Phase equilibria and the pressure-temperature path of the highest-grade Ryoke metamorphic rocks in the Yanai district, SW Japan

The garnet-cordierite zone, the highest-grade zone of the Ryoke metamorphic rocks in the Yanai district, SW Japan, is defined by the coexistence of garnet and cordierite in pelitic rocks. Three assemblages in this zone are studied in detail, i.e. spinel + cordierite + biotite, garnet + cordierite + biotite and garnet + biotite, all of which contain quartz, K-feldspar and plagioclase. The Mg/(Fe + Mg) in the coexisting minerals decreases in the following order: cordierite, biotite, garnet and spinel. Two facts described below are inconsistent with the paragenetic relation in the K₂OFeOMgOAl₂O₃SiO₂H₂O (KFMASH) system in terms of an isophysical variation. First, garnet and biotite in the last assemblage have Mg/(Fe + Mg) higher than those in the second. Second, the first two assemblages are described by the reaction,

An isotopic study of siderites,dolomites and ankerites at high temperatures

Siderite, dolomite and ankerite were reacted with “>103°” phosphoric acid at temperatures up to 150°C with >99° yields achieved in less than two hours, using a modification of the McCrea (1950) technique. The oxygen fractionation factors, α, between the δ¹⁸O of the carbonate and that of the acid-extracted CO₂ are:      

3.

Low-temperature heat capacities of synthetic pyrope,grossular, and pyrope₆₀grossular₄₀     

H.T. Haselton  E.F. Westrum 《Geochimica et cosmochimica acta》1980,44(5):701-709

The heat capacities of synthetic pyrope (Mg₃Al₂Si₂O₁₂), grossular (Ca₃Al₂Si₃O₁₂) and a solid solution pyrope₆₀grossular₄₀ (Mg_1.8Ca_1.2Al₂Si₃O₁₂) have been measured by adiabatic calorimetry in the temperature range 10–350 K. The samples were crystallized from glasses in a conventional piston-cylinder apparatus.The molar thermophysical properties at 298.15 K (J mol^?1 K^?1) are:

Low-temperature heat capacities of synthetic pyrope,grossular, and pyrope60grossular40

The heat capacities of synthetic pyrope (Mg₃Al₂Si₂O₁₂), grossular (Ca₃Al₂Si₃O₁₂) and a solid solution pyrope₆₀grossular₄₀ (Mg_1.8Ca_1.2Al₂Si₃O₁₂) have been measured by adiabatic calorimetry in the temperature range 10–350 K. The samples were crystallized from glasses in a conventional piston-cylinder apparatus.The molar thermophysical properties at 298.15 K (J mol^?1 K^?1) are:

High-temperature heat capacity and thermodynamic properties for end-member titanite (CaTiSiO5)

 The heat capacity of end-member titanite and (CaTiSiO₅) glass has been measured in the range 328–938 K using differential scanning calorimetry. The data show a weak λ-shaped anomaly at 483 ± 5 K, presumably associated with the well-known low-pressure P2₁/a ⇆ A2/a transition, in good agreement with previous studies. A value of 0.196 ± 0.007 kJ mol⁻¹ for the enthalpy of the P2₁/a ⇆ A2/a transition was determined by integration of the area under the curve for a temperature interval of 438–528 K, bracketing the anomaly. The heat capacity data for end-member titanite and (CaTiSiO₅) glass can be reproduced within <1% using the derived empirical equations (temperature in K, pressure in bars):

Supercooled diopside melt: confirmation of temperature-dependent expansivity using container-based dilatometry

The expansivity of supercooled diopside liquid has been determined using techniques of container-based dilatometry. Two thermal strategies have been employed, one in which the sample is brought to volumetric equilibrium by long-duration dwells at low temperatures (817 °C) and one in which scanning dilatometry of the sample has been performed at somewhat higher temperatures (890–913 °C). The results of both experiments yield a supercooled liquid expansivity for diopside liquid in the temperature range of 817–913 °C of 84.4 ± 2.8 × 10⁻⁴ cm³/mol K. The expansivity is 65% higher than that obtained for diopside melt obtained at superliquidus temperatures using the double bob Archimedean method. Combined fitting of the new low temperature, volume–temperature data from the present study and the superliquidus data from the literature has been performed. The combined fit yields the following equations for the volume–temperature relationship of diopside liquid (T=temperature in °C):

