A Pulsar Time Scale Based on Parkes Observations in 1995–2010

Timing of highly stable millisecond pulsars provides the possibility of independently verifying terrestrial time scales on intervals longer than a year. An ensemble pulsar time scale is constructed based on pulsar timing data obtained on the 64-m Parkes telescope (Australia) in 1995–2010. Optimal Wiener filters were applied to enhance the accuracy of the ensemble time scale. The run of the time-scale difference PT_ens?TT(BIPM2011) does not exceed 0.8 ± 0.4 μs over the entire studied time interval. The fractional instability of the difference PT_ens?TT(BIPM2011) over 15 years is σ _z = (0.6 ± 1.6) × 10^?15, which corresponds to an upper limit for the energy density of the gravitational-wave background Ω _g h² ~ 10^?10 and variations in the gravitational potential ~10^?15 Hz at the frequency 2 × 10^?9 Hz.     

Measurement of the inner turbulence scale of the interstellar plasma toward the pulsar PSR B2111+46

The pulsar PSR B2111+46 has been observed at 112 MHz, and a new approach to analyzing pulsar pulses scattered in turbulent interstellar plasma applied. This method is based on the dependence of the normalized energy in the trailing part of a pulse on the intrapulse time. Since the trailing edge of a pulse follow exponential law to high accuracy, the inner turbulence scale of the interstellar plasma exceeds the field coherence scale. The measured scattering parameter is τ _sc = 147 ± 1 ms. Analysis of the parameters of diffractive and refractive scintillations of the pulsar at 610 MHz together with the 112 MHz data shows that the spectrum of the interstellar plasma toward PSR B2111+46 is a piecewise power law: on scales of 10¹³–10¹⁴ cm, the exponent of the turbulence spectrum is n ≃ 4, whereas n = 3.5 on scales of 2 × 10⁸−10¹³ cm. The spectrum flattens with approach to the inner turbulence scale l: n = 3–3.2. The obtained inner turbulence scale is l = (3.5 ± 1.5) × 10⁷ cm. The distribution of the interstellar plasma toward the pulsar is close to statistically homogeneous. The local density (N _e = 0.4 cm⁻³) and filling factor (F = 0.04) of the interstellar plasma have been estimated. The similarity of N _e estimates obtained from the inner scale of the inhomogeneities and the ratio of the emission measure to the dispersion measure provides evidence that the inner turbulence scale corresponds to the ion inertial length.     

Chemical composition of rock-forming minerals in gold-related granitoid intrusions,southwestern New Brunswick,Canada: implications for crystallization conditions,volatile exsolution,and fluorine-chlorine activity

Chemical composition of rock-forming minerals in Appalachian Siluro-Devonian granitoid intrusions, southwestern New Brunswick, was systematically determined by electron microprobe. The mineral chemical data together with petrographic examination was used to test magmatic equilibration and to constrain crystallization conditions, volatile exsolution, and fluorine-chlorine activity of fluids associated with these intrusions. Mineralogical distinction between Late Silurian to Early Devonian granodioritic to monzogranitic series (GMS) and Late Devonian granitic series (GS) rocks is evident, although both are subsolvus I-type to evolved I-type granitoids. Oxidized to reduced GMS rocks consist of quartz, plagioclase (An>10), K-feldspar, biotite, apatite, titanite, zircon, monazite, ± hornblende, ± pyroxene, ± magnetite, ± ilmenite, and ± sulfide. GS rocks comprise quartz, K-feldspar, plagioclase (An<10), mica group minerals, zircon, monazite, apatite, sulfide, ± ilmente, ± magnetite, ± topaz, ± columbite, and ± xenotime. Inter-intrusion and intra-intrusion variations in mineral chemistry are interpreted to reflect petrogenetic processes (e.g., assimilation and fractional crystallization) during granitoid evolution. Although magmatic equilibration among rock-forming minerals are disturbed by subsolidus hydrothermal processes, GMS rocks appear to have higher magmatic temperatures, variable levels of emplacement, a range of (i.e., reduced intrusions 10^−16.7∼10^−13.4 and oxidized intrusions 10^−14.0∼10^−10.5 bars), and relatively low f _HF/f _HCl ratios (10^−3.0∼10^−1.0) in exsolved fluids, compared to GS rocks. Reduced GMS intrusions bear higher gold potential and thus may be prospective targets for intrusion-related gold systems. Electronic Supplementary Material Supplementary material is available for this article at     

