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     

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

Die Verbindung Cu2FeSnSe3,8 im Vergleich zum Zinnkies

Zusammenfassung Die Phase Cu₂FeSnSe_3,8 ist tetragonal, Raumgruppe mit ₀=5.69 undc ₀=11,26 Å.Z=2,D _x=5,441. Synthesetemperatur: 410°C.

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The compound Cu₂FeSnSe_3,8 in comparison to stannite

Summary The phase Cu₂FeSnSe_3,8 is tetragonal, space-group with ₀=5.69 andc ₀=11.26 Å.Z=2,D _x=5.441. Temperature of synthesis: 410°C.

     

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.     

Colquiriit,ein neues Fluoridmineral aus der Zinnlagerstätte von Colquiri in Bolivien

Zusammenfassung Colquiriit tritt in Vergesellschaftung mit Ralstonit, Gearksutit, Zinkblende, Madocit und Pyrit im Bereich der Zinnlagerstätte von Colquiri in Bolivien auf. Das als selten zu betrachtende Mineral bildet maximal cm-große xenomorphe durchscheinende bis durch-sichtige Körner von weißlicher Farbe. Es zeigt keine Spaltbarkeit. Härte ca. 4; Dichte (gem.) 2,94, (ber.) 2,95 g/cm³;n 1,385±0.002,n 1,388±0,002, einachsig oder schwach zweiachsig, negativ. Colquiriit kristallisiert trigonal, Raumgruppe oderP31c,a ₀ 5,02,c ₀ 9,67 Å,Z=2. Stärkste Linien des Pulverdiagramms: 3,98(7) ; 3,23(10) ; 2,22(9) ; 1,736(8) . Eine chemische Analyse ergab: Li 3,1, Na 0,34, Mg 0,55, Ca 22,8, Al 13,4, F 58,0, Gewichtsverlust (105 °C) 0,5, Summe 98,69%, woraus sich die idealisierte Formel LiCaAlF₆ ableiten läßt. Beim Erhitzen wird das Gitter zwischen 800 und 900°C zerstört.

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Colquiriite, a new fluoride mineral from the Colquiri tin deposit in Bolivia

Summary Colquiriite occurs at the Colquiri tin deposit in Bolivia and is associated with ralstonite, gearksutite, sphalerite, madocite and pyrite. The mineral, which probably is a rare species, forms anhedral translucent to transparent white grains reaching up to 1 cm in size. No cleavage; hardness about 4; density (meas.) 2.94, density (calc.) 2.95 g/cm³;n 1.385±0.002,n 1.388±0.002, uniaxial or weakly biaxial, negative. Colquiriite is trigonal,a ₀ 5.02,c ₀ 9.67 Å, space group orP31c,Z=2. The strongest lines of the powder pattern are: 3.98(7) ; 3.23(10) ; 2.22(9) ; 1.736(8) . The chemical analysis gave: Li 3.1, Na 0.34, Mg 0.55, Ca 22.8, Al 13.4, F 58.0, weight loss (105 °C) 0.5, sum 98.69%, leading to the idealized formula LiCaAlF₆. Heating experiments show that the lattice breaks down between 800 and 900 °C. The new mineral and its name have been approved by the I.M.A. Commission on New Minerals and Mineral Names.

     

Röntgenuntersuchung der wasserfreien Sulfate der dreiwertigen Metalle Eisen,Chrom und Gallium

Zusammenfassung Wasserfreies Eisen(III)sulfat, Fe₂(SO₄)₃, existiert in zwei Modifikationen. Nach Einkristallaufnahmen kristallisiert die eine wahrscheinlich in Raumgruppe (a_rh=8,791±0,004 Å, =55°52±2; Z=2), die andere in Raumgruppe C _2h ⁵ –P2₁/n (a=8,296±0,002 Å, b=8,515±0,002 Å, c=11,60±0,002 Å, =90°30; Z=4). Von Cr₂(SO₄)₃ und Ga₂(SO₄)₃ konnten für die rhomboedrischen Modifikationen, die isotyp zu jener von Fe₂(SO₄)₃ sind, aus Pulveraufnahmen die Gitterkonstanten bestimmt werden.

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Summary Anhydrous iron(III)sulfate exists in two modifications. From single-crystal work, one of the modifications crystallizes probably in space group (a_rh=8.791±0.004 Å, =55°52±2; Z=2), whereas the other in space group C _2h ⁵ –P2₁/n (a=8.296±0.002 Å, b=8.515±0.002 Å, c=11.60±0,002 Å, =90°30; Z=4). The lattice constants of the rhombohedral modifications of Cr₂(SO₄)₃ and Ga₂(SO₄)₃, which are isomorphous with rhombohedral Fe₂(SO₄)₃, have been determined from powder photographs.

