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.     

Hydration and phase relations of grossular-spessartine garnets at P H 2O=2 Kb

The phase relations in the system grossular-spessartine-H₂O were investigated at 2.0 Kb aqueous fluid pressure and at subsolidus temperatures down to 420 ° C. Despite metastable persistence of a compositional gap found in some intermediate members, a complete solid solution between grossular and spessartine exists.Linear relations between the unit cell edge, a ₀, and composition were readily observed down to 620 ° C with a ₀=11.849(2) Å and 11.613(2) Å for grossular and spessartine, respectively. Hydrated garnets began to appear at higher temperature for the Ca-rich members. Grossular and spessartine formed at 420 ° C have a ₀=11.901(2) Å and 11.632(2) Å, indicating the presence of 0.6 and 0.2 mol H₂O, respectively. Intermediate members show varying degrees of hydration. Infrared spectra of the more hydrated members show a major and minor absorption bands at 3,620 cm^–1 and 3,660 cm^–1, respectively, in addition to a broad band around 3,430 cm^–1. All the hydrogarnets formed at 420 ° C were proven to be metastable.The rare occurrence of the intermediate grossular-spessartine garnets may be attributed to the lack of appropriate bulk chemistry of the rock rather than to the P-T conditions to which the rock is subjected. There may be a stability field for hydrogrossular below 420 ° C at 2 Kb, but not for hydrospessartine. Any occurrence of hydrogarnet may be used as a temperature indicator setting the maximum of formation for the hydrogarnet-bearing assemblage below 420 ° C at 2 Kb.     

The structure of metamict zircon: A temperature-dependent EXAFS study

The thermal annealing (300–1700 K) of two metamict zircons (Ampagabe, Madagascar and Näegy, Japan) has been studied using X-Ray Diffraction (XRD) and Extended X-ray Absorption Fine Structure spectroscopy (EXAFS) at Zr K-edge. Two stages of thermal annealing within the aperiodic zircon are evidenced between 293 and 1700 K. The first stage (up to 600° C) shows a decrease of the a ₀-cell parameter from 6.674 (at 300° C) to 6.610 (at 600° C)± 0.005 Å. In that temperature range, the average local environment around Zr (presence of ^VIIZr and d(Zr-Zr) 3.3–3.6 Å) shows a weak, but significant increase of the Zr-Zr correlations located at 3.3–3.4 Å, undetectable by XRD. At temperatures up to 700° C (stage 2), the XRD-Bragg component arising from crystalline zircon increases in magnitude, whereas, Zr-K EXAFS analysis indicates a progressive ^VIIZr^VIIIZr transition, associated with a recovery of the crystalline zircon medium-range environment. For both techniques, the zircon structure is fully recovered at annealing temperatures up to 900° C.Electrostatic modelings suggest that the ^VIIIZr^VIIZr transition observed in zircon with increasing alpha-decay damage creates significantly overbonded oxygen atoms around Zr. With increasing temperature, those oxygen atoms are better bonded to ^VIIZr, due to the thermal expansion of the Zr-O bond. The congruent recovery of the zircon structure should therefore be favoured with increasing temperature. On the other hand, the metamict network can be also partially reorganized around 400–500° C, with the creation of Zr-rich domains, as measured by EXAFS. However, the growth of these domains after 3 hours annealing affects only minor portions of the aperiodic network. This model is corroborated by a similar thermal behaviour observed for a synthetic sol-gel of ZrO₂ · SiO₂ composition.     

