalysen und einer Kristallstrukturuntersuchung ermittelt. Letztere wurde mit Einkristall-Röntgendaten durchgeführt:a = 11,882(4) Å,b = 12,760(4) Å,c = 6,647(2) Å, = 112,81(2)°, Raumgruppe C2/c,Z = 4;R = 0,053 undR _w = 0,033 für 984 beobachtete Daten und 102 freie Variable. Nickenichit zeigt enge strukturelle Beziehungen zu den Mineralen O'Danielit und Johillerit. Die zwei kristallographisch verschiedenen oktaedrisch koordinierten KationpositionenMe = (Mg, Fe, Al) haben mittlereMe-O-Abstände von 2,108 Å und 2,056 Å, die Oktaeder werden über Kanten zu zick-zack-artigen Ketten in verknüpft, diese werden untereinander über AsO₄-Tetraeder vernetzt. Des weiteren ist die Verbindung durch partiell besetzte Na^[4+4]-, Ca^[6+2]- und Cu^[4]-Positionen charakterisiert.

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With 2 Figures     

P total,P_{H_2 O} and the occurrence of cummingtonite in volcanic rocks

The phenocryst assemblage of cummingtonite, orthopyroxene, quartz, titanomagnetite and ilmenite in rhyolites of New Zealand has been used to calculate P _total and . The values of P _total and depend strongly upon whether an ideal mixing, or an ordered, model is used for the solid-solutions, but in both cases P _total.The rhyolite magma contained over 9 per cent water (by weight) when the cummingtonite phenocrysts precipitated, and possibly as much as 12 per cent, so that it is surprising that one of these rhyolites is a coherent lava. The calculated values of P _total and are very sensitive to uncertainty in both the composition of the solid-solutions and temperature. Calculations show that >0.7–0.8 P _total for cummingtonite to precipitate in rhyolites, and that iron-rich olivine and cummingtonite could only exist in rhyolites over a small temperature range at a pressure near 5 kilobars. Hornblende phenocrysts co-existing with fayalitic olivine in rhyolites accordingly have a very low activity of Mg₇Si₈O₂₂(OH)₂.     

The TiO2 frequency in volcanic rocks

The authoress calculates the frequency of the TiO₂-content in the lavas of the active volcanoes and shows by the aid of a quotient =Al₂O₃ – Na₂O/TiO₂ the pronounced bimodality of the frequency curve from which she concludes that the great variety of the magmas cannot be explained by a magmatic differentiation but only by a double origin of the magmas from the upper mantle and from the sialic crust of the earth.

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Zusammenfassung Die Verfasserin berechnet die Häufigkeit des TiO₂-Gehalts in den Laven der tätigen Vulkane und zeigt vermittelst eines Quotienten =Al₂O₃ – Na₂O/TiO₂ die ausgesprochene Bimodalität der Häufigkeitskurve, woraus sie den Schluß zieht, daß die große Verschiedenheit der Magmen nicht durch eine magmatische Differentiation erklärt werden kann, sondern daß man eine zwiefache Herkunft der Magmen annehmen muß: aus dem oberen Mantel und aus der sialischen Kruste der Erde.

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Résumé L'auteur calcule la fréquence du pourcentage de TiO₂ dans les laves des volcans la bimodalité cans actifs et montre, à 1 aide d un quotient =Al₂O₃ – Na₂O/TiO₂ la bimodalité prononcée des courbes de fréquence, et en tire la conclusion que la grande variété des magmas ne peut pas être expliquée par une différenciation magmatique, mais par l'origine double des magmas: du manteau supérieur et de la crôute sialique de la terre.

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Riassunto L'autrice calcola la frequenza del contenuto in TiO₂ nelle lave dei vulcani attivi e dimostra mediante un quoziente =Al₂O₃ – Na₂O/TiO₂ la pronunziata bimodalità delle curve di frequenza e ne trae la conclusione che la grande varietà dei magmi non è dovuta a differenziazione magmatica ma ad una duplice provenienza: dal mantello superiore e dalla crosta sialica della terra.

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. , , , : 1. , 2. .

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Dedicated to Professor Dr. A.Rittmann on the occasion of his 75. birthday

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This study is a part of the researches, carried out with the funds of the National Research Council of Italy under the direction of Prof. A.Rittmann.     