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Herrn Professor Dr.F. Machatschki zum 70. Geburtstag gewidmet.     

Der Strukturtyp von Emmonsit, {Fe2[TeO3]3·H2O}·xH2O (x=0−1)

Zusammenfassung Emmonsit kristallisiert triklin, RaumgruppeP , Gitterkonstanten:a ₀=7,90 Å,b ₀=8,00 Å,c ₀=7,62 Å, =96^o44, =95^o 0, =84^o 28,Z=2. Der Strukturtyp wurde aus 3-dimensionalen photographischen Röntgendaten ermittelt. Die Eisenatome werden je von 6 Sauerstoffen verzerrt oktaedrisch koordiniert. Jedes Telluratom wird von 3 Sauerstoffen in einem Abstand <2,0 Å umgeben. Ein vierter Sauerstoff hat bezüglich dieser drei einen um etwa 25–35% größeren Abstand, so daß jedes Telluratom im weiteren Sinne eine (3+1)-Koordination aufweist.

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The structure type of emmonsite, {Fe₂[TeO₃]₃·H₂O}·xxH₂O (x=0–1)

Summary Emmonsite is triclinic with space groupP , and lattice constantsa ₀=7.90 Å,b ₀=8.00 Å,c ₀=7.62 Å, =96^o 44, =95^o 0, =84⁰ 28,Z=2. The structure type is derived from 3-dimensional photographic X-ray data. The iron atoms are coordinated by six oxygens in the form of a distorted octahedron. Each tellurium atom is coordinated to 3 oxygens at a distance <2.0 Å. Compared with these 3 Te–O distance the distance of a fourth oxygen is only 25 to 35% greater; therefore each tellurium atom has a (3+1)-coordination of oxygens.

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Mit 2 Abbildungen     

Late Archean metamorphism in the Buksefjorden region,Southwest Greenland

Standard state thermodynamic data extracted from experimental studies and applied to mineral assemblages in orthogneisses, metasedimentary gneisses and metabasites show that conditions of late Archean (2,850 m.y.) upper amphibolite facies were P _solid7.0 kb, T630° C, and rose to P _solid10.5 kb, T810° C in adjacent granulite facies. The estimates of solid pressure for the granulite facies suggest a late Archean crustal thickness of ca. 35 km, comparable to present day continental crust. Upper amphibolite facies assemblages were in equilibrium with about one half P _solid, while granulite assemblages equilibrated at much lower , varying from about one tenth P _solid in quartzofeldspathic gneisses to one third P _solid in more basic layers.     

Systematic study of liquidas phase relations in olivine melilitite +H2O +CO2 at high pressures and petrogenesis of an olivine melilitite magma

Near-liquidus phase relationships of a spinel lherzolite-bearing olivine melilitite from Tasmania were investigated over a P, T range with varying , , and . At 30 kb under MH-buffered conditions, systematic changes of liquidus phases occur with increasing ( = CO₂/CO₂ +H₂O+olivine melilitite). Olivine is the liquidus phase in the presence of H₂O alone and is joined by clinopyroxene at low . Increasing eliminates olivine and clinopyroxene becomes the only liquidus phase. Further addition of CO₂ brings garnet+orthopyroxene onto the liquidus together with clinopyroxene, which disappears with even higher CO₂. The same systematic changes appear to hold at higher and lower pressures also, only that the phase boundaries are shifted to different . The field with olivine- +clinopyroxene becomes stable to higher with lower pressure and approaches most closely the field with garnet+orthopyroxene+clinopyroxene at about 27 kb, 1160 °C, 0.08 and 0.2 (i.e., 6–7% CO₂+ 7–8% H₂O). Olivine does not coexist with garnet+orthopyroxene+clinopyroxene under these MH-buffered conditions. Lower oxygen fugacities do not increase the stability of olivine to higher and do not change the phase relationships and liquidus temperatures drastically. Thus, it is inferred that olivine melilitite 2927 originates as a 5% melt (inferred from K_{2 O} and P₂O₅ content) from a pyrolite source at about 27kb, 1160 dg with about 6–7% CO₂ and 7–8% H₂O dissolved in the melt. The highly undersaturated character of the melt and the inability to find olivine together with garnet and orthopyroxene on the liquidus (in spite of the close approach of the respective liquidus fields) can be explained by reaction relationships of olivine and clinopyroxene with orthopyroxene, garnet and melt in the presence of CO₂.     