Thermal expansion and glass transition temperatures of synthetic glasses of plagioclase-like compositions

The glass transition temperatures and the thermal expansions both below and above the glass transition temperature region of synthetic glasses of compositions close to those of plagioclases have been determined. The linear thermal expansion coefficient of the rigid glasses decreases on average from 7.4×10^–6/dgC for albite glass to 4.9×10^–6/dgC for glass close to anorthite composition. The glass transition temperature of the glasses initially decreases from 763° C for albite glass to 752°C for An_9.7 glass and then increases nearly linearly with further increasing anorthite content to 813° C for glass close to anorthite composition.—Measurements made for comparison on a glass prepared from Madagascar orthoclase yielded a linear thermal expansion coefficient of 6.1×10^–6/dgC and a glass transition temperature of 905° C.The variations in thermal expansion and glass transition temperature of the feldspar glasses with composition are discussed in terms of structural changes which are assumed to be associated with cation replacement.     

The peristerite gap in low-grade metamorphic rocks

Coexisting Na-plagioclases from greenschists both in the thermal aureole of the Kasugamura Granite, Japan, and in the low-P metamorphic zone of Yap Island, western Pacific were analyzed in great detail; the peristerite solvus was determined for each suite. The asymmetric solvus has steep albite-rich and gentle oligoclase-rich limbs that are similar to those for higher pressure series. The present results together with those from Vermont, New Zealand, and the Sanbagawa belt indicate that the peristerite solvus shifts toward the albite component and higher temperature with increasing pressure. With increasing pressure, albite co-existing with oligoclase (An=100 Ca/Ca+ Na=20) varies in composition from An 8–9 (in Kasugamura), through An 3 (in Yap Island and Vermont), to An 1 (in New Zealand) and An less than 0.5 (in the Sanbagawa belt). The consolute temperatures for the peristerite solvus estimated from available geothermometry are 420° C in Kasugamura, 450–550° C in Vermont and 550°–600° C in the Sanbagawa belt. The variation of plagioclase composition in progressive metamorphic zones is explained by intersection of a plagioclase-forming reaction and the peristerite immiscibility gap in an isobaric T-X _An diagram. The greenschist zone is characterized by albite, the transition zone by occurrence of peristerite pairs and the amphibolite zone by plagioclase of An 20–50.     

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     

High-temperature X-ray investigation of natural columbites

Structural investigations at high temperature were carried out on natural columbite samples across the join Fe(Nb_0.95Ta_0.05)₂O₆–Mn(Nb_0.95Ta_0.05)₂O₆. The samples were preliminarily annealed to attain the complete cation-ordered state and avoid the superimposition of the effects of cation ordering during high-temperature studies. Unit-cell parameters of three columbites with different X_Fe content were measured at regular intervals in the temperature range 25–900 °C using single-crystal X-ray diffraction techniques. The crystal structures of completely ordered ferrocolumbite and manganocolumbite were also refined from intensity data collected at room temperature, 300 and 600 °C. Structural thermal expansion coefficients show positive, linear expansion of a, b, c lattice constants and cell volume. In general, slightly higher expansion occurs along a and c directions. However, anisotropy decreases sharply with decreasing Fe content. Reversibility of thermal expansion in the investigated temperature range was checked by high-temperature diffraction studies under heating-up and cooling-down conditions. Impurities do not play an important role in thermal expansion of columbites; expansion coefficients measured on two crystals of the same sample characterized by different Ti content are in fact almost identical. Structural changes with temperature essentially affect bond lengths: volumes of both A and B octahedral sites increase linearly with temperature, whereas interpolyhedral geometrical parameters do not vary significantly.     

Thermally induced phase transitions in tridymite: an infrared spectroscopy study

The temperature dependence of the infrared active modes of meteoritic and synthetic tridymite have been investigated between 23 K and 1073 K in IR absorption and IR emission experiments. At room temperature both tridymite samples consist of a mixture of low temperature forms, in different proportions, due to the grinding. The sequence of phase transitions in Steinbach tridymite deduced from the IR data agrees well with recent X-ray and calorimetry studies using identical samples (Cellai et al. 1994). The previously suspected structural phase transition P6₃22P6₃/mmc is confirmed by the disappearance of the 470 cm^-1 mode and a temperature anomaly of the spectral shift of the 790 cm^-1 mode. Changes in the infrared spectra of synthetic tridymite give a different sequence of phase transitions from those of the meteoritic sample, consistent with the structural phase transitions observed in a ²⁹Si MAS NMR investigation using the same sample (Xiao et al. 1993).     