Origin and regional significance of late Precambrian and early Palaeozoic granitoids in the Pan-African belt of Somalia

Granitoids within the Precambrian basement of north-eastern and southern Somalia are subdivided on the basis of geology, geochronology and petrology into three different assemblages. The post-kinematic assemblage in north-eastern Somalia ( 630 Ma) comprises granodiorites and granites which belong to a medium-K calc-alkaline suite. Average initial Sr, Nd and Pb isotopic ratios [Sr_i = 0.7048, _Nd = –1.8,²⁰⁶Pb/²⁰⁴Pb(i) = 17.704 and²⁰⁷Pb/²⁰⁴Pb(i) = 15.611] indicate that these melts were derived from a mantle or juvenile crustal source with only slight involvement of pre-existing crust as a contaminant. Two different assemblages are found in southern Somalia. The older assemblage is composed of crustal anatectic, synkinematic, parautochthonous granites ( 600 Ma) related to amphibolite facies retrogression of an intensively reworked pre-Pan-African crust [Sr_i = 0.7100, _Nd = –8.4,²⁰⁶Pb/²⁰⁴Pb(i) = 15.403 and²⁰⁷Pb/²⁰⁴Pb(i) = 15.259]. These monzo- and syenogranites are moderately potassic and peraluminous. The younger assemblage ( 470 Ma) consists of post-kinematic monzonites to syenogranites with A-type affinities. Initial Sr, Nd and Pb isotopic data for this metaluminous assemblage [Sr_i = 0.7114, _Nd = –13.1,²⁰⁷Pb/²⁰⁴Pb(i) = 16.913 and²⁰⁷Pb/²⁰⁴Pb(i) = 15.512] indicate a significant lower crustal component but, however, also a mantle signature. The late Proterozoic to early Palaeozoic granitoids in Somalia thus express contrasting regimes, characterized by strong juvenile input in the north, close to the Arabian-Nubian Shield, whereas intense crustal reworking with little addition of juvenile material prevailed in the south. Somalia was definitively not a cratonic area during the Pan-African, but a zone of high crustal mobility.     

Reaction progress during mylonitization of basaltic dikes along the Särv thrust,Swedish Caledonides

The mylonite zone at the base of the Särv thrust sheet, Swedish Caledonides, contains diabase dikes which record intense deformation and syntectonic greenschist facies metamorphism. An angular shear strain of 100 is calculated for a single dike which can be followed for 50 m in the mylonite zone and abundant centimeter thick greenschist layers imply shear strains in excess of 1000. This extraordinary amount of deformation is comparable to the largest strains attained during experimental superplastic deformation of metals and alloys and, by analogy, suggests that dike deformation was macroscopically superplastic. The progress of five syntectonic reactions was measured as a function of increasing strain for the continuously exposed dike in order to assess the contribution of reactionenhanced ductility and fluid-rock interactions to strain localization along the thrust. Reaction progress calculations suggest that the breakdown of amphibole to form weaker phyllosilicates (which are added to the incompetent matrix fraction) is the important strain softening mechanism below 100. The ultimate tectonite is a stable biotite-epidote schist comprised of a uniformly fine grain size (< 200 m), constant grain shapes and strain free grains. Below 40, metamorphism was isochemical and shear strain was independent of H₂O in the reactions. Petrologic fluid:rock ratios are low and suggest that deformation could have occurred under relatively dry conditions.Deformation micromechanisms were probably dominated by diffusive mass transfer processes throughout the life of the shear zone. The absence of cataclasis and the fine grain size of the protolith basalt suggest that fluids were introduced via grain boundary diffusion. Incongruent pressure solution at low strains and K-metasomatism above 40 also support diffusional flow. Diffusion-accomodated grain boundary sliding is thought to be the dominant micromechanism once the stable biotite-epidote tectonite forms.     

Die Verteilung der Lanthaniden im Tholeyit von Tholey (Saar) und in Palatiniten,Pseudopegmatiten und Apliten des permischen Vulkanismus im Saar-Nahe-Pfalz-Gebiet