Heat capacity and thermodynamic properties of GdPO<Subscript>4</Subscript> in the temperature range 0–1600 K

The heat capacity of gadolinium orthophosphate (GdPO₄) measured in the temperature range 11.15–344.11 K by adiabatic calorimetry and available literature data were used to calculate its thermodynamic functions at 0–1600 K. At 298.15 K, these functions are as follows: C _p ⁰(298.15 K) = 101.85 ± 0.05 J K⁻¹ mol⁻¹, S ⁰(298.15 K) = 123.82 ± 0.18 J K⁻¹ mol⁻¹, H ⁰(298.15 K)–H ⁰(0) = 17.250 ± 0.012 kJ mol⁻¹, and Φ ⁰(298.15 K) = 65.97 ± 0.18 J K⁻¹ mol⁻¹ The calculated Gibbs free energy of formation from the elements of GdPO₄ is Δ _f G ⁰ (298.15 K) = −1844.3 ± 4.7 kJ mol⁻¹.     

Experimental study of Pd hydrolysis in aqueous solutions at 25–70°C

The hydrolysis of the Pd²⁺ ion in HClO₄ solutions was examined at 25–70°C, and the thermodynamic constants of equilibrium K ₍₁₎⁰ and K ₍₂₎⁰were determined for the reactions Pd²⁺ + H₂O = PdOH⁺ + H⁺ and Pd²⁺ + 2H₂O = Pd(OH)₂⁰ + 2H⁺, respectively. The values of log K ₍₁₎⁰ = −1.66 ± 0.5 (25°C) and −0.65 ± 0.25 (50°C) and log K ₍₂₎⁰ = −4.34 ± 0.3 (25°C) and −3.80 ± 0.3 (50°C) were derived using the solubility technique at 0.95 confidence level. The values of log K ₍₁₎⁰ = −1.9 ± 0.6 (25°C), −1.0 ± 0.4 (50°C), and −0.5 ± 0.3 (70°C) were obtained by spectrophotometric techniques. The palladium ion is significantly hydrolyzed at elevated temperatures (50–70°C) even in strongly acidic solutions (pH 1–1.5), and its hydrolysis is enhanced with increasing temperature.     

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.     

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.     

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

The heat capacity of synthetic pretulite ScPO₄(c) was measured by adiabatic calorimetry within a temperature range of 12.13–345.31 K, and the temperature dependence of the pretulite heat capacity at 0–1600 K was derived from experimental and literature data on H ⁰(T)-H ⁰(298.15 K) for Sc orthophosphate. This dependence was used to calculate the values of the following thermodynamic functions: entropy, enthalpy change, and reduced Gibbs energy. They have the following values at 298.15 K: C _p ⁰ (298.15 K) = 97.45 ± 0.06 J K⁻¹ mol⁻¹, S ⁰(298.15 K) = 84.82 ± 0.18 J K⁻¹ mol⁻¹, H ⁰(298.15 K)-H ⁰(0) = 14.934 ± 0.016 kJ mol⁻¹, and Φ ⁰(298.15 K) = 34.73 ± 0.19 J K⁻¹mol⁻¹. The enthalpy of formation Δ _f H ⁰(ScPO₄, 298.15 K) = − 1893.6 ± 8.4 kJ mol⁻¹.     

Diffusion of tetravalent cations in zircon

Diffusion rates for the three tetravalent cations U, Th and Hf have been measured in synthetic zircon. Diffusant sources included oxide powders and ground pre-synthesized silicates. Rutherford backscattering spectrometry (RBS) was used to measure depth profiles. Over the temperature range 1400–1650 °C, the following Arrhenius relations were obtained (diffusion coefficients in m²sec⁻¹): log D _Th = (1.936 ± 0.9820) + (− 792 ± 34 kJ mol⁻¹ /2.303 RT) log D _U = (0.212 ± 2.440) + (− 726 ± 83 kJ mol⁻¹ /2.303 RT) log D _Hf = (3.206 ± 1.592) + (− 812 ± 54 kJ mol⁻¹ /2.303 RT) The data show a systematic increase in diffusivity with decreasing ionic radius (i.e., faster diffusion rates for Hf than for U or Th), a trend also observed in our earlier study of rare earth diffusion in zircon. Diffusive fractionation may be a factor in the Lu-Hf system given the much slower diffusion rates of tetravalent cations when compared with the trivalent rare earths. The very slow diffusion rates measured for these tetravalent cations suggest that they are essentially immobile under most geologic conditions, permitting the preservation of fine-scale chemical zoning and isotopic signatures of inherited cores. Received: 12 July 1996 / Accepted: 2 December 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     