Experimental study of a biotite-bearing granitic system under water-saturated and water-undersaturated conditions

Phase relationships in haplogranitic melts containing ferromagnesian minerals were investigated in the temperature range 760–850°C, atP _total=2 kbar, =0.25 1.00, and at NNO buffer conditions. The compositions of coexisting biotite, orthopyroxene, magnetite and granitic melt were determined by electron microprobe. Biotite was the only Fe–Mg mineral in the starting material. It disappeared in water-undersaturated melts at temperatures above 830°C and in melts saturated with water above 810°C. Magnetite was present in all runs. Orthopyroxene became stable between 780 and 800°C. The Mg/(Mg+Fe) ratios of biotite (0,63–0,72) and orthopyroxene (0,63–0,71) are similar in water-saturated and undersaturated melts at comparable temperatures and increase slightly with increasing temperature. The solubility of Mg in haplogranitic melts is very low (0,07–0,24 wt% MgO). It increases slightly with temperature and is independent of the prevailing water activity. The solubility of Fe is low (0,91–1,37 wt% FeO); it also increases with increasing temperature, and it is higher in water-saturated than in water-undersaturated melts.     

Structural changes and valence states in the MgCr<Subscript>2</Subscript>O<Subscript>4</Subscript>–FeCr<Subscript>2</Subscript>O<Subscript>4</Subscript> solid solution series

The influence on the structure of Fe²⁺ Mg substitution was studied in synthetic single crystals belonging to the MgCr₂O₄–FeCr₂O₄ series produced by flux growth at 900–1200 °C in controlled atmosphere. Samples were analyzed by single-crystal X-ray diffraction, electron microprobe analyses, optical absorption-, infrared- and Mössbauer spectroscopy. The Mössbauer data show that iron occurs almost exclusively as ^IVFe²⁺. Only minor Fe³⁺ (<0.005 apfu) was observed in samples with very low total Fe. Optical absorption spectra show that chromium with few exceptions is present as a trivalent cation at the octahedral site. Additional absorption bands attributable to Cr²⁺ and Cr³⁺ at the tetrahedral site are evident in spectra of end-member magnesiochromite and solid-solution crystals with low ferrous contents. Structural parameters a₀, u and T–O increase with chromite content, while the M–O bond distance remains nearly constant, with an average value equal to 1.995(1) Å corresponding to the Cr³⁺ octahedral bond distance. The ideal trend between cell parameter, T–O bond length and Fe²⁺ content (apfu) is described by the following linear relations: a₀=8.3325(5) + 0.0443(8)Fe²⁺ (Å) and T–O=1.9645(6) + 0.033(1)Fe²⁺ (Å) Consequently, Fe²⁺ and Mg tetrahedral bond lengths are equal to 1.998(1) Å and 1.965(1) Å, respectively.     

Schultenit,PbHAsO4, und PbHPO4: Synthesen und Kristallstrukturen nebst einer Diskussion zur Symmetrie

Zusammenfassung Schultenit, PbHAsO₄ [a=4,859(1) Å,b=6,756(1) Å,c=5,843(1) Å, =95,40(1)°] und PbHPO₄ [a=4,6838(3) Å,b=6,6451(2) Å,c=5,7817(3) Å, =97,138(4)°] sind isotyp und kristallisieren monoklin. Für beide Verbindungen war bei einer Temperatur vonT _c312 K der Übergang von RaumgruppeP _c nachP2/c bekannt. Der Strukturtyp von Schultenit ist durch das Vorliegen einer kurzen Wasserstoffbrückenbindung zwischen zwei in RaumgruppeP2/c über ein Symmetriezentrum ineinander überführbarer XO₄-Tetraeder charakterisiert. Die O–H...O-Bindungslänge beträgt in beiden Verbindungen übereinstimmend 2,46 Å. Mit Hilfe von Röntgen-Einkristallstrukturuntersuchungen konnte gezeigt werden, daß dieser Übergang vonPc nachP2/c offensichtlich nur auf einer Ordnung des H-Atoms beruht, während alle anderen Atome auch bei Zimmertemperatur innerhalb des Fehlers eine zentrosymmetrische Atomanordnung aufweisen.