Dissolution Kinetics of Dolomite in Water at Elevated Temperatures

Kinetic experiments of dolomite dissolution in water over a temperature range from 25 to 250°C were performed using a flow through packed bed reactor. Authors chose three different size fractions of dolomite samples: 18–35 mesh, 35–60 mesh, and 60–80 mesh. The dissolution rates of the three particle size samples of dolomite were measured. The dissolution rate values are changed with the variation of grain size of the sample. For the sample through 20–40 mesh, both the release rate of Ca and the release rate of Mg increase with increasing temperature until 200°C, then decrease with continued increasing temperature. Its maximum dissolution rate occurs at 200°C. The maximum dissolution rates for the sample through 40–60 mesh and 60–80 mesh happen at 100°C. Experimental results indicate that the dissolution of dolomite is incongruent in most cases. Dissolution of fresh dolomite was non-stoichiometric, the Ca/Mg ratio released to solution was greater than in the bulk solid, and the ratio increases with rising temperatures from 25 to 250°C. Observations on dolomite dissolution in water are presented as three parallel reactions, and each reaction occurs in consecutive steps as

An empirical garnet (YAG) – xenotime thermometer

 A pronounced negative correlation between the yttrium concentration in garnet ([Y]_Grt) and temperature has been observed in xenotime (YPO₄)-bearing metapelites from central New England, USA. The [Y]_Grt decreases roughly two orders of magnitude (∼5500 to less than 100 ppm Y) over a 150 °C interval. A regression of ln([Y]_Grt) against estimated reciprocal temperature yields the following relationship:

The MgO-Al2O3-SiO2 system: free energy of pyrope and Al2O3-enstatite

Using the model of fictive ideal components, Gibbs free energies of formation of pyrope and Al₂O₃-enstatite have been determined from the experimental data on coexisting garnet and orthopyroxene and orthopyroxene and spinel in the temperature range of 1200–1600 K. The negative free energies in kJ/mol are:

     

9.

The Equation of State for Caspian Sea Waters     

Frank J. Millero  Abzar Mirzaliyev  Javid Safarov  Fen Huang  Mareva Chanson  Astan Shahverdiyev  Egon Hassel 《Aquatic Geochemistry》2008,14(4):289-299

The density ρ of Caspian Sea waters was measured as a function of temperature (273.15–343.15) K at conductivity salinities of 7.8 and 11.3 using the Anton-Paar Densitometer. Measurements were also made on one of the samples (S = 11.38) diluted with water as a function of temperature (T = 273.15–338.15 K) and salinity (2.5–11.3). These latter results have been used to develop an equation of state for the Caspian Sea (σ = ±0.007 kg m⁻³)

TK	1200	1300	1400	1500	1600
Pyrope	4869.92	4747.05	4614.26	4462.63	4311.00
Al2O3-enstatite	1257.25	1244.28	1191.93	1158.67	1125.64

where ρ⁰ is the density of water and the parameters A, B and C are given by Measurements of the density of artificial Caspian Sea water at 298.15 K agree to ± 0.012 kg m⁻³ with the real samples. These results indicate that the composition of Caspian Sea waters must be close to earlier measurements of the major components. Model calculations based on this composition yield densities that agree with the measured values to ± 0.012 kg m⁻³. The new density measurements are higher than earlier measurements. This may be related to a higher concentration of dissolved organic carbon found in the present samples (500 μM) which is much higher than the values in ocean waters (~65 μM).     