An almandine garnet isograd in the Rogers Pass area,British Columbia: The nature of the reaction and an estimation of the physical conditions during its formation

In the Rogers Pass area of British Columbia the almandine garnet isograd results from a reaction of the form: 5.31 ferroan-dolomite+8.75 paragonite+4.80 pyrrhotite+3.57 albite+16.83 quartz+1.97 O₂=1.00 garnet+16.44 andesine+1.53 chlorite+2.40 S₂+1.90 H₂O+10.62 CO₂. The coefficients of this reaction are quite sensitive to the Mn content of ferroan-dolomite.Experimental data applied to mineral compositions present at the isograd, permits calculation of two intersecting P, T equilibrium curves. P=29088–39.583 T is obtained for the sub-system paragonite-margarite (solid-solution), plagioclase, quartz, ferroan-dolomite, and P=28.247 T–14126 is obtained for the sub-system epidote, quartz, garnet, plagioclase. These equations yield P=3898 bars and T=638° K (365° C). These values are consistent with the FeS content of sphalerite in the assemblage pyrite, pyrrhotite, sphalerite and with other estimates for the area.At these values of P and T the composition of the fluid phase in equilibrium with graphite in the system C-O-H-S during the formation of garnet is estimated as: bars, bars, bars, bars, bars, bars, bars, bars, , bars, bars.     

The crystal structure of a triclinic roscherite

Summary The crystallography of roscherite is more complicated than previously thought. Single crystal X-ray work on material from Foote Mine (California) gave triclinic symmetry. The unit cell corresponding to the one adopted for monoclinic roscherite hasa=15.921,b=11.965,c=6.741 Å, =91°04, =94°21, =89°59 1/2, space group . The least-squares refinement of the structure using 2380 non zero reflections with anisotropic temperature factors resulted in a conventional reliability factorR=0.060.The X-ray study indicates the formula while that proposed for monoclinic roscherite is The atomic arrangements of both varieties of roscherite are very similar. The lowering of symmetry is caused by the segregation of the trivalent cations into only half of the sites of a monoclinic point position. Crystallochemical considerations suggest that the symmetry of roscherite does not depend on the kind of trivalent cations occupying the 6-coordinated position, but rather by the ratio between trivalent and divalent metal ions.

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Die Kristallstruktur eines triklinen Roscherites

Zusammenfassung Die Kristallographie des Roscherites ist komplizierter als man bisher annahm. Einkristall-Röntgenuntersuchungen an Material von Foote Mine (Kalifornien) ergaben trikline Symmetrie. Die Elementarzelle, welche der für monoklinen Roscherit angenommenen entspricht, hata=15,921,b=11,965,c=6,741 Å, =91°04, =94°21, =89°59 1/2, Raumgruppe . Die Verfeinerung der Struktur mit der Methode der kleinsten Quadrate ergab unter Verwendung anisotroper Temperaturfaktoren für 2380 beobachtete Reflexe einen konventionellen ZuverlässigkeitsindexR=0,060.Die Röntgenuntersuchung weist auf die Formel , während für monoklinen Roscherit vorgeschlagen wurde. Die Atomanordnungen beider Abarten des Roscherites sind sehr ähnlich. die Symmetrieerniedrigung wird dadurch hervorgerufen, daß die dreiwertigen Kationen nur die Hälfte der Positionen einer monoklinen Punktlage besetzen. Kristallchemische Überlegungen weisen darauf hin, daß die Symmetrie nicht von der Art der dreiwertigen Kationen, welche eine 6-koordinierte Punktlage besetzen, abhängt, sondern vielmehr von dem Mengenverhältnis zwischen 3-wertigen und 2-wertigen Metallionen.

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With 1 Figure     

Die Kristallstruktur von Warikahnit,Zn3[(H2O)2|(AsO4)2]

Zusammenfassung Die Kristallstruktur des neuen Minerals Warikahnit, Zn₃[(H₂O)₂|(AsO₄)₂], wurde mit Diffraktometerdaten bestimmt und bis zuR=0,038 für 3428 unabhängige Reflexe verfeinert.Warikahnit ist triklin, , mita=6,710(1),b=8,989(2),c=14,533(2) Å, =105,59(1), =93,44(1), =108,68(1)°,Z=4.Die Kristallstruktur des Warikahnits enthält sechs unterschiedliche Koordinationspolyeder des Zinks mit den Koordinationszahlen 6, 5 und 4 und mit fünf verschiedenen Ligandenkombinationen. Die Wasserstoffbrückenbindungen werden mit Hilfe der Ladungsbilanz und des IR-Spektrums diskutiert.