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Schultenite, PbHAsO₄, and PbHOP₄: Syntheses and crystal structures with a discussion on their symmetry

Summary Schultenite PbHAsO₄ [a=4.859(1) Å,b=6.756(1) Å,c=5,843(1) Å, =95.40(1)°] and PbHPO₄ [a=4,6838(3) Å,b=6,6451(2) Å,c=5.7817(3) Å =97.138(4)°] are isotypic and crystallize monoclinic. For both compounds a transition from space groupPc toP2/c has been described atT _c312 K. The structure type of schultenite is characterized, by a short hydrogen bond between two XO₄ tetrahedra which are combined by a center of symmetry in space groupP2/c. The O–H...O bond length is for both these compounds 2.46 Å. Based on X-ray single crystal structure refinements it has been shown, that the transition fromPc toP2/c is obviously caused only by an ordering of the H atom; all the other atoms are also at room temperature centrosymmetrically arranged within limits of error.

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Hern Prof.Dr.K.Komarek zum 60.Geburtstag gewidmet

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Mit 1 Abbildung     

Die Kristallstruktur des Johannits,Cu(UO2)2(OH)2(SO4)2·8H2O

Zusammenfassung Die Kristallstruktur des Johannits wurde anhand eines verzwillingten Kristalls von Joachimsthal, Böhmen, mit dreidimensionalen Röntgendaten bestimmt und für 2005 unabhängige Reflexe aufR=0,039 verfeinert. Johannit kristallisiert triklin, RaumgruppeP1, mita=8,903 (2),b=9,499 (2),c=6,812 (2) Å, =109,87 (1) =112,01 (1), =100,40 (1)° undV=469,9 ų. Chemische Formel und Zellinhalt lauten Cu(UO₂)₂(OH)₂(SO₄)₂·8H₂O, das ist um zwei H₂O-Moleküle mehr als bisher angenommen. In der Struktur sind pentagonal dipyramidale (UO₂)(OH)₂O₃-Polyeder paarweise über eine von zwei OH-Gruppen gebildete Kante zu Doppelpolyedern und diese wiederum durch SO₄-Gruppen zu (UO₂)₂(OH)₂(SO₄)₂-Schichten parallel (100) verknüpft. Die Schichten sind parallel über gestreckte Cu(H₂O)₄O₂-Oktaeder und Wassermoleküle miteinander verbunden. Folgende Bindungslängen wurden gefunden: U–O=1,78 Å (2x) und 2,34–2,39 Å (5x); Cu–O=1,97 Å (4x) und 2,40 Å (2x); =1,47 Å; O–O in Wasserstoffbrücken 2,71–2,91 Å (8x) und 3,30 Å.

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The crystal structure of johannite, Cu(UO₂)₂(OH)₂(SO₄)₂·8H₂O

Summary The crystal structure of johannite has been determined from threedimensional X-ray data measured on a twinned crystal from Joachimsthal, Böhmen, and has been refined toR=0.039 for 2005 independent reflections. Johannite crystallizes triclinic, space groupP1, witha=8.903 (2),b=9.499 (2),c=6.812 (2) Å, =109.87(1), =112.01(1), =100.40 (1)° andV=469.9 ų. Chemical formula and cell content are Cu(UO₂)₂(OH)₂(SO₄)₂·8H₂O, by two H₂O molecules more than previously assumed. Pairs of pentagonal dipyramidal (UO₂) (OH)₂O₃ polyhedra form double polyhedra by edgesharing via two OH groups. The double polyhedra are linked by the SO₄ tetrahedra to form layers (UO₂)₂(OH)₂(SO₄)₂ parallel zu (100). These layers are interconnected parallel toa by elongated Cu(H₂O)₄O₂ octahedra and water molecules. Following bond lengths have been observed: U–O=1.78 Å (2x) and 2.34–2.39 Å (5x); Cu–O=1.97 Å (4x) and 2.40 Å (2x); =1.47 Å; O–O for hydrogen bonds 2.71–2.91 Å (8x) and 3.30 Å.