Zusammenfassung Ein Teil der im Unterperm (Wende Unterrotliegendes/Oberrotliegendes) gebildeten magmatischen Gesteine des Saar-Nahe-Pfalz-Gebietes wurde auf Lanthaniden untersucht: Gesteins-Gruppe 1: doleritischer Olivinbasalt, Pigeonit-Tholeyit, Tholeyit (Originalvorkommen) aus dem Schaumberg-Sill bei Tholey (Saar), und Plagiaplit. Gesteins-Gruppe 2: Palatinit, Pseudopegmatit, Aplit.Gesteins-Gruppe 1: Der Tholeyit aus dem Schaumberg-Sill zeigt deutlich höhere absolute Lanthanidengehalte (180 und 230 ppm Y, La-Lu) und eine stärkere Anreicherung der leichteren Lanthaniden La-Eu im Vergleich zu den ozeanischen und kontinentalen tholeiitischen Basalten (100 ppm Y, La-Lu). Das ist ein weiterer Hinweis dafür, daß der Tholeyit vom Locus typicus nicht identisch ist mit dem als tholeiitischer Basalt bezeichneten Gesteinstyp. Im Gegensatz zu den absoluten Lanthanidengehalten bestehen aber praktisch keine Unterschiede bei der relativen Lanthanidenverteilung zwischen dem Liegenden und dem Hangenden des Sill. Mit ansteigendem K₂O/Na₂O-Verhältnis wird in der Reihenfolge: doleritischer Olivinbasalt, Pigeonit-Tholeyit, Tholeyit aus dem Schaumberg-Sill und Plagiaplit eine Zunahme der absoluten Lanthanidengehalte und eine fortschreitende Fraktionierung zwischen den leichteren und den schwereren Lanthaniden festgestellt. Eine aus petrographischen Befunden von Jung (1958) vermutete Differentiation zwischen den genannten Gesteinstypen deutet sich somit auch in der Lanthanidenverteilung an.Gesteins-Gruppe 2: Ähnliche Zusammenhänge bestehen zwischen Palatiniten (180 ppm Y, La-Lu, 3 Proben), Pseudopegmatit (290 ppm Y, La-Lu, 1 Probe) und Apliten (270 ppm Y, La-Lu, 3 Proben), jedoch hier ohne klar erkennbare Abgängigkeit von den K₂O/Na₂O-Verhältnissen.

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Distribution of the lanthanide elements in the tholeyite from tholey (saar, W.-Germany) and in palatinite, pseudopegmatite, and aplite of the permian volcanism in the saar-nahe-pfalz area

Several types of magmatic rocks from the Saar-Nahe-Pfalz area (lower Permian) have been analysed for the 14 lanthanide elements and yttrium: rocks of group 1. doleritic olivine basalt, pigeonite tholeyite, tholeyite (type locality) from the Schaumberg sill near Tholey (Saar), and plagiaplite; rocks of group 2. palatinite, pseudopegmatite, aplite.Rocks of group 1. It is important to note the higher absolute Y and La-Lu contents (180 and 230ppm Y, La-Lu) and the relative enrichment of the lighter lanthanides in the tholeyite from the Schaumberg sill as compared with oceanic and continental tholeiitic basalts (100 ppm Y, La-Lu). This is additional evidence against the assumption that the tholeyite from the type locality has genetic relations to the so-called oceanic and continental tholeiitic basalts. The lanthanide elements in the tholeyite increase in concentration from the lower to the upper part of the Schaumberg sill, but there is little change in relative abundances within the sill. Increasing K₂O/Na₂O ratios are accompanied by an increase of the absolute lanthanide concentrations and by a progressive accumulation of the lighter lanthanides in the sequence: doleritic olivine basalt, pigeonite tholeyite, tholeyite from the Schaumberg sill, plagiaplite. The distribution pattern of the lanthanides in these rocks confirms the explanation of the petrographic observation by Jung (1958) as a magmatic differentiation series.Rocks of group 2. Similar relations were observed between palatinites (180 ppm Y, La-Lu, 3 samples), pseudopegmatite (290 ppm Y, La-Lu, 1 sample), and aplites (270 ppm Y, La-Lu, 3 samples), but there was no clear evidence for a correlation of lanthanide distribution with K₂O/Na₂O ratios.

     

Quantitative P-T paths from zoned minerals: Theory and tectonic applications

An analytical approach to the analysis of zoning profiles in minerals is presented that simultaneously accounts for all of the possible continuous reactions that may be operative in a given assemblage. The method involves deriving a system of simultaneous linear differential equations consisting of a Gibbs-Duhem equation for each phase, a set of linearly independent stoichiometric relations among the chemical potentials of phase components in the assemblage, and a set of equations describing the total differential of the slope of the tangent plane to the Gibbs free energy surface of solid solution phases. The variables are the differentials of T, P, chemical potentials of all phase components, and independent compositional terms of solid solution phases. The required input data are entropies, volumes, the compositions of coexisting phases at a reference P and T, and an expression for the curvature of the Gibbs functions for solid solution phases. Results derived are slopes of isopleths (dP/dT, dX/dT or dX/dP) which can be used to contour P-T diagrams with mineral composition.To interpret mineral zoning, T and P can be expressed as functions of n independent composition parameters, where n is the variance of the mineral assemblage. The total differentials of P and T are differential equations that can be solved by finite difference techniques using the derivatives obtained from the analytical formulation of phase equilibria.Results calculated from Zone I and Zone IV garnets of Tracy et al. (1976) indicate that Zone I garnets grew while T increased (T+72° C) and P decreased sharply (P–3 kb). Zone IV garnets zoned in response to decreasing T (T–17° C) and P (P–1 kb). A P-T path calculated for a zoned garnet from the Greinerschiefer series, western Tauern Window, Austria, also indicates growth during decompression (–3kb) and heating (T+15° C). A P-T path calculated for the Wissahickon schist (Crawford and Mark 1982) indicates growth during cooling and compression (T–25 C, P+2.2 kb). The calculated P-T paths differ according to structural environment and can be used to relate mineral growth to tectonic processes.     