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The crystal structure of warikahnite, Zn₃[(H₂O)₂|(AsO₄)₂]

Summary The crystal structure of the new mineral warikahnite, Zn₃[(H₂O)₂|(AsO₄)₂], was determined from diffractometer data and refined toR=0,038 for 3428 observed independent reflections.Warikahnit is triclinic, , witha=6.710(1),b=8.989(2),c=14.533(2) Å, =105.59(1), =93.44(1), =108.68(1)°,Z=4.The crystal structure of warikahnite contains 6 different coordination polyhedra of zinc with the coordination numbers 6,5 and 4 and with 5 different combinations of ligand. The hydrogen bonds are discussed on the basis of charge balance and IR spectra.

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Mit 3 Abbildungen     

Synthesis and stability of bastnaesites in a part of the system (Ce,La)-F-H-C-O

Summary Bastnaesites of Ce and La and their OH-analogs were synthesized and their stability relations were determined atPf = 1 kbar andT = 400 to 900°C in a part of the system (Ce,La)-F-H-C-0. The initial fluid compositions were such that and HF/(HF + H₂O) ratios were 0 to 0.172. XRD and IR studies indicate that bastnaesites equilibrated in initial fluids low in HF are all F-enriched. The hydroxylbastnaesite-(La) is stable up to 810°C and the fluorbastnaesite-(La) is stable up to 860°C. Their condensed breakdown products are La₂O₂CO₃ and LaOF, respectively. The stability of Ce bastnaesites is slightly dependent. The hydroxylbastnaesite-(Ce) is stable up to 660°C at the defined by the IQF buffer and up to 640°C by the MH buffer. The fluorbastnaesite-(Ce) is stable up to 800°C at the defined by the IQF and up to 760°C by the MH buffer. The condensed breakdown product for the hydroxyl end-member is simply CeO₂ but for the fluorine one is a combination of CeO₂, CeF₃, and CeOF. Factors, such as OH vs F, , and bulk composition, that affect the stability of individual species are discussed. Petrogenic implications resulting from the present study include that bastnaesites can be stable from hydrothermal to magmatic conditions, that F-enriched species can form in an environment relatively low in F content, and that OH-species are rare and occur only in low-temperature environments essentially devoid of F.

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Synthese und Stabilität von Bastndsil in einem Teil des Systems (Ce,La)-F-H-C-O

Zusammenfassung Ce- und La-Bastnäsite, sowie deren OH-Analoga wurden synthetisiert und ihre Stabilitätsbeziehunger beiP _f = 1 kbar undT = 400 bis 900°C wurden im System (Ce,La)F-H-C-O bestimmt. Die anfänglichen Flüssigkeitszusammensetzungen waren so, daß und die HF/(HF + H₂O)-Verhältnisse 0–0.172 waren. Röntgenpulver- und Ultrarot-Untersuchungen zeigten, daß Bastnäsite, die mit anfänglich HF-armen Flüssigkeiten equilibriert wurden, alle an F angereichert sind. Hydroxilbastndsit-(La) ist bis 810°C und Fluorbastnäsit-(La) bis 860°C stabil. Ihre festen Zersetzungsprodukte sind La₂O₂O₃, bzw. LaOF. Die Stabilität der Ce-Bastnäsite hängt etwas von ab. Hydroxilbastnäsit-(Ce) ist bei des Eisen-Quarz-Fayalit-Puffers bis 660°C stabil und mit Magnetit-Hämatit-Puffer bis 640°C. Das feste Zerfallsprodukt ist für das Hydroxil-Glied nur CeO₂, für das Fluor-Glied eine Mischung aus CeO₂, CeF₃ und CeOF. Faktoren, welche die Stabilität der einzelnen Spezies beeinflussen, werden diskutiert, wie das Verhältnis OH zu F, und die Gesamtzusammensetzung. Petrogenetische Folgerungen aus der vorliegenden Studie schließen ein, daß Bastnäsite von hydrothermalen bis zu magmatischen Bedingungen stabil sein können, daß sich an F angereicherte Glieder in relativ F-armer Umgebung bilden können, und daß OH-Glieder selten sind und nur unter Bildungsbedingungen niedriger Temperatur und weitgehender Abwesenheit von F auftreten.