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Mit 2 Abbildungen     

Non-linear temperature dependence of liquid volumes in the system albite-anorthite-diopside

The temperature-dependent thermal expansivities of glasses and liquids in the ternary albite-anorthite-diopside have been determined using a combination of calorimetry, dilatometry and Pt and Ir double bob Archimedean densitometry. Supercooled liquid volumes and molar thermal expansivities were determined across the glass transition using a combination of scanning calorimetry and dilatometry, based upon the equivalence of relaxation of volume and enthalpy in the vicinity of the glass transition. Superliquidus volumes were determined using double Pt bob Archimedean densitometry at temperatures up to 1,650°C and double Ir bob densitometry at 1,800°C. Experimental access to liquid volumes near the glass transition temperatures (680–920°C) and at superliquidus temperatures (1,400–1,800°C) for these compositions results in the observation of a nonlinear temperature dependence of molar volume, i.e., temperature-dependent thermal expansivities. The diopside composition wxhibits the largest temperature dependence of thermal expansivity, decreasing by 50% between 800 and 1,500°C. Linear extrapolation of the high-temperature volume data of diopside to 810°C would result in a 3% overestimation of the molar voltime. The temperature dependence of the molar volume of anorthite is approximately linear. The thermal expansivities of the liquids in the albite-anorthite-diopside system appear to converge at high temperature. This study uses a combination of methods that allows interpolation rather than extrapolation of the extant melt-volume data into the petrologically meaningful (subliquidus) temperature range.     

Compressional wave velocity of granite and amphibolite up to melting temperatures at 1 GPa

Compressional wave velocities (V_P) at above-solidus temperatures and at 1 GPa were obtained for a granite and amphibolite, which are considered to be major constituents of the continental crust. The temperature variation of velocities showed that the V_P values of granite decreased with rising temperature, but substantially increased beyond the melting temperature (850–900 °C). Such an increase may be caused by the α–β transition of quartz. The velocities of amphibolite decreased linearly with increasing temperature and dropped sharply at temperatures above the solidus (700 °C), indicating that partial melting of amphibolite acts to significantly lower the seismic velocities.     

Four- and five-phase peridotites from a continental rift system: evidence for upper mantle uplift and cooling at the Ross Sea margin (Antarctica)