The Equation of State for Caspian Sea Waters

The density ρ of Caspian Sea waters was measured as a function of temperature (273.15–343.15) K at conductivity salinities of 7.8 and 11.3 using the Anton-Paar Densitometer. Measurements were also made on one of the samples (S = 11.38) diluted with water as a function of temperature (T = 273.15–338.15 K) and salinity (2.5–11.3). These latter results have been used to develop an equation of state for the Caspian Sea (σ = ±0.007 kg m⁻³)

Single clinopyroxene thermobarometry for garnet peridotites. Part I. Calibration and testing of a Cr-in-Cpx barometer and an enstatite-in-Cpx thermometer

Experimental clinopyroxenes synthesized at 850–1500 °C and 0–60 kbar in the CMS and CMAS-Cr systems and in more complex lherzolitic systems have been used to calibrate a Cr-in-Cpx barometer and an enstatite-in-Cpx thermometer for Cr-diopsides derived from garnet peridotites. The experiments cover a wide range of possible natural peridotitic compositions, from fertile pyrolite to refractory, high-Cr lherzolite. The barometer is based on the Cr exchange between clinopyroxene and garnet. Pressure is formulated as a function of temperature and clinopyroxene composition:

Heat capacity, entropy, and magnetic properties of jarosite-group compounds

Jarosite phases are common minerals in acidic, sulfate-rich environments. Here, we report heat capacities (C _p) and standard entropies (S°) for a number of jarosite samples. Most samples are close to the nominal composition AFe₃(SO₄)₂(OH)₆, where A = K, Na, Rb, and NH₄. One of the samples has a significant number of defects on the Fe sites and is called the defect jarosite; others are referred to as A-jarosite. The samples, their compositions, and the entropies at T = 298.15 K are:

The magnesiowüstite: iron equilibrium and its implications for the activity-composition relations of (Mg,Fe)<Subscript>2</Subscript>SiO<Subscript>4</Subscript> olivine solid solutions

The chemical potential of oxygen (µO₂) in equilibrium with magnesiowüstite solid solution (Mg, Fe)O and metallic Fe has been determined by gas-mixing experiments at 1,473 K supplemented by solid-cell EMF experiments at lower temperatures. The results give:

Fe–Mg diffusion in olivine II: point defect chemistry,change of diffusion mechanisms and a model for calculation of diffusion coefficients in natural olivine

Analysis of existing data and models on point defects in pure (Fe,Mg)-olivine (Phys Chem Miner 10:27–37,1983; Phys Chem Miner 29:680–694, 2002) shows that it is necessary to consider thermodynamic non-ideality of mixing to adequately describe the concentration of point defects over the range of measurement. In spite of different sources of uncertainties, the concentrations of vacancies in octahedral sites in (Fe,Mg)-olivine are on the order of 10⁻⁴ per atomic formula unit at 1,000–1,200 °C according to both the studies. We provide the first explicit plots of vacancy concentrations in olivine as a function of temperature and oxygen fugacity according to the two models. It is found that in contrast to absolute concentrations at ∼1,100 °C and dependence on fO₂, there is considerable uncertainty in our knowledge of temperature dependence of vacancy concentrations. This needs to be considered in discussing the transport properties such as diffusion coefficients. Moreover, these defect models in pure (Fe,Mg)-olivine need to be extended by considering aliovalent impurities such as Al, Cr to describe the behavior of natural olivine. We have developed such a formulation, and used it to analyze the considerable database of diffusion coefficients in olivine from Dohmen et al. (Phys Chem Miner this volume, 2007) (Part - I) and older data in the literature. The analysis documents unequivocally for the first time a change of diffusion mechanism in a silicate mineral—from the transition metal extrinsic (TaMED) to the purely extrinsic (PED) domain, at fO₂ below 10⁻¹⁰  Pa, and consequently, temperatures below 900 °C. The change of diffusion mechanism manifests itself in a change in fO₂ dependence of diffusivity and a slight change in activation energy of diffusion—the activation energy increases at lower temperatures. These are consistent with the predictions of Chakraborty (J Geophys Res 102(B6):12317–12331, 1997). Defect formation enthalpies in the TaMED regime (distinct from intrinsic defect formation) lie between −66 and + 15 kJ/mol and migration energies of octahedral cations in olivine are most likely ∼ 260 kJ/mol, consistent with previous inferences (Phys Chem 207:147–162, 1998). Plots are shown for diffusion at various constant fO₂ as well as along fO₂ buffers, to highlight the difference in behavior between the two. Considering all the diffusion data and constraints from the point defect models, (Fe–Mg) diffusion in olivine along [001] is best described by the Master equations: (1) At oxygen fugacities greater than 10⁻¹⁰ Pa:

An experimental study of Ca-(Fe,Mg) interdiffusion in silicate garnets

Ca-(Fe,Mg) interdiffusion experiments between natural single crystals of grossular (Ca_2.74Mg_0.15 Fe_0.23Al_1.76Cr_0.04Si_3.05O₁₂) and almandine (Ca_0.21Mg_0.40 Fe_2.23Mn_0.13Al_2.00Cr_0.08Si_2.99O₁₂ or Ca_0.43Mg_0.36Fe_2.11 Al_1.95Si_3.04O₁₂), were undertaken at 900–1100 °C and 30 kbar, and pressures of 15.0–32.5 kbar at 1000 °C. Samples were buffered by Fe/FeO in most cases. Diffusion profiles were determined by electron microprobe. Across the experimental couples the interdiffusion coefficients (D˜) were almost independent of composition. The diffusion rates in an unbuffered sample were significantly faster than in buffered samples. The temperature dependence of the D˜ (Ca-Fe,Mg) interdiffusion coefficients may be described by

Compositional dependence of REE partitioning between diopside and melt at 1 atmosphere

The effects of composition on pyroxene-melt partitioning of several REE (rare earth elements), Y, and Sr were experimentally evaluated. Using the synthetic model systems anorthite–diopside, diopside–titanite and anorthite–diopside–titanite different diopsides were grown at atmospheric conditions in a double-ellipsoid mirror furnace. The single samples were melted and crystallised in a Pt/Au crucible with compositions corresponding to the invariant points of these systems. Rotational motion with approximately 25 rpm around the longitudinal axis of the crucible increases the prevailing convection flows. By this means, the exclusively diffusional transport of assembly groups onto the growing crystals is avoided. Quenching is achieved by dropping the crucible into water. Crystals up to 2 mm were obtained and analysed by electron microprobe. No inhomogeneities or compositional zonation, either in the diopsides or in the coexisting melts, were observed within the analytical uncertainty of the electron microprobe. The crystallised diopsides occur as both euhedral single crystals and large symplectitic lamellar intergrowths with anorthite or titanite. The chemical homogeneity and the texture indicate near-equilibrium conditions. The analyses show strong positive correlations between D_REE and tetrahedrally coordinated Al in diopside but are not affected by octahedral Al or Ti-concentration. By means of correlations and mass balances the incorporation of REE can be described by 2 different coupled substitutions:

Influence of hydrogen on Fe–Mg interdiffusion in (Mg,Fe)O and implications for Earth’s lower mantle

Interdiffusion of Fe and Mg in (Mg,Fe)O has been investigated experimentally under hydrous conditions. Single crystals of MgO in contact with (Mg_0.73Fe_0.27)O were annealed hydrothermally at 300 MPa between 1,000 and 1,250°C and using a Ni–NiO buffer. After electron microprobe analyses, the dependence of the interdiffusivity on Fe concentration was determined using a Boltzmann–Matano analysis. For a water fugacity of ∼300 MPa, the Fe–Mg interdiffusion coefficient in Fe _x Mg_1−x O with 0.01 ≤ x ≤ 0.25 can be described by with and C = −80 ± 10 kJ mol⁻¹. For x = 0.1 and at 1,000°C, Fe–Mg interdiffusion is a factor of ∼4 faster under hydrous than under anhydrous conditions. This enhanced rate of interdiffusion is attributed to an increased concentration of metal vacancies resulting from the incorporation of hydrogen. Such water-induced enhancement of kinetics may have important implications for the rheological properties of the lower mantle.

Oxygen and carbon isotope geochemistry of the Krivoy rog iron formation,Ukranian SSR

Oxygen and carbon isotope analyses of samples from three mines in the Krivoy Rog iron formation, Ukranian SSR, are reported here. Maximum and minimum quartz-magnetite fractionation values ($\text{Δ}{}_{\mathrm{<mtext>QM</mtext>}}$) and inferred temperature range in degrees centrigrade for each mine are:

     

18.