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With 8 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.     

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.     

Estimation of covariance matrix from geochemical data with observations below detection limits

Multivariate statistical analyses have been extensively applied to geochemical measurements to analyze and aid interpretation of the data. Estimation of the covariance matrix of multivariate observations is the first task in multivariate analysis. However, geochemical data for the rare elements, especially Ag, Au, and platinum-group elements, usually contain observations the below detection limits. In particular, Instrumental Neutron Activation Analysis (INAA) for the rare elements produces multilevel and possibly extremely high detection limits depending on the sample weight. Traditionally, in applying multivariate analysis to such incomplete data, the observations below detection limits are first substituted, for example, each observation below the detection limit is replaced by a certain percentage of that limit, and then the standard statistical computer packages or techniques are used to obtain the analysis of the data. If a number of samples with observations below detection limits is small, or the detection limits are relatively near zero, the results may be reasonable and most geological interpretations or conclusions are probably valid. In this paper, a new method is proposed to estimate the covariance matrix from a dataset containing observations below multilevel detection limits by using the marginal maximum likelihood estimation (MMLE) method. For each pair of variables, sayY andZ whose observations containing below detection limits, the proposed method consists of three steps: (i) for each variable separately obtaining the marginal MLE for the means and the variances, , , , and forY andZ: (ii) defining new variables by and and lettingA=C+D andB=C–D, and obtaining MLE for variances, and forA andB; (iii) estimating the correlation coefficient _YZ by and the covariance _YZ by . The procedure is illustrated by using a precious metal geochemical data set from the Fox River Sill, Manitoba, Canada.     

The genesis of emeralds and their host rocks from Swat,northwestern Pakistan: a stable-isotope investigation

Emerald deposits in Swat, northwestern Pakistan, occurring in talc-magnesite and quartz-magnesite assemblages, have been investigated through stable isotope studies. Isotopic analyses were performed on a total of seven emeralds, associated quartz (seven samples), fuchsite (three samples) and tourmaline (two samples) from the Mingora emerald mines. The oxygen isotopic composition ( ¹⁸O SMOW) of emeralds shows a strong enrichment in¹⁸O and is remarkably uniform at + 15.6 ± 0.4 (1,n = 7). Each of the two components of water in emerald (channel and inclusion) has a different range of hydrogen isotopic composition: the channel waters being distinctly isotopically heavier (D = –51 to –32 SMOW) than the other inclusion waters (D = –96 to –70 SMOW). Similarly the oxygen isotopic compositions of tourmaline and fuchsite are relatively constant ( ¹⁸O = + 13 to + 14 SMOW) and show enrichment in¹⁸O. The ¹⁸O values of quartz, ranging from + 15.1 to + 19.1 SMOW, are also high (+ 16.9 ± 1.4 1, n = 7). The meanD of channel waters measured from emerald (–42 ± 6.6 SMOW) and that of fluid calculated from hydrous mineralsD_calculated (–47 ± 7.1 SMOW) are consistent with both metamorphic and magmatic origin. However, the close similarity between the measuredD values of the hydroxyl hydrogen in fuchsite (–74 to –6 SMOW) and tourmaline (–84 and –69 SMOW) with pegmatitic muscovite and tourmaline suggests that the mineralization was probably caused by modified (¹⁸O-enriched) hydrothermal solutions derived from an S-type granitic magma. The variation in the carbon and oxygen isotopic composition of magnesite, locally associated with emerald mineralization, is also very restricted ( ¹³ –3.2 ± 0.7%, PDB; ¹⁸O + 17.9 ± 1.27 SMOW). On the basis of the isotopic composition of fluid ( ¹³C –1.8 ± 0.7 PDB; ¹⁸O + 13.6 ± 1.2 SMOW calculated for the 250-550 °C temperature), it is proposed that the Swat magnesites formed due to the carbonation of previously serpentinized ultramafic rocks by a CO₂-bearing fluid of metamorphic origin.     