Upper mantle plagioclase+spinel- and spinel-peridotite xenoliths occur in basanitic and tephritic lavas of the 2.7 my to Recent Mt. Melbourne Volcanic Field (Antarctica). This field belongs to the Cenozoic McMurdo volcanic group which is located between the deep western trough of the Ross Sea rift system and the uplifted rift shoulder of the Transantarctic Mountains. Our samples cover the transition zone between rift and shoulder. We examined texture and composition of plagioclase+spinel and normal spinel peridotites and determined temperatures and pressures of formation using the internally consistent Ca-ol/cpx and 2px-thermobarometer of Köhler and Brey (1990) and Brey and Köhler (1990). Distinct calcium distribution patterns in olivines correspond to three different petrographic textures: type ELZ have equigranular textures, and low calcium concentrations of 60 ppm in the olivine cores which are strongly zoned to 200 ppm in their rims. Type PLH are protogranular to porphyroclastic and have low and homogeneous calcium contents in the range of 120 to 200 ppm. Type EHH peridotites are equigranular and have olivines with high and homogeneous calcium values of 467–485 ppm. The application of the 2 px-thermometer give rim temperatures of 800 to 860 °C for Type ELZ, 900 to 1080 °C for type PLH and 1030 to 1050 °C for type EHH. Pressures of 13 to 17 kb calculated with the Ca-ol/epx-barometer for EHH peridotites are consistent with the Ross Rift geotherm. For the other two types, this barometer yields unreasonable high pressures exceeding 30 kb for both, plagioclase-bearing and normal spinel-peridotites. This indicates disequilibrium and continued calcium-loss from the olivines during cooling below the closure temperature for the 2 px-thermometer. Inversion of the Ca-in-olivine-barometer into a thermometer and application to core compositions of ELZ olivines (60 ppm) suggests that cooling occurred to temperatures of ca. 580 °C. Based on petrographical and geothermobarometric results and diffusion arguments, a four stage model is developed for the evolution of the upper mantle beneath the margin of the Ross Rift: (1) adiabatic uplift into the plagioclase/spinel-peridotile field; (2) subsequent cooling below the blocking temperature (800 °C) of the 2 px-thermometer to about 600 °C as indicated by low Ca in olivine cores; followed by (3) reheating to 760 °C as suggested by zonation to high calcium concentrations of up to 200 ppm in olivine rims. Calcium concentrations of up to 800 ppm were measured in one ELZ-olivine in the outermost rim (10 m) reflecting (4) a last heating event during transport and ascent in the basanitic host magma. Timing for the latter two stages has been roughly calculated from Ca-diffusivities in olivine. A minimum duration of 1200 to a few million years is indicated for stage 3 and 90 h to 22–23 days for stage 4, respectively. This timing of events correlates to increased mantle temperatures for the duration of magmatic activity of the Mt. Melbourne Volcanic Field and the short-term transport in host magmas. Our results also indicate that anomalous shallow mantle exists at the transition from the Ross Rift into the uplifted Transantarctic Mountains.     

Hydrothermal recrystallization and transformation of tridymite

Well ordered tridymites containing atmost 0.016% Na (0.004% Na) were prepared at 1400° C from Na₂WO₄-(K₂WO₄-) fluxes using high purity amorphous silica as starting material. No further reduction of these Na-contents was attainable by soxhlet extraction. These tridymites were treated hydrothermally at temperatures between 815 and 950° C and 200 bars H₂O. The products obtained were investigated optically as well as by powder X-ray methods and were analyzed for Na-contents: the hydrothermal treatment resulted either in recrystallization of tridymite or transformation into quartz mostly depending on Na-contents. Na-contents below about 0.015% tend to favour recrystallization of tridymite within the quartz field (<870° C), Na-contents above about 0.03% tend to favour formation of quartz within the tridymite field (>870° C). This may be due to influences of Na-traces either on the kinetics or on the equilibrium temperature of tridymite-quartz transformation.     

Hydrogen isotopic fractionation factor between brucite and water in the temperature range from 100° to 510° C

The hydrogen isotopic fractionation factor between brucite and water has been determined in the temperature range of 100°–510° C. Brucite is always depleted in deuterium relative to the coexisting water, and the degree of depletion becomes larger with decreasing temperature. The fractionation factor changes smoothly in the temperature range of 144°–510° C and its temperature dependence was obtained by the method of least square fit in the following form: 10³In=8.72×10⁶ T ^–2–3.86×10⁴ T ^–1+14.5However, a marked decrease of about 5 was observed at 100°–144° C. The D/H fractionation factor for the brucite-water system is not similar to that for serpentine-water system presented by Sakai and Tsutsumi (1978), though all the hydroxyl ions coordinate to magnesium ion in both minerals. This discrepancy cannot be attributed to hydrogen bonding but to distortion of Mg-octahedron of serpentine, in which the Mg-OH bonding length is shorter than the sum of ionic radius of Mg²⁺ and O^2– and there is no distortion in brucite. It is indicated that aside from hydrogen bonding, the structure effect also controls the D/H fractionation between hydrous mineral and water.     

Sulfide mineralogy in the polymetallic cassiterite deposits of Dachang,P.R. China

Several important mineral deposits of Sn, Zn, Cu, Pb, and other metals associated with Devonian sediments and Yanshanian (Cretaceous) granitic rocks are known in the Dachang district (Guangxi). Early genetic hypotheses related the origin of the deposits entirely to the Yanshanian granites. Recently, it was suggested that in Devonian times an earlier syngenetic metal concentration may have occurred, later overprinted by the Yanshanian metallogeny. This contribution is aimed at placing constraints on the physicochemical conditions during the Yanshanian ore formation-remobilization by studying the sulfide chemistry (arsenopyrite, sphalerite, stannite) and fluid inclusion data on the two major deposits in the area, i.e., the polymetallic cassiterite deposit of Changpo and the Zn-Cu skarn deposit of Lamo. Sphalerite and arsenopyrite are quite abundant in both deposits; stannite is minor, but fairly widespread at Changpo, and quite rare at Lamo. They are accompanied by pyrite, pyrrhotite, galena, chalcopyrite, cassiterite, fluorite, and a large variety of other sulfides and sulfosalts. The main compositional data for sphalerite and arsenopyrite are summarized as follows:Changpo: arsenopyrite associated with pyrrhotite 31.4–36.1 at% As; Associated with pyrite 31.9–33.1 at% As; sphalerite associated with pyrrhotite 18.3–22.2 mol% FeS; associated with pyrite 10.6–18.6 mol% FeS.Lamo: arsenopyrite associated with pyrrhotite 32.9–35.3 at% As; associated with pyrite 30.3–31.7 at% As; sphalerite associated with pyrrhotite, 17.2–24.4 mol% FeS; associated with pyrite 4.2–19.6 mol% FeS.Partitioning of Fe and Zn between coexisting sphalerite and stannite from Changpo indicates temperatures of 300°–350°C. For Lamo, the following fluid inclusion data are available: fluorite, salinities of 0–9.5 equiv. wt% NaCl, and homogenization temperatures between 160°C and 250°C; quartz, moderate salinities (0–4.6 equiv. wt% NaCl), and homogenization temperatures of 208°–260°C. Combining the mineralogical evidence with the compositional and fluid inclusion data, it is suggested that the evolution of the environment during the Yanshanian event was characterized by the following parameters: pressure was relatively low (on the order of 1–1.5 kb); temperature may have been as high as 500°C during deposition of the As-richest arsenopyrites, but eventually dropped below 200°–250°C in the latest stages; with an increase in sulfur activity and/or the decrease in temperature pyrrhotite was no longer stable in the latest stages of mineralization.     

Ca−Sr substitution in clinopyroxenes along the join CaMgSi2O6−SrMgSi2O6

Summary In order to define the limits of expansion of the M2 polyhedron in theC2/c clinopyroxenes of formulaX ^M2Mg^M1 [Si₂O₆] as the mean ionic radius in the M2 site increases, the join CaMgSi₂O₆–SrMgSi₂O₆ (Di–SrPx) has been investigated atP=1 atm and between 1090°C and 1350°C. The extent of the clinopyroxene solid solutions is limited to the compositional range Di₁₀₀–Di₇₀SrPx₃₀. Within this range the unit-cell parameters of the clinopyroxenes show a linear variation with the increase of Sr content. The comparison of the variations caused in the unit-cell dimensions by the increase of the mean ionic radius in the M2 site (Di–SrPx series) with those caused by the decrease of the mean ionic radius in M2 (Di–En series) displays a different trend ofb in the two series. This different trend ofb suggests a different mechanism of the structure deformation in the two solid solution series. The narrow extent of the Di–SrPx solid solutions atT=1200°C shows that the increase of the mean ionic radius in the M2 site is restricted to the range 1.12–1.16 Å.

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La substitution Ca–Sr dans les clinopyroxènes le long du joint CaMgSi₂O₆–SrMgSi₂O₆

Résumé Le joint CaMgSi₂O₆–SrMgSi₂O₆ (Di–SrPx) a été étudié entre 1090°C et 1350°C à 1 atm dans le but d'établir quelles sont les limites de l'expansibilité du polyhèdre M2 dans les clinopyroxènesX ^M2Mg^M1 [Si₂O₆] (group spatialC2/c) avec l'augmentation du rayon jonique moyen dans le site M2. La solution solide est limitée à l'intervalle de composition Di₁₀₀–Di₇₀ SrPx₃₀. Dans ce domaine les paramètres de la maille varient d'une façon linéaire avec la teneur croissante de Sr. Si on compare les variations de la maille, déterminées par le rayon jonique moyen croissant dans le site M2 (série Di–SrPx), avec celles causées par la diminution du rayon jonique moyen dans le site M2 (série Di–En), on observe une tendance différente du paramètreb dans les deux séries. Ceci indique un mécanisme différent de la déformation structuralle dans les deux séries de solutions solides. Puisque àT=1200°C le domaine des solutions solides Di–SrPx est étroit, l'augmentation du rayon ionique moyen dans le site M2 est bornée à l'intervalle 1.12–1.16 Å.

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With 5 Figures     

Fluid inclusions as petrogenetic indicators in granulite xenoliths,Pali-Aike volcanic field,Chile

Granulite xenoliths within alkali olivine basalts of the Pali-Aike volcanic field, southern Chile, contain the mineral assemblage orthopyroxene + clinopyroxene + plagioclase + olivine + green spinel. These granulites are thought to be accidental inclusions of the lower crust incorporated in the mantle-derived basalt during its rise to the surface. Symplectic intergrowths of pyroxene and spinel developed between olivine and plagioclase imply that the reaction olivine+plagioclase = Al-orthopyroxene + Al-clinopyroxene + spinel (1) occurred during subsolidus cooling and recrystallization of a gabbroic protolith of the granulites.Examination of fluid inclusions in the granulites indicates the ubiquitous presence of an essentially pure CO₂ fluid phase. Inclusions of three different parageneses have been recognized: Type I inclusions occur along exsolution lamellae in clinopyroxene and are thought to represent precipitation of structurally-bound C or CO₂ during cooling of the gabbro. These are considered the most primary inclusions present. Type II inclusions occur as evenly distributed clusters not associated with any fractures. These inclusions probably represent entrapment of a free fluid phase during recrystallization of the host grains. IIa inclusions are found in granoblastic grains and have densities of 0.68–0.88 g/cm³. Higher density (=0.90–1.02 g/cm³) IIb inclusions occur only in symplectite phases. Secondary Type III CO₂+glass inclusions with =0.47–0.78 g/cm³ occur along healed fractures where basalt has penetrated the xenoliths. Type III inclusions appear related to exsolution of CO₂ from the host basalt during its ascent to the surface. These data suggest that CO₂ is an important constituent of the lower crust under conditions of granulite facies metamorphism, indicated by Type I and II fluid inclusions, and of the mantle, as indicated by Type III inclusions.Correlation of fluid inclusion densities with P-T conditions calculated from both two-pyroxene geothermometry and reation (1) indicate emplacement of a gabbroic pluton at 1,200–1,300° C, 4–6 kb; cooling was accompanied by a slight increase in pressure due to crustal thickening, and symplectite formation occurred at 850±35° C, 5–7 kb. Capture of the xenoliths by the basalt resulted in heating of the granulites, and CO₂ from the basalt was continuously entrapped by the xenoliths over the range 1,000–1,200° C, 4–6 kb. Examination of fluid inclusions of different generations can thus be used in conjunction with other petrologic data to place tight constraints on the specific P-T path followed by the granulite suite, in addition to indicating the nature of the fluid phase present at depth.