Low T heat capacity measurements and new entropy data for titanite (sphene): implications for thermobarometry of high-pressure rocks

The accepted standard state entropy of titanite (sphene) has been questioned in several recent studies, which suggested a revision from the literature value 129.3 ± 0.8 J/mol K to values in the range of 110–120 J/mol K. The heat capacity of titanite was therefore re-measured with a PPMS in the range 5 to 300 K and the standard entropy of titanite was calculated as 127.2 ± 0.2 J/mol K, much closer to the original data than the suggested revisions. Volume parameters for a modified Murgnahan equation of state: V _P,T  = V ₂₉₈° × [1 + a°(T − 298) − 20a°(T − 298)] × [1 – 4P/(K ₂₉₈ × (1 – 1.5 × 10⁻⁴ [T − 298]) + 4P)]^1/4 were fit to recent unit cell determinations at elevated pressures and temperatures, yielding the constants V ₂₉₈° = 5.568 J/bar, a° = 3.1 × 10⁻⁵ K⁻¹, and K = 1,100 kbar. The standard Gibbs free energy of formation of titanite, −2456.2 kJ/mol (∆H°_f = −2598.4 kJ/mol) was calculated from the new entropy and volume data combined with data from experimental reversals on the reaction, titanite + kyanite = anorthite + rutile. This value is 4–11 kJ/mol less negative than that obtained from experimental determinations of the enthalpy of formation, and it is slightly more negative than values given in internally consistent databases. The displacement of most calculated phase equilibria involving titanite is not large except for reactions with small ∆S. Re-calculated baric estimates for several metamorphic suites yield pressure differences on the order of 2 kbar in eclogites and 10 kbar for ultra-high pressure titanite-bearing assemblages.     

Pressure-dependent stability of cadmium chloride complexes: Potentiometric measurements at 1–1000 bar and 25°C

Potentiometric measurements were performed in the Cd(NO₃)₂-KCl-H₂O system at 25°C and 1–1000 bar using an isothermal cell with a liquid junction and equipped with a solid contact Cd-selective electrode. At 1 bar, the stepwise equilibrium constant of the fourth cadmium chloride complex CdCl₄²⁻ has been determined (log K₄⁰ = −0.88 ± 0.25). The pressure-dependent stability constants for all cadmium chloride complexes have been experimentally established for the first time. As pressure increases from 1 to 1000 bar, the stability constants for the first, third, and fourth complexes change by less than 0.05 logarithmic units, whereas that for the second complex decreases by 0.33 logarithmic units. On the basis of these data, the partial molar volumes of four cadmium chloride complexes have been determined under standard state conditions: V ⁰(CdCl⁺) = 2.20 ± 3, V ⁰(CdCl_{2 (aq)}) = 42.21 ± 5, V ⁰(CdCl₃⁻) = 63.47 ± 10, and V ⁰(CdCl₄²⁻) = 81.35 ± 15 cm³mol⁻¹. The linear correlation between the nonsolvation contributions of molar volumes and the number of ligands corresponds to the change in coordination from octahedral in Cd²⁺ and CdCl⁺ to tetrahedral in CdCl_{2 (aq)}, CdCl₃⁻, and CdCl₄²⁻ complexes. Using theoretical correlations, the HKF parameters allowing calculation of the volumetric properties of cadmium chloride complexes in a wide range of temperature and pressure have been obtained. The pressure effect on cadmium concentration in sphalerite in equilibrium with the H₂O-NaCl hydrothermal fluid has been estimated. It is shown that the Cd content in sphalerite increases with pressure.     

Refinement of the parameters of the binary pulsar B0655+64 based on 111 MHz observations

An analysis of monitoring observations for the pulsar PSR B0655+64, which is located in a binary system, at 111 MHz during 2002–2015 are presented. The Keplerian parameters of the pulsar have been refived: the longitude of periastron ω = 276_.^°5785 ± 0_.^°0005 and the orbital semi-major axis is a_p sin i = 4.124976± 0.000003 s. The parameters of the perturbed motion have been determined: the motion of periastron ω = 0_.^°315 ± 0_.^°005/ year, and the derivative of the period of the binary system ? = (-1.66 ± 0.11) × 10^-14 s/s = (-0.524 ± 0.038) µs/year. The estimated time scale for the decay of the PSR 0655+64 system is (1.7 ± 0.1) × 10¹¹ yrs.     

Monitoring of the radio emission of the Crab Nebula pulsar at low frequencies

Results of long-term (2002–2010) monitoring of giant radio pulses of the pulsar PSR B0531+21 in the Crab Nebula at ν = 44, 63, and 111 MHz are reported. The observations were conducted on the LPA and DKR-1000 radio telescopes of the Lebedev Physical Institute. The giant pulses were analyzed using specialized software for calculating the magnitude of the scattering τ _sc , signal-to-noise ratio, and other required parameters by modeling the propagation of a pulse in the scattering interstellar medium. Three pronounced sharp increases in the scattering were recorded in 2002–2010. Analysis of the dependence between the variations of the scattering and dispersion measure (data of Jodrell Bank Observatory) shows a strong correlation at all frequencies, ≈0.9. During periods of anomalous increase in scattering and the dispersion measure, the index γ in the frequency dependence of the scattering in the Crab Nebula, τ _sc (ν) ∝ ν ^−γ , was smaller than the generally accepted values γ = 4.0 for a Gaussian and γ = 4.4 for a Kolmogorov distribution. This difference in combination with the piece-wise power-law spectrum may be due to the presence of a dense plasma structure with developed Langmuir turbulence in the nebula, along the pulsar’s line of sight. The magnetic field in the Crab Nebula estimated from measurements of the rotation measure toward the pulsar is 100 μG.     

Low-temperature thermodynamic properties of disordered zeolites of the natrolite group

 The heat capacity of paranatrolite and tetranatrolite with a disordered distribution of Al and Si atoms has been measured in the temperature range of 6–309 K using the adiabatic calorimetry technique. The composition of the samples is represented with the formula (Na_1.90K_0.22Ca_0.06)[Al_2.24Si_2.76O₁₀]·nH₂O, where n=3.10 for paranatrolite and n=2.31 for tetranatrolite. For both zeolites, thermodynamic functions (vibrational entropy, enthalpy, and free energy function) have been calculated. At T=298.15 K, the values of the heat capacity and entropy are 425.1 ± 0.8 and 419.1 ±0.8 J K⁻¹ mol⁻¹ for paranatrolite and 381.0 ± 0.7 and 383.2 ± 0.7 J K⁻¹ mol⁻¹ for tetranatrolite. Thermodynamic functions for tetranatrolite and paranatrolite with compositions corrected for the amount of extraframework cations and water molecules have also been calculated. The calculation for tetranatrolite with two water molecules and two extraframework cations per formula yields: C _p (298.15)=359.1 J K⁻¹ mol⁻¹, S(298.15) −S(0)=362.8 J K⁻¹ mol⁻¹. Comparing these values with the literature data for the (Al,Si)-ordered natrolite, we can conclude that the order in tetrahedral atoms does not affect the heat capacity. The analysis of derivatives dC/dT for natrolite, paranatrolite, and tetranatrolite has indicated that the water- cations subsystem within the highly hydrated zeolite may become unstable at temperatures above 200 K. Received: 30 July 2001 / Accepted: 15 November 2001     

Pressure–volume–temperature equation of state of andradite and grossular, by high-pressure and -temperature powder diffraction

 The thermoelastic parameters of natural andradite and grossular have been investigated by high-pressure and -temperature synchrotron X-ray powder diffraction, at ESRF, on the ID30 beamline. The P–V–T data have been fitted by Birch-Murnaghan-like EOSs, using both the approximated and the general form. We have obtained for andradite K ₀=158.0(±1.5) GPa, (dK/dT )₀=−0.020(3) GPa K⁻¹ and α₀=31.6(2) 10⁻⁶ K⁻¹, and for grossular K ₀=168.2(±1.7) GPa, (dK/dT)₀=−0.016(3) GPa K⁻¹ and α₀=27.8(2) 10⁻⁶ K⁻¹. Comparisons between the present issues and thermoelastic properties of garnets earlier determined are carried out. Received: 7 July 2000 / Accepted: 20 October 2000     

Thermodynamic mixing behavior of synthetic Ca-Tschermak–diopside pyroxene solid solutions: I. Volume and heat capacity of mixing

The unite cell parameters and heat capacities of a series of synthetic clinopyroxenes on the join Ca-Tschermak (CaTs)−diopside (Di) were measured using X-ray powder diffraction and calorimetric methods, respectively. The volume of mixing at 298 K shows a negative asymmetric deviation from ideality. A two-parameter Margules fit to the data yields W _CaTs−Di ^V = −0.29 ± 0.11 cm³ mol⁻¹ and W _Di−CaTs ^V = −1.14 ± 0.14 cm³ mol⁻¹. Heat capacities were determined between 5 and 923 K by heat-pulse at 5−302 K and differential-scanning calorimetry at 143−923 K. The precision of the low and high temperature C _p data is better than ±1%. Polynomials of the form C _p = a + bT ^−1/2 + cT ⁻² + dT ⁻³ were fitted to the C _p data in the temperature range between 250 and 925 K. Thermal entropy values [S ₂₉₈ − S ₀] and [S ₉₀₀ −S ₀] as well as enthalpies [H ₂₉₈ − H ₀] and [H ₉₀₀ − H ₀] were calculated for all members of the solid solution series. No significant deviation from ideal mixing behavior was observed.     

Dehydration and partial melting of tremolitic amphibole coexisting with zoisite, quartz, anorthite, diopside, and water in the system H2O-CaO-MgO-Al2O3-SiO2

The greenschist to amphibolite transition as modeled by the reaction zoisite+tremolite + quartz= anorthite+diopside+water has been experimentally investigated in the chemical system H₂O−CaO− MgO−Al₂O₃−SiO₂ over the range of 0.4–0.8 GPa. This reaction is observed to lie within the stability fields of anorthite + water and of zoisite + quartz, in accord with phase equilibrium principles, and its position is in excellent agreement with the boundary calculated from current internally-consistent data bases. The small dP/dT slope of 0.00216 GPa/K (21.6 bars/K) observed for this reaction supports the pressure-dependency of this transition in this chemical system. Experimental reversals of the Al content in tremolitic amphibole coexisting with zoisite, diopside, quartz, and water were obtained at 600, 650, and 700^°C and indicated Al total cations (atoms per formula unit, apfu) of only up to 0.5±0.08 at the highest temperature. Thermodynamic analysis of these and previous compositional reversal data for tremolitic amphibole indicated that, of the activity/composition relationships considered, a two-site-coupled cation substitution model yielded the best fit to the data and a S ⁰ (1 bar, 298 K) of 575.4±1.6 J/K · mol for magnesio-hornblende. The calculated isopleths of constant Al content in the amphibole are relatively temperature sensitive with Al content increasing with increasing temperature and pressure. Finally, several experiments in the range of 1.0–1.3 GPa were conducted to define the onset of melting, and thus the upper-thermal limit, for this mineral assemblage, which must involve an invariant point located at approximately 1.05 GPa and 770^°C. Received: 24 January 1997 / Accepted: 2 October 1997     

High-pressure transitions and thermochemistry of MGeO3 (M=Mg, Zn and Sr) and Sr-silicates: systematics in enthalpies of formation of A2+B4+O3 perovskites