Machatschkiit,ein neues Arsenatmineral aus der Grube Anton im Heubachtal bei Schiltach (Schwarzwald,Bundesrepublik Deutschland)

Zusammenfassung Machatschkiit ist ein neues wasserhaltiges Calciumarsenat, das in der Grube Anton bei Schiltach im mittleren Schwarzwald (BRD) 1960 gefunden wurde. Es kommt zusammen mit Gips, Pharmakolith, Pikropharmakolith und Sainfeldit als Sekundärbildung krustenförmig auf Granit vor.Als charakteristische Form tritt das Rhomboeder auf. Keine Spaltbarkeit, Bruch muschelig, Härte 2–3,G=2,5 bis 2,6 g·cm^–3,D _x =2,50 g·cm^–3, farblos, durchsichtig bis durchscheinend. Optische Daten:n =1,585±0,002,n =1,593±0,002, einachsig oder schwach zweiachsig, negativ.Gitterkonstanten:a ₀=15,10,c ₀=22,59 Å,a ₀c ₀=11,4960,Z=12;a _rh =11,52 Å, =81°52,Z=4. Mögliche Raumgruppen:R32,R3m, . Stärkste Linien des Pulverdiagramms: 8,59 (10) (110), 5,34 (8) (210), 3,59 (8) . Eine chemische Analyse ergab nach Umrechnung folgende Zusammensetzung: CaO 29,5%, As₂O₅ 40,8%, SO₃ 0,5%, H₂O 29,2%, Summe 100,0%. Dies kommt der Formel Ca₃(AsO₄)₂ · 9 H₂O sehr nahe. In verdünnter HCl und HNO₃ ist der Machatschkiit leicht löslich.

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Machatschkiite, a new arsenate mineral from the Anton Mine in the Heubach valley near Schiltach (Black Forest, Federal Republic of Germany)

Summary Machatschkiite is a new hydrous calcium arsenate which was found 1960 in the Anton Mine near Schiltach in the central Black Forest. It is a secondary mineral which occurs in crusts on granite in association with gypsum, pharmacolite, picropharmacolite and sainfeldite.The characteristic form is the rhombohedron . No cleavage, fracture conchoidal, hardness 2–3,G=2.5–2.6 g·cm^–3,D _x =2.50 g·cm^–3, colourless, transparent to translucent. Optical data:n =1.585±0.002,n =1.593±0.002, uniaxial or weakly biaxial, negative.Unit-cell dimensions:a ₀=15.10,c ₀=22.59 Å,a ₀c ₀=11.4960,Z=12;a _rh =11.52 Å, =81°52,Z=4. Possible space groups:R32,R3m, . Strongest lines of the powder pattern: 8.59 (10) (110), 5.34 (8) (210), 3.59 (8) . A chemical analysis gave the following composition after recalculation: CaO 29.5%, As₂O₅ 40.8%, SO₃ 0.5%, H₂O 29.2%, total 100.0%. This agrees well with the formula Ca₃(AsO₄)₂ · 9 H₂O. Machatschkiite is easily soluble in diluted HCl and HNO₃.

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Mit 3 Abbildungen     

The potassic feldspar in metamorphic rocks from the western Hohe Tauern area,eastern Alps

Zusammenfassung Es wurden Kalifeldspäte aus Orthogneisen, Paragneisen und Glimmerschiefern des westlichen Tauemfensters (Hohe Tauern, Tirol) mit optischen und röntgenographischen Methoden im Hinblick auf ihren Strukturzustand untersucht.Es zeigte sich, daß in den Randbereichen des Tauemfensters in Gesteinen der Grünschieferfazies weitgehend geordneter Mikroklin mit einem optischen Achsenwinkel 2 V_x 80°, Auslöschungswinkel Z (010)=15–20°, Doppelbrechung n_z-n_x= 0,0065, Triklinität=0,90-–0,95, ca. 0,88 Al auf T₁O-Position und einem Ab-Gehalt von ca. 5 Gew.% auftritt. Dagegen wurden in Gesteinen der schwachtemperierten Amphibolitfazies des zentralen Bereichs Orthoklase bis intermediäre Mikrokline mit stark schwankenden optischen Eigenschaften, mit Triklinitäten zwischen 0 und 0,7, 0,8 bis 0,9 Al in T₁-Positionen, 0,45–0,8 Al auf T₁O und Ab-Gehalten von ca. 10 Gew.% festgestellt. Die Kalifeldspatkristalle zeigen ungleichmäßige Auslöschung mit Winkeln von Z (010) zwischen 0 und 15°, 2 V_x zwischen 50 und 75° und n_z-n_x=0,005 bis 0,006. Teilweise ist Zonarbau mit geringerer Triklinität am Kornrande erkennbar. Diese undulös auslöschenden Kalifeldspäte enthalten einzelne schmale Lamellen von maximal triklinem Mikroklin mit Z (010)=15–20° und n_z-n_x= 0,006–0,007.Die Grenze zwischen dem Verbreitungsgebiet von maximalem Mikroklin einerseits und Orthoklas bis intermediärem Mikroklin andererseits verläuft in den westlichen Hohen Tauern ungefähr konform mit der Albit-Oligoklas-Grenze (Morteani &Raase, 1974) und mit der aus Sauerstoff-Isotopen-Untersuchungen bestimmten 500° C-Isotherme (Hoernes &Friedrichsen, 1974).

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The potassic feldspar in orthogneisses, paragneisses, and mica schists from the western Tauernfenster (Hohe Tauern, Tyrol) were studied by optical and X-ray methods with regard to their structural state and in relation to grade of metamorphism.In the peripheral region of the Tauernfenster in greenschist-facies rocks highly triclinic microcline occurs with an optic angle 2 V_x of about 80°, extinction angle Z (010) =15–20°, birefringence n_z-n_x=0.0065, triclinicity=0.90–0.95, approx. 0.88 Al in T₁O-site, and an Ab-content of about 5 wt.%. In the central area with rocks of the low-grade amphibolite facies, on the other hand, orthoclase to intermediate microcline with highly variable optical properties, triclinicities in the range of 0–0.7, 0.8–0.9 Al in T₁-sites, 0.45–0.8 Al in T₁O-site, and an Ab-content of about 10 wt.% was recognized. The K-feldspar grains have nonuniform extinction Z (010) scattering in the range of 0–15°, 2 V_x in the range of 50–75°, and n_z-n_x= 0.005–0.006. Sometimes a zonal structure with lower triclinicity exists at the rim. These undulatory K-feldspar grains usually contain small lamellae of highly triclinic microcline with Z (010) =15–20° and n_z-n_x=0.006–0.007.From the occurrence of maximum microcline and of orthoclase to intermediate microcline in the Hohe Tauern area an isograd was defined that is approximately conformable with the albite-oligoclase isograd (Morteani &Raase, 1974) and with the 500° C isotherm based on oxygen isotope analyses (Hoernes &Friedrïchsen, 1974).

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Résumé Les feldspaths potassiques d'orthogneiss, de paragneiss et de micaschistes de la Fenêtre des Tauern occidental (Hohe Tauern, Tirol) ont été étudiés du point de vue de leur état structural.Dans les roches du faciès schistes verts de la région périphérique de la Fenêtre des Tauern les microclines sont caractérisés par un angle des axes optiques 2 V_p =80°, un angle d'extinction n_g (010)=15–20°, une biréfringence n_g-n_p=0,0065, une triclinicité= 0,90–0,95, 0,88 Al dans le site T₁O et par une teneur en albite d'environ 5%. Au contraire, dans les roches du faciès amphibolite à faible degré de la région centrale, ont été observées des orthoses allant à des microclines intermédiaires avec des propriétés optiques très variables, un degré de triclinicité de 0 à 0,7, 0,8–0,9 Al dans les sites T₁, 0,45–0,8 Al dans T₁O et avec une teneur en albite d'environ 10%.Les cristaux de feldspath montrent une extinction irrégulière avec des angles Z (010) variable de 0 à 15°, 2 V_p de 50 à 75° et n_g-n_p=0,005–0,006.On peut voir quelquefois une structure zonée avec une triclinicité moindre au bord des cristaux. Ces feldspaths potassiques contiennent de minces lamelles de microcline à triclinicité maximum, avec n_g (010)=15–20° et n_g-n_p 0,006–0,007.La limite entre les régions à microcline maximum d'une part, et à orthose ou microcline intermédiaire d'autre part, suit, dans les Hohe Tauern, sensiblement l'isograde albite-oligoclase (Morteani &Raase, 1974) et, l'isotherme de 500° C telle qu'elle fut determinée les isotopes de l'oxygène (Hoernes &Friedrichsen, 1974).

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, ( , ) ., 2 V_x80°, Z (010)=15–20°, n_z–n_x=0,0065, =0,90–0,95, 0,88 l T₁O Ab 5 .-%. , 0 0,7, 0,8-0,9 1 T₁ l 10 .-%. Z V (010) 0 15°, 2 V_x 50 75° n_z–n_x=0,005–0,006. . Z V (010) =15-20° n_z–n_x=0,006–0,007. , Morteani & Raase (1974) 500° , Hoernes & Friedrichsen (1974).

     

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

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

Water in microcrystalline quartz of volcanic origin: Agates

Agates of volcanic origin, containing the different quartz species, fibrous, length-fast chalcedony (CH), granular fine quartz (FQ), and fibrous, length-slow, to lepidospheric quartzine (QN), have been investigated to evaluate possible relations between microstructure, i.e. crystallite size and texture, refractive indices, densities, contents of trace elements and of water, as well as dehydration behaviour. By means of near infrared spectroscopy, total water contents , could be differentiated quantitatively into contents of molecular water, , and silanole-group water, . Despite the low total water contents of the agates studied ( between 1 and 2 wt.%), near infrared spectroscopy results in reliable data on and .Wall-layering CH consists of fibrous quartz crystals and exhibits higher C-ratios, , than horizontally layered FQ which consists predominantly of granular quartz crystals (C _CH=0.45±0.11 (N=6), C _FQ=0.36±0.10 (N=4). This result is interpreted to be due to analogy with the behaviour of C-ratios in fluid phase-deposited opals-AN (hyalithe) and liquid phase-deposited opals-AG (non-crystalline opal) or -CT (common opal) (Langer and Flörke 1974).Translucent layers of CH show mostly lower refractive indices, when measured parallel than when measured perpendicular to the axes of the quartz fibers. The same is true for milky layers of CH. Crystallite sizes are smaller in the latter than in the former.For all samples studied, exists a positive correlation between at% (1/2Ca+1/2Mg+Na+K+Li) and at% (Al³⁺+Fe³⁺). This indicates that at least parts of (A1³⁺+ Fe³⁺) substitute for Si in the quartz structure. The charge is balanced by incorporation of di- and mono-valent cations in structural interstices. When the quantity at % H⁺, as obtained from , is included into the sum at% (1/2 Me²⁺+Me⁺), the above correlation is destroyed. This result could be indicative for a strong concentration of the Si-OH groups in the surface of the quartz microcrystallites.     

Johillerit,Na(Mg,Zn)3 Cu(AsO4)3, ein neues Mineral aus Tsumeb,Namibia

Zusammenfassung Die chemische Analyse des neuen Minerals Johillerit mit der Elektronenmikrosonde ergab: Na₂O 5,4, MgO 18,3, ZnO 5,4, CuO 15,8 und As₂O₅ 55,8, Summe 100.7%. Aus diesem Ergebnis wurde die idealisierte Formel Na(Mg, Zn)₃ Cu(AsO₄)₃ abgeleitet. Johillerit ist monoklin mit der RaumgruppeC2/c. Die Gitterkonstanten sind:a=11,870 (3),b=12,755 (3),c=6,770 (2) , =113,42 (2)°,Z=4. Die stärksten Linien des Pulverdiagramms sind: 4,06 (5) (22 ), 3,50 (4) (310), 3,25 (8) (11 ), 2,75 (10) (330, 240), 2,64 (5) (311, 13 , 40 ), 1,952 (4) (13 , 35 ), 1,682 (4) (20 , 460), 1,660 (5) (40 , 71 , 550, 64 ), 1,522 (4) (442, 153, 13 ). Es bestehen enge strukturelle Beziehungen zwischen Johillerit und O'Danielit, Na(Zn, Mg)₃H₂(AsO₄)₃, sowie einigen synthetischen. Verbindungen.Johillerit ist violett durchscheinend. Die Spaltbarkeit nach {010} ist ausgezeichnet und nach {100} und {001} gut.H (Mohs)3.D=4,15 undD _X =4,21 g·cm^–3. Das Mineral ist optisch zweiachsig positiv, 2V80 (5)°. Die Werte der Lichtbrechung sindn =1,715 (4),n =1,743 (4) undn =1,783 (4). Die Auslöschung istn b und auf (010)n c16°. Johillerit ist stark pleochroitisch mit den AchsenfarbenX=violett-rot,Y = blauviolett undZ = grünblau. Das neue Mineral kommt in radialstrahligen Massen gemeinsam mit kupferhaltigem Adamin und Konichalcit in zersetzem Kupfererz von Tsumeb, Namibia, vor. Die Benennung erfolgte nach Prof. Dr.J.-E. Hiller (1911–1972).

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Johillerite, Na(Mg, Zn) ₃ Cu(AsO ₄ ) ₃ , a new mineral from Tsumeb, Namibia

Summary Electron microprobe analysis of the new mineral johillerite gave Na₂O 5.4, MgO 18.3, ZnO 5.4, CuO 15.8, and As₂O₅ 55.8, total 100.7%. From this result, the ideal formula is given as Na(Mg, Zn)₃ Cu(AsO₄)₃. Johillerite crystallizes monoclinic,C2/c. The unit cell dimensions are:a=11.870(3),b=12.755 (3),c=6.770 (2) , =113.42 (2)°,Z=4. The strongest lines on the X-ray powder diffraction pattern are: 4,06 (5) (22 ), 3,50 (4) (310), 3,25 (8) (11 ), 2,75 (10) (330, 240), 2,64 (5) (311, 13 , 40 ), 1,952 (4) (13 , 35 ), 1,682 (4) (20 , 460), 1,660 (5) (40 , 71 , 550, 64 ), 1,522 (4) (442, 153, 13 ). There is a close relationship between johillerite, o'danielite, Na(Zn, Mg)₃H₂(AsO₄)₃, and some synthetic compounds. Johillerite is violet in colour, transparent. Cleavage is {010} perfect, {100} and {001} good.H (Mohs)3.D=4.15 andD _X =4.21 g·cm^–3. The mineral is optically biaxial positive, 2V80 (5)°. The refractive indices are:n =1.715 (4),n =1.743 (4),n =1.783 (4). The extinction isn b and on (010)n c16°. Strongly pleochroic with axial coloursX=violet-red,Y=bluish violet andZ=greenish blue. The new mineral was found in radiated masses together with cuprian adamite and conichalcite in an oxidized copper ore from Tsumeb, Namibia. It is named in honour of Prof. Dr.J.-E. Hiller (1911–1972).

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Mit 1 Abbildung     

Tridymite: Effect of hydrostatic pressure to 6 kbar on temperatures of two rapidly reversible transitions

Trajectories of two reversible phase transitions in a low-Na synthetic tridymite have been determined to 6 kbar by differential thermal analysis (DTA) in hydrostatic apparatus using Ar or CO₂. The temperature of the lower transition increases from 111 ° C at 1 bar linearly with pressure with slope 1₅ deg kbar^–1. Pressure raises the temperature of the upper transition from 157 ±2 ° or 159 ° C (independently determined) at 1 bar wit a slope of 53 deg kbar^–1, up to 0.7 kbar; for the data above that pressure, the initial slope is 64 deg kbar^–1. Above 2–1/2 kbar, the variation is linear with slope 70 deg kbar^–1. No evidence for other transitions was found at any of the apparent changes of slope. Hystereses for both transitions decreased at high pressures compared to 1-bar. Preferred values for the transition enthalpies, together with these slopes and the Clausius-Clapeyron equation, yield estimates for the volume changes at the transitions of 0.01 (lower) and 0.15 to 0.25 (upper) cm³ gfw^–1. These calculated volume changes are not consonant with many of the high temperature volumetric data on tridymites of varying origins.     

Mariner Jura im westlichen Hindukusch (Afghanistan)

Zusammenfassung Am Westrand des Hindukusch konnten erstmalig stark gefaltete und geschieferte Gesteine des Oberjura (Tithon) in Geosynklinalfazies nachgewiesen werden. Schwach geneigte Sedimente des transgredierenden Oberkreidemeeres (Cenoman bis Turon) liegen diskordant darüber.Dieser Befund erlaubt es, die mesozoische Faltung im W-Hindukusch auf den Zeitraum zwischen Tithon und tiefe Oberkreide einzuengen. Daraus ergibt sich, daß der NE-Sporn des Zentralafghanischen Blockes (Wirtz, 1964) zumindest im Oberjura in das Geosynklinalgebiet der Tethys einbezogen war.

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Strongly folded and schistose beds of Upper Jurassic (Tithonian) age in géosynclinal facies are demonstrated for the first time in the western Hindukush. They are overlain unconformably by deposits of the transgressive Upper Cretaceous (Cenomanian—Turonian) sea.This discovery allows to date the Mesozoic orogeny in the western Hindukush as being younger than Tithonian but older than Upper Cretaceous. Hence it follows that the northeast prong of the Central Afghanistan block (Wirtz, 1964) was incorporated into the Tethys geosynclinal belt at least during the Upper Jurassic.

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Résumé L'existence du Jurassique supérieur (Tithonique) à faciès géosynclinal au bord occidental de I'Hindou-Kouch est démontrée pour la première fois. Il s'agit de roches fortement plissées et très schisteuses qui sont superposées par le Crétacé supérieur (Cenomanien-Turonien) transgressif faiblement incliné.Ainsi, dans l'Hindou-Kouch occidental, il est possible de situer l'âge du plissement mésozoique entre le Tithonique et le Crétacé supérieur. Donc on peut dire que l'éperon nord-est du Zentralafghanischer Block (Wirtz, 1964) a appartenu au géosynclinal de la tethys au moins pendant le Jurassique supérieur.

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Herrn Professor Dr.Roland Brinkmann zum 70. Geburtstag gewidmet.     

Al-Si ordering in Sr-feldspar SrAl2Si2O8: IR,TEM and single-crystal XRD evidences

Al-Si ordering in Sr-feldspar has been followed by isothermal annealing, starting from a disordered metastable configuration. Ordering could not be followed by changes in the spontaneous strain as cell parameters did not show significant changes with thermal treatment from 0.016 h to 452 h at T=1350° C, while, on the contrary, significant changes in IR spectra are observed. A single crystal obtained from melt (Q _od 0) has been progressively heated up to 678 h at T=1350° C and the relevant structural refinements enabled to monitor changes in degree of Al-Si order up to Q_od = 0.86. In isothermal treatment for Sr-feldspar it is observed a significantly lower Q _od than in anorthite after the same annealing time. TEM observation has shown in Sr-feldspar, also for shortest annealing, b type reflections, while in anorthite, in the same conditions, e type reflections have been observed (Carpenter 1991a). In the first stages of ordering b APDs sized 100 Å (at T=1350° C, 0.33 h) have been observed in Sr-feldspar; APD coarsening occurs with an activation energy of 120±7 kcal mol^-1, not significantly different from anorthite. The ordering process seems to be a slower process in Sr-feldspar than in anorthite, even though data from longer annealing suggest that the Q _od close to the equilibrium is the same in Sr and Ca-feldspar (Q _od = 0.86 at T=1350° C).     

Characterization of subsurface geometry and radioactivity distribution in the trench containing Chernobyl clean-up wastes

Several radiometric and geophysical methods were applied to characterize the subsurface geometry and radioactivity distribution (especially ¹³⁷Cs) in a trench with low-level wastes at the Chernobyl site. While surface dose rate measurements and electromagnetic soil conductivity survey produced uninterpretable fields of signals, the ground penetrating radar appeared to be an efficient method for characterization of the subsurface geometry of the waste burial. It was established that the trench had the following dimensions: the length was 70 m; average width 6–8 m, and depth 2–2.5 m. Data on ¹³⁷Cs distribution in the trench were obtained by means of a borehole gamma-logging technique. The total inventory of ¹³⁷Cs was estimated at 600±200 GBq. Geostatistical analysis using the semivariogram function has shown regular spatial correlation patterns for the logarithm-transformed ¹³⁷Cs activity of waste material. The correlation length along the trench was 17 m, while across the trench, and in the vertical direction, it was 4 m. The observed correlation patterns supposedly were caused by the method used to dispose the contaminated topsoil: the bulldozing in the direction perpendicular to a trench axis. Obtained results may be useful for selecting a characterization method and for optimization of sampling strategies for similar waste sites.     

Über Strontioginorit,eine neue Ginorit-Varietdt aus dem Zechsteinsalz

Zusammenfassung Strontioginorit (Sr, Ca)₂B₁₄O₂₃ 8 H₂O mit Sr: Ca1,3:0,7 tritt in gut ausgebildeten Kristallen im Alteren Steinsalz von Reyershausen bei Göttingen auf. Es ergaben sich folgende Daten : ₀ = 12,85₀ Å,b ₀ = 14,48 Å,c ₀, = 12,85₅, Å, = 101° 35, RaumgruppeP 2_I/a,Z = 4, Dichte=2,25 gcm^–3,n = 1,512,n _/b = 1,524,n //[101] = 1,577.