Lithium lines in the spectra of M dwarfs: UX Tau C

The results of numerical modeling of lithium lines in the spectra of M dwarfs are discussed. The behavior of the lithium lines relative to the local pseudocontinuum formed by molecular bands is analyzed as a function of model atmosphere parameters: effective temperature T _eff, gravity logg, and metallicity μ The molecular opacity was computed using the just overlapping line approximation (JOLA) and “line-by-line” methods. The pseudo-equivalent widths of lithium lines depend appreciably on metallicity μ and weakly on T{nteff}. The lithium abundance in the atmosphere of UX Tau C is redetermined. Previous studies underestimated the lithium abundance in this star as a result of the use of insufficiently accurate molecular-line lists. The new lithium abundance log N (Li)=3.2±0.3was derived by comparing the observed profiles of the 670.8 nm resonance doublet lines with profiles calculated using the new TiO line list of Plez.¹ The new abundance agrees with the atmospheric lithium abundances of the other two components in the stellar system, providing further evidence that the three stars in the UX Tau system have the same age. A comparison of the observed spectra of UX Tau C near the lithium resonance doublet (665–680 nm) with spectra computed using JOLA and line-by-line methods suggests that the list of Plez is the best currently available.     

On the Stability of the <Emphasis Type="Italic">AlOSi</Emphasis>(<Emphasis Type="Italic">OH</Emphasis>)<Stack><Subscript>3</Subscript><Superscript>2+</Superscript></Stack> Complex in Aqueous Solution

Summary The complexation of aluminium(III) and silicon(IV) was studied in a simplified seawater medium (0.6 M Na(Cl)) at 25 °C. The measurements were performed as potentiometric titrations using a hydrogen electrode with OH ⁻ ions being generated coulometrically. The total concentrations of Si(IV) and Al(III) respectively [Si _tot ] and [Al _t ot], and −log[H ⁺] were varied within the limits 0.3 < [Si _tot ] < 2.5 mM, 0.5 < [Al _tot ] < 2.6 mM, and 2 ≤ -log[H ⁺] ≤ 4.2. Within these ranges of concentration, evidence is given for the formation of an AlSiO(OH) ₃ ²⁺ complex with a formation constant log β_1,1-1 = −2.75 ± 0.1 defined by the reaction Al ³⁺+Si (OH)₄ ↔ AlOSi(OH) ₃ ²⁺ +H ⁺ An extrapolation of this value to I=0 gives log β_1,1-1 = −2.30. The calculated value of log K (Al ³⁺+SiO(OH) ₃ ⁻ ↔ AlOSi(OH) ₃ ²⁺ ) = 6.72 (I=0.6 M) can be compared with corresponding constants for the formation of AlF ²⁺ and AlOH ²⁺ , which are equal to 6.16 and 8.20. Obviously, the stability of these Al(III) complexes decreases within the series OH ⁻>SiO(OH) ₃ ⁻  > F ⁻     

Atmospheric chemical abundances of the components of the quadruple system ADS 11061. 40 Draconis

As part of our study of the components of the hierarchic quadruple system ADS 11061, we acquired spectroscopic observations of the binary 40 Dra. Echelle spectra showing the separation of the components’ lines were obtained in the spectral range 3700–9200 Å. Effective temperatures and surface gravities were derived for the components from BV photometry and the hydrogen-line profiles. The components of the 40 Dra system have parameters close to T _eff ^a = 6420 K, log g _a = 4.17, T _eff ^b = 6300 K, and log g _b = 4.20. We find the microturbulence velocity in the component atmospheres to be V _t = 2.6 km/s. The abundances of iron, carbon, nitrogen, and oxygen in the atmospheres of both components are estimated to be log N(Fe)^a = 7.50, log N(Fe)^b = 7.46, log N(C)^a = 8.39, log N(C)^b = 8.45, log N(N)^a = 8.12, log(N)^b = 8.15, log N(O)^a = 8.77, log N(O)^b = 8.74.     

Phase relations, singularities and thermobarometry of metamorphic assemblages containing phengite, chlorite, biotite, K-feldspar, quartz and H2O

The phase relations of divariant and trivariant assemblages involving combinations of phengite, chlorite, biotite, K-feldspar, quartz and H₂O in the KFASH, KMASH and KFMASH systems were calculated using a single thermodynamic data set (Holland and Powell 1998). The stability fields of the various equilibria are represented in P-T projections by contouring sets of compositional isopleths for the Tschermak (Al₂(Fe,Mg)₋₁Si₋₁) and FeMg₋₁ exchanges controlled by the coexisting phases. Five multivariant continuous equilibria, which occur in different regions of P-T-X space, are calibrated as thermobarometers in metamorphic rocks of pelitic to quartzofeldspathic composition. More subtle P-T information, relating to the trajectories (dT/dz) along which reacting rocks have been buried or exhumed, can be extracted from the continuous reactions by investigating the recorded compositional trends in the Al₂(Fe,Mg)₋₁Si₋₁ and FeMg₋₁ solutions. Singularities in P-T space are associated with some of these reactions and may result in unusual mineral textures and compositional trends. A fluid-absent singularity has particular petrological significance because it marks the transition between hydration and dehydration along a single reaction with increasing pressure and temperature. This behaviour causes the sequence of reactions among these minerals observed during metamorphism to be critically dependent on the P-T trajectory. Thermobarometric calculations show good agreement with respect to experimental and field-based data for phengite compositions less than about 50 mol% celadonite (<∼3.5 Si p.f.u. phengite). Received: 15 November 1999 / Accepted: 3 April 2000     

Isotope and Trace Element Geochemistry of Fuchuan Ophiolite Suite,Anhui,China

The Fuchuan ophiolite suite in Shexian County, Anhui Province, was formed in the Middle-Late Proterozoic. It is characterized by varying Nd [∈_Nd (T) =0.7−3.8], Sr [∈_Sr(T) = 30.7−53.9] and O(δ¹⁸O=3.2−11.0%.) and low ratios of Nd/La (<0.8), Ti/Y (<350) and Ti/V (<30). These characteristics, in combination with geological features, indicate that the ophiolite suite was formed in the axial part of the back-arc basin of the Jiangnan ancient island arc at the southeastern margin of the Yangtze Plate. The varying ∈_Nd (T) was caused by the contamination of the underlying inmature sialic crust during the formation of the ophiolite and variations in ∈_Sr(T) and δ¹⁸ O may have resulted from hydrothermal alteration by seawater during or shortly after its formation.     

Nature of the crust in Maine,USA: evidence from the Sebago batholith

 Neodymium and lead isotope and elemental data are presented for the Sebago batholith (293±2 Ma), the largest exposed granite in New England. The batholith is lithologically homogeneous, yet internally heterogeneous with respect to rare earth elements (REE) and Nd isotopic composition. Two-mica granites in the southern/central portion of the batholith (group 1) are characterized by REE patterns with uniform shapes [Ce_N/Yb_N (chondrite normalized) = 9.4–19 and Eu/Eu* (Eu anomaly) = 0.27–0.42] and ɛ _Nd(t) = −3.1 to −2.1. Peripheral two-mica granites (group 2), spatially associated with stromatic and schlieric migmatites, have a wider range of total REE contents and patterns with variable shapes (Ce_N/Yb_N = 6.1–67, Eu/Eu* = 0.20–0.46) and ɛ _Nd(t) = −5.6 to −2.8. The heterogeneous REE character of the group 2 granites records the effects of magmatic differentiation that involved monazite. Coarse-grained leucogranites and aplites have kinked REE patterns and low total REE, but have Nd isotope systematics similar to group 2 granites with ɛ _Nd(t) = −5.5 to −4.7. Rare biotite granites have steep REE patterns (Ce_N/Yb_N = 51–61, Eu/Eu* = 0.32–0.84) and ɛ _Nd(t) = −4.6 to −3.8. The two-mica granites have a restricted range in initial Pb isotopic composition (²⁰⁶Pb/²⁰⁴Pb = 18.41–18.75; ²⁰⁷Pb/²⁰⁴Pb = 15.60–15.68; ²⁰⁸Pb/²⁰⁴Pb = 38.21–38.55), requiring and old, high U/Pb (but not Th/U) source component. The Nd isotope data are consistent with magma derivation from two sources: Avalon-like crust (ɛ _Nd>−3), and Central Maine Belt metasedimentary rocks (ɛ _Nd<−4), without material input from the mantle. The variations in isotope systematics and REE patterns are inconsistent with models of disequilibrium melting which involved monazite. Received: 8 December 1995 / Accepted: 29 April 1996     

Thermodynamic data of the high-pressure phase Mg5Al5Si6O21(OH)7 (Mg-sursassite)

 Calorimetric and P–V–T data for the high-pressure phase Mg₅Al₅Si₆O₂₁(OH)₇ (Mg-sursassite) have been obtained. The enthalpy of drop solution of three different samples was measured by high-temperature oxide melt calorimetry in two laboratories (UC Davis, California, and Ruhr University Bochum, Germany) using lead borate (2PbO·B₂O₃) at T=700 ^∘C as solvent. The resulting values were used to calculate the enthalpy of formation from different thermodynamic datasets; they range from −221.1 to −259.4 kJ mol⁻¹ (formation from the oxides) respectively −13892.2 to −13927.9 kJ mol⁻¹ (formation from the elements). The heat capacity of Mg₅Al₅Si₆O₂₁(OH)₇ has been measured from T=50 ^∘C to T=500 ^∘C by differential scanning calorimetry in step-scanning mode. A Berman and Brown (1985)-type four-term equation represents the heat capacity over the entire temperature range to within the experimental uncertainty: C _P (Mg-sursassite) =(1571.104 −10560.89×T ^−0.5−26217890.0 ×T ⁻²+1798861000.0×T ⁻³) J K⁻¹ mol⁻¹ (T in K). The P V T behaviour of Mg-sursassite has been determined under high pressures and high temperatures up to 8 GPa and 800 ^∘C using a MAX 80 cubic anvil high-pressure apparatus. The samples were mixed with Vaseline to ensure hydrostatic pressure-transmitting conditions, NaCl served as an internal standard for pressure calibration. By fitting a Birch-Murnaghan EOS to the data, the bulk modulus was determined as 116.0±1.3 GPa, (K ^′=4), V _T,0 =446.49 ³ exp[∫(0.33±0.05) × 10⁻⁴ + (0.65±0.85)×10⁻⁸ T dT], (K _T/T) _P  = −0.011± 0.004 GPa K⁻¹. The thermodynamic data obtained for Mg-sursassite are consistent with phase equilibrium data reported recently (Fockenberg 1998); the best agreement was obtained with Δ_f H ⁰ ₂₉₈ (Mg-sursassite) = −13901.33 kJ mol⁻¹, and S ⁰ ₂₉₈ (Mg-sursassite) = 614.61 J K⁻¹ mol⁻¹. Received: 21 September 2000 / Accepted: 26 February 2001     

Phosphorus distribution between potassic alkali feldspar and metaluminous haplogranitic liquid at 200 MPa (H<Subscript>2</Subscript>O): the effect of undercooling on crystal–liquid systematics

To evaluate the applicability of P₂O₅ concentration in potassic alkali feldspar as a monitor of P₂O₅ in melt for undercooled systems, crystal–melt partitioning for P was evaluated via feldspar growth experiments in P-bearing ((3 wt% P₂O₅), water-saturated haplogranitic liquids at 200 MPa, with liquidus undercoolings (ΔT) of 25, 50, 100, 200, and 300°C. Increasing undercooling in the range ΔT=25–200°C shows an evolution of crystal morphologies, from euhedral and well-filled individuals at ΔT=25–50°C to radial clusters with increasingly skeletal habit at greater undercooling. Experiments at ΔT=100–200°C also document the development of P- (up to (9 wt% P₂O₅) and Si-enriched, more alkaline boundary layers adjacent to crystals. Experiments at ΔT=300°C show an additional change in crystallization fabric in which spherulites of skeletal crystals form in open (vapor) space created by the dissolution of bulk silicate, and compositional boundary layers are not observed. We interpret the changes in reaction products at ΔT=300°C to indicate conditions below a glass transition; hence, partition coefficients were not determined for this undercooling. Values of K _d(P)^Kfs/melt from experiments at ΔT=25–200°C, calculated from pairs of crystal and immediately adjacent liquid compositions (including boundary layers at higher undercooling), are mostly in the range of 0.25–0.55 and show no effective change with increased undercooling. Essentially no change in K _d(P)^Kfs/melt with undercooling apparently stems from an interplay between boundary layer composition and a change in the substitution mechanism for P in feldspar from AlPSi₋₂, common in peraluminous to metaluminous liquids near equilibrium, to increasing proportions of ([ ],P)(M⁺,Si)₋₁ with increased undercooling. Bulk glass and liquid beyond boundary layers in experiments with significant percentages of crystallization are homogeneous, and show pronounced fractionation primarily due to the removal of an orthoclase component. Because crystallization was still in progress in experiments with ΔT≤200°C, compositional homogeneity in the bulk liquid requires extremely rapid diffusion of most haplogranite components (Na, K, and Al), apparently resulting from chemical potential gradients stemming from the removal of components from the liquid by crystal growth. Similar homogeneity and bulk fractionation in experiments with ΔT=300°C requires rapid diffusive equilibration for the alkalis even at temperatures below an apparent glass transition. Unlike the haplogranite components, P is only concentrated in liquid boundary layers (ΔT≤200°C) or low-density aqueous vapor (ΔT=300°C) adjacent to crystals. Hence, the P₂O₅ contents of melt inclusions likely are not representative of bulk melt concentrations in significantly undercooled systems (ΔT≤50–100°C).     

Rare-earth elements as source indicators of Pan-African granites from Obudu Plateau,Southeastern Nigeria

The rare-earth element （REE） concentrations of representative granite samples from the southeast of the Obudu Plateau, Nigeria, were analyzed with an attempt to determine the signatures of their source, evolutionary history and tectonic setting. Results indicated that the granites have high absolute REE concentrations （190×10^-6-1191×10^-6; av.=549×10^-6） with the chondrite-normalized REE patterns characterized by steep negative slopes and prominent to slight or no negative Eu anomalies. All the samples are also characterized by high and variable concentrations of the LREE （151×10^-6-1169×10^-6; av.= 466×10^-6）, while the HREE show low abundance （4×10^-6-107×10^-6; av.=28×10^-6）. These are consistent with the variable levels of REE fractionation, and differentiation of the granites. This is further supported by the range of REE contents, the chondrite-normalized patterns and the ratios of LaN/YbN （2.30-343.37）, CeN/YbN （5.94-716.87）, LaN/SmN （3.14-11.68） and TbN/YbN （0.58-1.65）. The general parallelism of the REE patterns, suggest that all the granites were comagmatic in origin, while the high Eu/Eu＊ ratios （0.085-2.807; av.=0.9398） indicate high fo2 at the source. Similarly, irregular variations in LaN/YbN, CeN/YbN and Eu/Eu＊ ratios and REE abundances among the samples suggest behaviors that are related to mantle and crustal sources.     

Atmospheric elemental abundances for the components of the multiple system ADS 11061. 41 Draconis

We obtained speckle interferometric and spectroscopic observations of the system 41 Dra during its periastron passage in 2001. The components’ lines are resolved in the spectral interval 3700–9200 Å. The observed wavelength dependence of the brightness difference between the components is used to estimate the B-V indices separately for each of the components: B-V = 0.511 for component a and B-V = 0.502 for component b. We derived improved effective temperatures of the components from their B-V values and hydrogen-line profiles. The observations can be described with the parameters for the components T _eff ^a = 6370 K, log g^a = 4.05 and T _eff ^b = 6410 K, log g^b = 4.20. The iron, carbon, nitrogen, and oxygen abundances in the atmospheres of the components are log N(Fe)^a = 7.55, log N(Fe)^b = 7.60, log N(C)^a = 8.52, log N(C)^b = 8.58, log N(N)^a = 8.05, log N(N)^b = 7.99, log N(O)^a = 8.73, log N(O)^b = 8.76.     

Excess heat capacity and entropy of mixing in the high-structural state (K,Ca)-feldspar binary

Low- and high-temperature heat capacities were measured for a series of synthetic high-structural state (K,Ca)-feldspars (Or–An) using both a relaxation and a differential scanning calorimeter. The data were collected at temperatures between 5 and 800 K on polycrystalline samples that had been synthesised and characterised in a previous study. Below T = 300 K, Or₉₀An₁₀, and Or₈₀An₂₀ showed excess heat capacities of mixing with maximum values of ~3 J mol⁻¹ K⁻¹. The other members of this binary (An > 20 mol%) had lower excess heat capacity values of up to ~1 J mol⁻¹ K⁻¹. Above T = 300 K, some compositions exhibited negative excess heat capacities of mixing (with maximum values of −2 J mol⁻¹ K⁻¹). The vibrational entropy at 298.15 K for Or₉₀An₁₀ and Or₈₀An₂₀ deviated strongly from the behaviour of a mechanical mixture, with excess entropy values of ~3.5 J mol⁻¹ K⁻¹. More An-rich members had only small excess vibrational entropies at T = 298.15 K. The difference in behaviour between members with An > 20 mol% and those with An ≤ 20 mol% is probably a consequence of the structural state of the (K,Ca)-feldspars, i.e., (K,Ca)-feldspars with An ≤ 20 mol% have monoclinic symmetry, whereas those with An > 20 mol% are triclinic. At T = 800 K, the vibrational entropy values were found to scatter around the values expected for a mechanical mixture and, thus, correspond to a quasi-ideal behaviour. The solvus for the (K,Ca)-feldspar binary was calculated based on the entropy data from this study in combination with enthalpy and volume of mixing data from a previous study.     

A thermodynamic analysis of the system LiAlSiO4-NaAlSiO4-Al2O3-SiO2-H2O based on new heat capacity, thermal expansion, and compressibility data for selected phases

Heat capacity, thermal expansion, and compressibility data have been obtained for a number of selected phases of the system NaAlSiO₄-LiAlSiO₄-Al₂O₃-SiO₂-H₂O. All C _p measurements have been executed by DSC in the temperature range 133–823 K. The data for T ≥ 223 K have been fitted to the function C _p (T) = a + cT ⁻² + dT ^−0.5 + fT ⁻³, the fit parameters being The thermal expansion data (up to 525 °C) have been fitted to the function V ⁰(T) = V ⁰(T) [1 + v ₁ (T−T ⁰) + v ₂ (T−T ⁰)²], with T ⁰ = 298.15 K. The room-temperature compressibility data (up to 6 GPa) have been smoothed by the Murnaghan equation of state. The resulting parameters are These data, along with other phase property and reaction reversal data from the literature, have been simultaneously processed by the Bayes method to derive an internally consistent thermodynamic dataset (see Tables 6 and 7) for the NaAlSiO₄-LiAlSiO₄-Al₂O₃-SiO₂-H₂O quinary. Phase diagrams generated from this dataset are compatible with cookeite-, ephesite-, and paragonite-bearing assemblages observed in metabauxites and common metasediments. Phase diagrams obtained from the same database are also in agreement with the cookeite-free, petalite-, spodumene-, eucryptite-, and bikitaite-bearing assemblages known to develop in the subsolidus phase of recrystallization of␣lithium-bearing pegmatites. It is gratifying to note that the cookeite phase relations predicted earlier by Vidal and Goffé (1991) in the context of the system Li₂O-Al₂O₃-SiO₂-H₂O agree with our results in a general way. Received: 19 May 1998 / Accepted: 25 June 1998     

Heat capacity and thermodynamic functions of xenotime YPO<Subscript>4</Subscript>(c) at 0–1600 K

The heat capacity of xenotime YPO₄(c) was measured by adiabatic calorimetry at 4.78–348.07 K. Our experimental and literature data on H ⁰(T)-H ⁰(298.15 K) of Y orthophosphate were utilized to derive the C _p ⁰(T) function of xenotime at 0–1600 K, which was then used to calculate the values of thermodynamic functions: entropy, enthalpy change, and reduced Gibbs energy. These functions assume the following values at 298.15 K: C _p ⁰ (298.15 K) = 99.27 ± 0.02 J K⁻¹ mol⁻¹, S ⁰(298.15 K) = 93.86 ± 0.08 J K⁻¹ mol⁻¹, H ⁰(298.15 K) − H ⁰(0) = 15.944 ± 0.005 kJ mol⁻¹, Φ⁰(298.15 K) = 40.38 ± 0.08 J K⁻¹ mol⁻¹. The value of the free energy of formation Δ _f G ⁰(YPO₄, 298.15 K) is −1867.9 ± 1.7 kJ mol⁻¹.     

Behavior of epidote at high pressure and high temperature: a powder diffraction study up to 10 GPa and 1,200 K

The thermo-elastic behavior of a natural epidote [Ca_1.925 Fe_0.745Al_2.265Ti_0.004Si_3.037O₁₂(OH)] has been investigated up to 1,200 K (at 0.0001 GPa) and 10 GPa (at 298 K) by means of in situ synchrotron powder diffraction. No phase transition has been observed within the temperature and pressure range investigated. P–V data fitted with a third-order Birch–Murnaghan equation of state (BM-EoS) give V ₀ = 458.8(1)ų, K _T0 = 111(3) GPa, and K′ = 7.6(7). The confidence ellipse from the variance–covariance matrix of K _T0 and K′ from the least-square procedure is strongly elongated with negative slope. The evolution of the “Eulerian finite strain” vs “normalized stress” yields Fe(0) = 114(1) GPa as intercept values, and the slope of the regression line gives K′ = 7.0(4). The evolution of the lattice parameters with pressure is slightly anisotropic. The elastic parameters calculated with a linearized BM-EoS are: a ₀ = 8.8877(7) Å, K _T0(a) = 117(2) GPa, and K′(a) = 3.7(4) for the a-axis; b ₀ = 5.6271(7) Å, K _T0(b) = 126(3) GPa, and K′(b) = 12(1) for the b-axis; and c ₀ = 10.1527(7) Å, K _T0(c) = 90(1) GPa, and K’(c) = 8.1(4) for the c-axis [K _T0(a):K _T0(b):K _T0(c) = 1.30:1.40:1]. The β angle decreases with pressure, β_P(°) = β_P0 −0.0286(9)P +0.00134(9)P ² (P in GPa). The evolution of axial and volume thermal expansion coefficient, α, with T was described by the polynomial function: α(T) = α₀ + α₁ T ^−1/2. The refined parameters for epidote are: α₀ = 5.1(2) × 10⁻⁵ K⁻¹ and α₁ = −5.1(6) × 10⁻⁴ K^1/2 for the unit-cell volume, α₀(a) = 1.21(7) × 10⁻⁵ K⁻¹ and α₁(a) = −1.2(2) × 10⁻⁴ K^1/2 for the a-axis, α₀(b) = 1.88(7) × 10⁻⁵ K⁻¹ and α₁(b) = −1.7(2) × 10⁻⁴ K^1/2 for the b-axis, and α₀(c) = 2.14(9) × 10⁻⁵ K⁻¹ and α₁(c) = −2.0(2) × 10⁻⁴ K^1/2 for the c-axis. The thermo-elastic anisotropy can be described, at a first approximation, by α₀(a): α₀(b): α₀(c) = 1 : 1.55 : 1.77. The β angle increases continuously with T, with β_T(°) = β_T0 + 2.5(1) × 10⁻⁴ T + 1.3(7) × 10⁻⁸ T ². A comparison between the thermo-elastic parameters of epidote and clinozoisite is carried out.     

Fluid inclusions in the Niquelândia and Barro Alto Complexes, Goias State, Brazil

Summary ?Fluid inclusions from two Mesoproterozoic, metamorphosed layered intrusive complexes, Niquelandia and Barro Alto, Goiás State, Brazil record multiple fluid influx events from the magmatic to granulitic and retrograde metamorphic stages. 1. The oldest inclusions contain high density CO₂ ± N₂ ± CH₄ and are found as primaries in plagioclase and orthopyroxene in mafic granulite with homogenization temperatures between − 48 and − 28 °C. These inclusions may correspond to the early, magmatic stage. This type was found in samples from both the Niquelandia and the Barro Alto complexes. 2. Intragranular, relatively high density CO₂ + N₂ inclusions (T_h between − 33 and − 26 °C) together with decrepitated and reequilibrated N₂ inclusions (T_h between − 160 and − 151 °C) in the rock-forming minerals can be associated with the granulite facies metamorphism. Such inclusions were found only in the Barro Alto complex. 3. Transgranular, high density, CO₂–N₂ inclusions (93% CO₂ and 7% N₂, according to Raman analysis, with T_h between − 66.6 and − 50.4 °C) as well as the low density, secondary CO₂ ± N₂ ± CH₄ inclusions (T_h between − 13.0 and + 18.7 °C) and the H₂O–NaCl–CaCl₂ hypersaline inclusions (with halite dissolution temperature between 132 and 354 °C, and T_h between 212 and 490 °C) are attributed to different fluid influx events during the retrograde metamorphism. This inclusion type can be found both in the Niquelandia and in the Barro Alto complexes. The fluid inclusion textures and compositions show several stages of fluid evolution. The fluid inclusion measurements and the geothermobarometric data indicate an anticlockwise P-T path for both the Barro Alto and the Niquelandia complexes. Received October 16, 2000; revised version accepted November 20, 2001     

Thermal expansion of gehlenite, Ca2Al[AlSiO7], and the related aluminates LnCaAl[Al2O7] with Ln = Tb, Sm

The thermal expansion of gehlenite, Ca₂Al[AlSiO₇], (up to T=830 K), TbCaAl[Al₂O₇] (up to T=1100 K) and SmCaAl[Al₂O₇] (up to T=1024 K) has been determined. All compounds are of the melilite structure type with space group Thermal expansion data were obtained from in situ X-ray powder diffraction experiments in-house and at HASYLAB at the Deutsches Elektronen Synchrotron (DESY) in Hamburg (Germany). The thermal expansion coefficients for gehlenite were found to be: α₁=7.2(4)×10⁻⁶×K⁻¹+3.6(7)×10⁻⁹ΔT×K⁻² and α₃=15.0(1)×10⁻⁶×K⁻¹. For TbCaAl[Al₂O₇] the respective values are: α₁=7.0(2)×10⁻⁶×K⁻¹+2.0(2)×10⁻⁹ΔT×K⁻² and α₃=8.5(2)×10⁻⁶×K⁻¹+2.0(3)×10⁻⁹ΔT×K⁻², and the thermal expansion coefficients for SmCaAl[Al₂O₇] are: α₁=6.9(2)×10⁻⁶×K⁻¹+1.7(2)×10⁻⁹ΔT×K⁻² and α₃=9.344(5)×10⁻⁶×K⁻¹. The expansion mechanisms of the three compounds are explained in terms of structural trends obtained from Rietveld refinements of the crystal structures of the compounds against the powder diffraction patterns. No structural phase transitions have been observed. While gehlenite behaves like a ‘proper’ layer structure, the aluminates show increased framework structure behavior. This is most probably explained by stronger coulombic interactions between the tetrahedral conformation and the layer-bridging cations due to the coupled substitution (Ca²⁺+Si⁴⁺)–(Ln ³⁺+Al³⁺) in the melilite-type structure. This article has been mistakenly published twice. The first and original version of it is available at .     

Thermodynamic functions of eskolaite Cr<Subscript>2</Subscript>O<Subscript>3</Subscript>(c) at 0–1800 K

The heat capacity of eskolaite Cr₂O₃(c) was determined by adiabatic vacuum calorimetry at 11.99–355.83 K and by differential calorimetry at 320–480 K. Experimental data of the authors and data compiled from the literature were applied to calculate the heat capacity, entropy, and the enthalpy change of Cr₂O₃ within the temperature range of 0–1800 K. These functions have the following values at 298.15 K: C _p ⁰ (298.15) = 121.5 ± 0.2 J K⁻¹mol⁻¹, S ⁰(298.15) = 80.95 ± 0.14 J K⁻¹mol⁻¹, and H ⁰(298.15)-H ⁰(0) = 15.30±0.02 kJ mol⁻¹. Data were obtained on the transitions from the antiferromagnetic to paramagnetic states at 228–457 K; it was determined that this transition has the following parameters: Neel temperature T _N = 307 K, Δ _tr S = 6.11 ± 0.12 J K⁻¹mol⁻¹ and δ _tr H = 1.87 ± 0.04 kJ mol⁻¹.     

Thermal expansion and structural transformations of stuffed derivatives of quartz along the LiAlSiO4–SiO2 join: a variable-temperature powder synchrotron XRD study

 The structural behavior of stuffed derivatives of quartz within the Li_{1− x} Al_{1− x} Si_{1+ x} O₄ system (0 ≤ x ≤ 1) has been studied in the temperature range 20 to 873 K using high-resolution powder synchrotron X-ray diffraction (XRD). Rietveld analysis reveals three distinct regimes whose boundaries are defined by an Al/Si order-disorder transition at x=∼0.3 and a β–α displacive transformation at x=∼0.65. Compounds that are topologically identical to β-quartz (0 ≤ x < ∼0.65) expand within the (0 0 1) plane and contract along c with increasing temperature; however, this thermal anisotropy is significantly higher for structures within the regime 0 ≤ x < ∼0.3 than for those with compositions ∼0.3 ≤ x < ∼0.65. We attribute this disparity to a tetrahedral tilting mechanism that occurs only in the ordered structures (0 ≤ x < ∼0.3). The phases with ∼0.65 ≤ x ≤ 1 adopt the α-quartz structure at room temperature, and they display positive thermal expansion along both a and c from 20 K to their α–β transition temperatures. This behavior arises mainly from a rotation of rigid Si(Al)-tetrahedra about the <100> axes. Landau analysis provides quantitative evidence that the charge-coupled substitution of Li+Al for Si in quartz dampens the α–β transition. With increasing Li+Al content, the low-temperature modifications exhibit a marked decrease in spontaneous strain; this behavior reflects a weakening of the first-order character of the transition. In addition, we observe a linear decrease in the α–β critical temperature from 846 K to near 0 K as the Li+Al content increases from x=0 to x=∼0.5. Received: 26 June 2000 / Accepted: 1 December 2000     

The thermoelastic behavior of clintonite up to 10?GPa and 1,000°C

The thermoelastic behavior of a natural clintonite-1M [with composition: Ca_1.01(Mg_2.29Al_0.59Fe_0.12)_Σ3.00(Si_1.20Al_2.80)_Σ4.00O₁₀(OH)₂] has been investigated up to 10 GPa (at room temperature) and up to 960°C (at room pressure) by means of in situ synchrotron single-crystal and powder diffraction, respectively. No evidence of phase transition has been observed within the pressure and temperature range investigated. P–V data fitted with an isothermal third-order Birch–Murnaghan equation of state (BM-EoS) give V ₀ = 457.1(2) ?³, K _T0 = 76(3)GPa, and K′ = 10.6(15). The evolution of the “Eulerian finite strain” versus “normalized stress” shows a linear positive trend. The linear regression yields Fe(0) = 76(3) GPa as intercept value, and the slope of the regression line leads to a K′ value of 10.6(8). The evolution of the lattice parameters with pressure is significantly anisotropic [β(a) = 1/3K _T0(a) = 0.0023(1) GPa⁻¹; β(b) = 1/3K _T0(b) = 0.0018(1) GPa⁻¹; β(c) = 1/K _T0(c) = 0.0072(3) GPa⁻¹]. The β-angle increases in response to the applied P, with: β_P = β₀ + 0.033(4)P (P in GPa). The structure refinements of clintonite up to 10.1 GPa show that, under hydrostatic pressure, the structure rearranges by compressing mainly isotropically the inter-layer Ca-polyhedron. The bulk modulus of the Ca-polyhedron, described using a second-order BM-EoS, is K _T0(Ca-polyhedron) = 41(2) GPa. The compression of the bond distances between calcium and the basal oxygens of the tetrahedral sheet leads, in turn, to an increase in the ditrigonal distortion of the tetrahedral ring, with ∂α/∂P ≈ 0.1°/GPa within the P-range investigated. The Mg-rich octahedra appear to compress in response to the applied pressure, whereas the tetrahedron appears to behave as a rigid unit. The evolution of axial and volume thermal expansion coefficient α with temperature was described by the polynomial α(T) = α₀ + α₁ T ^−1/2. The refined parameters for clintonite are as follows: α₀ = 2.78(4) 10⁻⁵°C⁻¹ and α₁ = −4.4(6) 10⁻⁵°C^1/2 for the unit-cell volume; α₀(a) = 1.01(2) 10⁻⁵°C⁻¹ and α₁(a) = −1.8(3) 10⁻⁵°C^1/2 for the a-axis; α₀(b) = 1.07(1) 10⁻⁵°C⁻¹ and α₁(b) = −2.3(2) 10⁻⁵°C^1/2 for the b-axis; and α₀(c) = 0.64(2) 10⁻⁵°C⁻¹ and α₁(c) = −7.3(30) 10⁻⁶°C^1/2for the c-axis. The β-angle appears to be almost constant within the given T-range. No structure collapsing in response to the T-induced dehydroxylation was found up to 960°C. The HP- and HT-data of this study show that in clintonite, the most and the less expandable directions do not correspond to the most and the less compressible directions, respectively. A comparison between the thermoelastic parameters of clintonite and those of true micas was carried out.     

IR photometry and models of dust shells for two RCB stars

We present JHKLM photometry obtained in 1984–2009 for the RCB stars UV Cas and SU Tau. No major fadings characteristic of RCB stars were detected during the observations of UV Cas, while two events of this kind occurred for SU Tau. The observed flux and color-index variations can be explained with a changing dust concentration in the line of sight, and possibly variations of the stellar temperature. We use the measured fluxes, supplemented with observations in the intermediate IR, to compute spherically symmetric dust-shell models for the stars. The mass-loss rate is estimated to be 1.7 × 10⁻⁶ M _⊙ yr⁻¹ for UV Cas and 4.1 × 10⁻⁶ M _⊙ yr⁻¹ for SU Tau.