Phase transitions in MgGeO₃ and ZnGeO₃ were examined up to 26 GPa and 2,073 K to determine ilmenite–perovskite transition boundaries. In both systems, the perovskite phases were converted to lithium niobate structure on release of pressure. The ilmenite–perovskite boundaries have negative slopes and are expressed as P(GPa)=38.4–0.0082T(K) and P(GPa)=27.4−0.0032T(K), respectively, for MgGeO₃ and ZnGeO₃. Enthalpies of SrGeO₃ polymorphs were measured by high-temperature calorimetry. The enthalpies of SrGeO₃ pseudowollasonite–walstromite and walstromite–perovskite transitions at 298 K were determined to be 6.0±8.6 and 48.9±5.8 kJ/mol, respectively. The calculated transition boundaries of SrGeO₃, using the measured enthalpy data, were consistent with the boundaries determined by previous high-pressure experiments. Enthalpy of formation (ΔH _f°) of SrGeO₃ perovskite from the constituent oxides at 298 K was determined to be −73.6±5.6 kJ/mol by calorimetric measurements. Thermodynamic analysis of the ilmenite–perovskite transition boundaries in MgGeO₃ and ZnGeO₃ and the boundary of formation of SrSiO₃ perovskite provided transition enthalpies that were used to estimate enthalpies of formation of the perovskites. The ΔH _f° of MgGeO₃, ZnGeO₃ and SrSiO₃ perovskites from constituent oxides were 10.2±4.5, 33.8±7.2 and −3.0±2.2 kJ/mol, respectively. The present data on enthalpies of formation of the above high-pressure perovskites were combined with published data for A²⁺B⁴⁺O₃ perovskites stable at both atmospheric and high pressures to explore the relationship between ΔH _f° and ionic radii of eightfold coordinated A²⁺ (R _A) and sixfold coordinated B⁴⁺ (R _B) cations. The results show that enthalpy of formation of A²⁺B⁴⁺O₃ perovskite increases with decreasing R _A and R _B. The relationship between the enthalpy of formation and tolerance factor ( R _o: O²⁻ radius) is not straightforward; however, a linear relationship was found between the enthalpy of formation and the sum of squares of deviations of A²⁺ and B⁴⁺ radii from ideal sizes in the perovskite structure. A diagram showing enthalpy of formation of perovskite as a function of A²⁺ and B⁴⁺ radii indicates a systematic change with equienthalpy curves. These relationships of ΔH _f° with R _A and R _B can be used to estimate enthalpies of formation of perovskites, which have not yet been synthesized.     

Gold mineralization in the Mazowe area, Harare-Bindura-Shamva greenstone belt, Zimbabwe: II. Genetic relationships deduced from mineralogical, fluid inclusion and stable isotope studies, and the Sm-Nd isotopic composition of scheelites

In the Mazowe area some 40 km NW of Harare in Zimbabwe, gold mineralization is hosted in a variety of lithologies of the Archean Harare-Bindura-Shamva greenstone belt, in structures related to the late Archean regional D2/3 event. Conspicuous mineralzogical differences exist between the mines; the mainly granodiorite-hosted workings at Mazowe mine are on pyrite-rich reefs, mines of the Bernheim group have metabasalt host rocks and are characterized by arsenopyrite-rich ores, and Stori's Golden Shaft and Alice mine, both in metabasalts, work sulfide-poor quartz veins. In contrast to the mineralogical diversity, near-identical fluid inventories were found at the different mines. Both H₂O-CO₂-CH₄ fluids of low salinity, and highly saline fluids are present and are regarded to indicate fluid mixing during the formation of the deposits. Notably, these fluid compositions in the Mazowe gold field markedly contrast to ore fluids “typical” of Archean mesothermal gold deposits on other cratons. Stable isotope compositions of quartz from the various deposits (δ¹⁸O=10.8 to 13.2‰ SMOW), calcite (δ¹⁸O=9.5 to 11.9‰ SMOW and δ¹³C=−3.2 to −8.0‰ PDB), inclusion water (δD=−28 to −40‰ SMOW) and sulfides (δ³⁴S=1.3 to 3.2‰ CDT) are uniform within the range typical for Archean lode gold deposits worldwide. The fluid and stable isotope compositions support the statement that the mineralization in the Mazowe gold field formed from relatively reduced fluids with a “metamorphic” signature during a single event of gold mineralization. Microthermometric data further indicate that the deposits formed in the PT range of 1.65–2.3 kbar and 250–380 °C. Ages obtained by using the Sm/Nd and Rb/Sr isotope systems on scheelites are 2604 ± 84 Ma for the mineralization at Stori's Golden Shaft mine, and 2.40 ± 0.20 Ga for Mazowe mine. The Archean age at Stori's is regarded as close to the true age of gold mineralization in the area, whereas the Proterozoic age at Mazowe mine probably reflects later resetting. Received: 30 September 1998 / Accepted: 17 August 1999