The role of CO2 in the genesis of olivine melilitite

The nature of the near-liquidus phases for a mantle-derived olivine melilitite composition have been determined at high pressure under dry conditions and with various water contents. Olivine and clinopyroxene occur on or near the liquidus and there are no conditions where orthopyroxene crystallizes in equilibrium with the olivine melilitite. We have determined the effect on the liquidus temperature and liquidus phases of substituting CO₂ for H₂O on a mole for mole basis at 30 kb, using olivine melilitite + 20 wt% H₂O at = 0 and = (CO₂)/(H₂+CO₂) (mole fraction) = 0.25, 0.5, 0.75 and 1.0 (i.e. olivine melilitite + 38 wt% CO₂). Experiments were buffered by the MH or NNO buffers. At 30 kb, CO₂ is only slightly less soluble than water for <0.5 as judged by the slight increase in liquidus temperature on mole-for-mole substitution of CO₂ for H₂O and at 30 kb, 1200° C, = = 0.5 the olivine melilitite contains 8.8 wt% H₂O and 21 wt% CO₂ in solution. For 1 the CO₂ saturated liquidus is depressed 70 ° C below the anhydrous liquidus and the magma dissolves approx. 17% CO₂ at 30kb, 1400 ° C, 1, 0. Infrared spectra of quenched glasses have absorption bands characteristic of CO ₃ ⁼ and OH- molecules and no evidence for HCO ₃ ^- . The effect of CO ₃ ⁼ molecules dissolved in the olivine melilitite at high pressure is to suppress the near-liquidus crystallization of olivine and clinopyroxene and bring orthopyroxene and garnet on to the liquidus. We infer that olivine melilitite magmas may be derived by equilibrium partial melting (<5%) of pyrolite at 30 kb, 1150–1200 ° C, provided that both H₂O and CO₂ are present in the source region in minor amounts. Preferred conditions are 0< <0.5, 0.5< <1, and at low oxygen fugacities (相似文献   

The pleochroism of a gem-quality enstatite in the region of the OH stretching frequency,with a stereochemical interpretation

Summary The pleochroic behaviour of a gem-quality enstatite from Tanzania was investigated in the region =2500 to 4000 cm^–1. Two sharp absorption bands at =3410 cm^–1 and =3510 cm^–1 are interpreted to be caused by OH stretching vibrations. As their absorption coefficients are considerably larger parallel to [001] (=direction of the silicate chains) than perpendicular to this direction, the OH dipoles have to be oriented approximately parallel to [001]. On this basis, a stereochemical interpretation of the incorporation of the OH groups into the structure is given.

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Der Pleochroismus eines Enstatits von Edelsteinqualität im Gebiet der OH-Streckfrequenz und seine kristallchemische Interpretation

Zusammenfassung Das pleochroitische Verhalten eines Enstatits von Edelsteinqualität aus Tansania wurde im Bereich =2500 bis 4000 cm^–1 untersucht. Von zwei scharfen Banden bei =3410 cm^–1 und 3510 cm^–1 wird angenommen, daß sie durch OH-Streckschwingungen herrühren. Da ihre Absorptionskoeffizienten parallel zu [001] (=Richtung der Silikatketten) beträchtlich größer sind als senkrecht dazu, müssen die OH-Dipole ungefähr parallel zu [001] liegen. Auf dieser Basis wird der Einbau der OH-Gruppen in die Struktur diskutiert.

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Manganese olivine I: Electrical conductivity

To investigate the point defect chemistry and the kinetic properties of manganese olivine Mn₂SiO₄, electrical conductivity () of single crystals was measured along either the [100] or the [010] direction. The experiments were carried out at temperatures T=850–1200 °C and oxygen fugacities atm under both Mn oxide (MO) buffered and MnSiO₃ (MS) buffered conditions. Under the same thermodynamic conditions, charge transport along [100] is 2.5–3.0 times faster than along [010]. At high oxygen fugacities, the electrical conductivity of samples buffered against MS is 1.6 times larger than that of samples buffered against MO; while at low oxygen fugacities, the electrical conductivity is nearly identical for the two buffer cases. The dependencies of electrical conductivity on oxygen fugacity and temperature are essentially the same for conduction along the [100] and [010] directions, as well as for samples coexisting with a solid-state buffer of either MO or MS. Hence, it is proposed that the same conduction mechanisms operate for samples of either orientation in contact with either solid-state buffer.The electrical conductivity data lie on concave upward curves on a log-log plot of vs , giving rise to two regimes with different oxygen fugacity exponents. In the low- regime , the exponent, m, is 0, the MnSiO₃-activity exponent, q, is 0, and the activation energy, Q, is 45 kJ/mol. In the high regime 10^{ - 7} {\text{atm}}} \right)$$ " align="middle" border="0"> , m=1/6, q=1/4–1/3, and Q=45 and 200 kJ/mol for T<1100 °c=" and=">T>1100 °C, respectively.