On the miscibility gap in monazite–xenotime systems     

P. Mogilevsky 《Physics and Chemistry of Minerals》2007,34(3):201-214

The regular solid solution model has been applied to solid solubility in the monazite–xenotime systems and is verified against the available experimental data for LaPO₄–YPO₄ and CePO₄–YPO₄ systems. The model is then used to predict the miscibility gaps in a number of other monazite–xenotime systems. The implications for prospective two-phase monazite–xenotime fiber coatings for applications in ceramic matrix composites (CMCs) are discussed.

---

Mine	$\text{Δ}{}_{\mathrm{<mtext>QM</mtext>}}$	Corresponding temperature
Sevgok	9.4 to 14.2	475° to 320°C
Ugok	10.0 to 12.7	450° to 355°C
Annovsky	10.5 to 12.6	430° to 360°C

P. MogilevskyEmail:

     

On the miscibility gap in monazite–xenotime systems

The regular solid solution model has been applied to solid solubility in the monazite–xenotime systems and is verified against the available experimental data for LaPO₄–YPO₄ and CePO₄–YPO₄ systems. The model is then used to predict the miscibility gaps in a number of other monazite–xenotime systems. The implications for prospective two-phase monazite–xenotime fiber coatings for applications in ceramic matrix composites (CMCs) are discussed.

---

The chemical classification of iron meteorites—VII. A reinvestigation of irons with Ge concentrations between 25 and 80 ppm

We report Ni, Ga, Ge and Ir concentrations for 193 irons. The compositional trends in groups IIIA and IIIB are redefined, and the suggestion by Wasson and Kimberlin that they represent a single fractionation sequence (group IIIAB) is confirmed. A new group, HIE, is similar in its properties to group IIIA but distinguished by lower Ga/Ni and Ge/Ni ratios, larger bandwidths and the formation of haxonite (Fe, Ni)₂₃C₆ in each of its members. A sixth member, Hassi-Jekna, has been added to group IIIC, extending its Ge range up to 70 ppm. The characteristics of these groups can be summarized as follows:

     

20.

Pallasites—metal composition,classification and relationships with iron meteorites     

Edward R.D Scott 《Geochimica et cosmochimica acta》1977,41(3):349-360

Concentrations of Au, As, Co, Ga, Ge, Ir, Ni and W were determined in the metal of 28 different pallasites plus 6 which are probably paired, to help elucidate their origin. Most divide into two clusters:

Group	Structure	Ni%	Ga(ppm)	Ge(ppm)	Ir(ppm)
IIIA	Om	7.1–9.3	7–23	32–47	0.17–19
IIIB	Om	8.4–10.5	16–21	27–46	0.014–0.17
IIIC	Off-Of	10.5–13.0	11–27	8.6–70	0.08–0.6
IIIE	Og	8.2–8.9	17–19	34–37	0.05–0.6 The Ge-Ni correlation is positive in IIIA, negative in IIIB and IIIC, and there is no significant correlation in IIIE. San Cristobal is identified as a member of group IAB, thereby extending the Ge and Ni range of this group to 25 ppm and 25 per cent, respectively. Previous reports of wide cooling-rate variations in group IIIAB are not substantiated, and current evidence favors a core over a raisin-bread model for this group. There appears to be no genetic relationship between group IIIAB and either the pallasites or the mesosiderites

     

	No.	Ni (%)	Ga (μg/g)	Ge (μg/g)	Au (μg/g)	Fa (mole %)
Main group	19	7.8–11.7	16–26	29–65	1.7–3.0	11–13
Eagle Station trio	3	14–16	4.5–6	75–120	0.8–1.0	19–20

Pallasites—metal composition,classification and relationships with iron meteorites

Concentrations of Au, As, Co, Ga, Ge, Ir, Ni and W were determined in the metal of 28 different pallasites plus 6 which are probably paired, to help elucidate their origin. Most divide into two clusters: