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.     

A comparative method for various approaches to the isothermal equation of state

Various three-parameter approximations of the isothermal equation of state of matter can be systematized and, in consequence, mutually compared by using the uniquely associated relationships between first and second pressure derivatives of the bulk modulus of any substance at zero pressure. Thus quantitative or, at least qualitative information on the capability of such approximations for volumetric contractions down to about 0.5 can be obtained directly. This comparative method will be discussed with the aid of 19 approximations considered in high-pressure physics and geophysics. Its application to the Grüneisen parameter analysis yields a number of additional practical approximations.     

Geological models of gas in place of the Longmaxi shale in Southeast Chongqing,South China

Gas-in-place (GIP) is one of the primary controlling factors in shale gas production, but studies examining GIP have been lacking for the Lower Silurian Longmaxi shale in South China. In the present study, a suite of Longmaxi shale samples was collected from an exploratory well in Southeast Chongqing, South China, and the adsorption parameters were fitted using a supercritical Dubinin-Radushkevich (SDR) model based on the high-pressure methane adsorption experiment data for the samples. The results show that the adsorbed phase density and the adsorbed gas capacity of the samples have a positive correlation with the content of total organic carbon (TOC) but a negative correlation with temperature. Combined with the geological characteristics of the Longmaxi shale in Southeast Chongqing, GIP models were constructed under three different fluid pressure conditions. The absolute adsorbed amount of the samples increases and later decreases with increasing depth with a maximum corresponding to depths between 800 and 1200 m. The fluid pressure coefficient has no obvious effect on the absolute adsorbed amount when burial depth is over 2000 m but controls the free gas content. Overpressure primarily increases the free gas content and thus increases the total gas content. The free gas content of the Longmaxi shale in the Pengshui Block is reduced to 47%–58% of that in the Fuling Block, which is the main reason for its low gas production. Further exploration of the Longmaxi Formation should be expanded to deeper burial shales in the eastern area of Southeast Chongqing.     

Paleoproterozoic migmatitic gneisses from the Tandilia belt (Argentina), Río de la Plata craton,record cooling at deep crustal levels

We studied high-grade metamorphic rocks of the El Cristo hill area of the Tandilia belt. Mineral analyses and thermodynamic calculations were carried out for two adjacent rock samples: an amphibole–biotite gneiss and a garnet–biotite-bearing migmatite. Peritectic garnets in the migmatite show core compositions of pyr_4.5(gro + andr)₁₀spes₆alm_79.5 changing to pyr_3.5(gro + andr)₁₇spes₆alm_73.5 at their thin rims. Garnet compositions in the gneiss are pyr_6.5(gro + andr)₂₆spes₁₂alm_55.5 and pyr_4.5(gro + andr)₃₄spes₁₂alm_49.5 for core and rim, respectively. A P–T path was constructed by calculating pseudosections in the 11-component system Si–Ti–Al–Fe–Mn–Mg–Ca–Na–K–O–H and contouring them by isopleths for garnet components using the PERPLE_X software package. Supra-solidus crystallization of garnet cores in the migmatite began at 5.8 kbar and 660 °C. Garnet rims equilibrated at 7.0 kbar and 640 °C compatible with garnet cores in the amphibole–biotite gneiss (7.6 kbar and 660 °C). The further chemical development of garnet in this rock points to P–T conditions of 11.6 kbar and 620 °C and 12.2 kbar and 595 °C (outermost garnet rim). At this high-pressure stage Ca-amphibole was not stable. Most biotite formed during exhumation whereas the high-pressure accessory minerals, titanite and epidote, persisted. According to the obtained anti-clockwise P–T path the originally partly melted material was tectonically transported from ∼22 km (middle crust) to ∼40 km (lower crust) depths reaching a geothermal gradient as low as 15 °C km⁻¹. This transport probably occurred along a major suture zone, which was active during the Paleoproterozoic (2.25–2.10 Ga), before a terminating collision of terranes near the SW boundary of the Rio de la Plata craton.     

Lattice preferred orientation in CaIrO<Subscript>3</Subscript> perovskite and post-perovskite formed by plastic deformation under pressure

Lattice preferred orientations (LPO) developed in perovskite and post-perovskite structured CaIrO₃ were studied using the radial X-ray diffraction technique combined with a diamond anvil cell. Starting materials of each phase were deformed from 0.1 MPa to 6 GPa at room temperature. Only weak LPO was formed in the perovskite phase, whereas strong LPO was formed in the post-perovskite phase with an alignment of the (010) plane perpendicular to the compression axis. The present result suggests that the (010) is a dominant slip plane in the post-perovskite phase and it is in good agreement with the crystallographic prediction, dislocation observations via transmission electron microscopy, and a recent result of simple shear deformation experiment at 1 GPa–1,173 K. However, the present result contrasts markedly from the results on MgGeO₃ and (Mg,Fe)SiO₃, which suggested that the (100) or (110) is a dominant slip plane with respect to the post-perovskite structure. Therefore it is difficult to discuss the behavior of the post-perovskite phase in the Earth’s deep interior based on existing data of MgGeO₃, (Mg,Fe)SiO₃ and CaIrO₃. The possible sources of the differences between MgGeO₃, (Mg,Fe)SiO₃ and CaIrO₃ are discussed.     

Aluminum substitution mechanisms in perovskite-type MgSiO<Subscript>3</Subscript>: an investigation by Rietveld analysis

Al-containing MgSiO₃ perovskites of four different compositions were synthesized at 27 GPa and 1,873 K using a Kawai-type high-pressure apparatus: stoichiometric compositions of Mg_0.975Si_0.975Al_0.05O₃ and Mg_0.95Si_0.95Al_0.10O₃ considering only coupled substitution Mg²⁺ + Si⁴⁺ = 2Al³⁺, and nonstoichiometric compositions of Mg_0.99Si_0.96Al_0.05O_2.985 and Mg_0.97Si_0.93Al_0.10O_2.98 taking account of not only the coupled substitution but also oxygen vacancy substitution 2Si⁴⁺ = 2Al³⁺ + V_O¨. Using the X-ray diffraction profiles, Rietveld analyses were performed, and the results were compared between the stoichiometric and nonstoichiometric perovskites. Lattice parameter–composition relations, in space group Pbnm, were obtained as follows. The a parameters of both of the stoichiometric and nonstoichiometric perovskites are almost constant in the X _Al range of 0–0.05, where X _Al is Al number on the basis of total cation of two (X _Al = 2Al/(Mg + Si + Al)), and decrease with further increasing X _Al. The b and c parameters of the stoichiometric perovskites increase linearly with increasing Al content. The change in the b parameter of the nonstoichiometric perovskites with Al content is the same as that of the stoichiometric perovskites within the uncertainties. The c parameter of the nonstoichiometric perovskites is slightly smaller than that of the stoichiometric perovskites at X _Al of 0.10, though they are the same as each other at X _Al of 0.05. The Si(Al)–O1 distance, Si(Al)–O1–Si(Al) angle and minimum Mg(Al)–O distance of the nonstoichiometric perovskites keep almost constant up to X _Al of 0.05, and then the Si(Al)–O1 increases and both of the Si(Al)–O1–Si(Al) angle and minimum Mg(Al)–O decrease with further Al substitution. These results suggest that the oxygen vacancy substitution may be superior to the coupled substitution up to X _Al of about 0.05 and that more Al could be substituted only by the coupled substitution at 27 GPa. The Si(Al)–O1 distance and one of two independent Si(Al)–O2 distances in Si(Al)O₆ octahedra in the nonstoichiometric perovskites are always shorter than those in the stoichiometric perovskite at the same Al content. These results imply that oxygen defects may exist in the nonstoichiometric perovskites and distribute randomly.     

Elastic behaviour and structural evolution of topaz at high pressure

The elastic behaviour and the high-pressure structural evolution of a natural topaz, Al_2.00Si_1.05O_4.00(OH_0.26F_1.75), have been investigated by means of in situ single-crystal X-ray diffraction up to 10.55(5) GPa. No phase transition has been observed within the pressure range investigated. Unit-cell volume data were fitted with a third-order Birch-Murnaghan Equation of State (III-BM-EoS). The III-BM-EoS parameters, simultaneously refined using the data weighted by the uncertainties in P and V, are: V ₀=345.57(7) ų, K _T0=164(2) GPa and K′=2.9(4). The axial-EoS parameters are: a ₀=4.6634(3) Å, K _T0(a)=152(2) GPa, K′(a)=2.8(4) for the a-axis; b ₀=8.8349(5) Å, K _T0(b)=224(3) GPa, K′(b)=2.6(6) for the b-axis; c ₀=8.3875(7) Å, K _T0(c)=137(2) GPa, K′(c)=2.9(4) for the c-axis. The magnitude and the orientation of the principal Lagrangian unit-strain ellipsoid were determined. At P−P ₀=10.55 GPa, the ratios ε₁:ε₂:ε₃ are 1.00:1.42:1.56 (with ε₁||b, ε₂||a, ε₃||c and |ε₃| > |ε₂| > |ε₁|). Four structural refinements, performed at 0.0001, 3.14(5), 5.79(5) and 8.39(5) GPa describe the structural evolution in terms of polyhedral distortions.     

Geochronological constraints on the evolution of high-pressure felsic granulites from an integrated electron microprobe and ID-TIMS geochemical study

A combined geochronological, geochemical, and Nd isotopic study of felsic high-pressure granulites from the Snowbird Tectonic Zone, northern Saskatchewan, Canada, has been carried out through the application of integrated electron microprobe and isotope dilution thermal ionization mass spectrometry (ID-TIMS) techniques. The terrane investigated is a 400 km² domain of garnet–kyanite–K–feldspar-bearing quartzofeldspathic gneisses. Monazite in these granulites preserves a complex growth history from 2.6 to 1.9 Ga, with well-armored, high Y and Th grains included in garnet yielding the oldest U–Pb dates at 2.62 to 2.59 Ga. In contrast, matrix grains and inclusions in garnet rims that are not well-armored are depleted in Y and Th, and display more complicated U–Pb systematics with multiple age domains ranging from 2.5 to 2.0 Ga. 1.9 Ga monazite occurs exclusively as matrix grains. Zircon is typically younger (2.58 to 2.55 Ga) than the oldest monazite. Sm–Nd isotope analysis of single monazite grains and whole rock samples indicate that inclusions of Archean monazite in garnet are similar in isotopic composition to the whole rock signature with a limited range of slightly negative initial _Nd. In contrast, grains that contain a Paleoproterozoic component show more positive initial _Nd, most simply interpreted as reflecting derivation from a source involving consumption of garnet and general depletion of HREE's. Our preferred interpretation is that the oldest monazite dates record igneous crystallization of the protolith. The ca. 2.55 Ga dates in zircon and monazite record an extensive melting event during which garnet and ternary feldspar formed. Very high-pressure (> 1.5 GPa) metamorphism during the Paleoproterozoic at 1.9 Ga produced kyanite from garnet breakdown, and resulted in limited growth of new monazite and zircon. In the case of monazite, this is likely due to the armoring and sequestration of early-formed monazite such that it could not participate in metamorphic reactions during the high-pressure event, as well as the depletion of the REE's due to melt loss following the early melting event.     

The enthalpy of transformation of Ca(OH)2-I (portlandite) to Ca(OH)2-II (EuI2 structure) by low-temperature DSC

 Thermodynamic properties of high-pressure minerals that are not recoverable from synthesis experiments by conventional quenching methods (“unquenchable” phases) usually are calculated from equation of state data and phase diagram topologies. The present study shows that, with cryogenic methods of recovery and sample treatment, phases with a suitable decomposition rate can be made accessible to direct thermodynamic measurements. A set of samples of Ca(OH)₂-II has been synthesized in a multianvil device and subsequently recovered by cooling the high-pressure assembly with liquid nitrogen. Upon heating from liquid nitrogen to room temperature, the material transformed back to Ca(OH)₂-I. The heat effect of this backtransformation was measured by differential scanning calorimetry. A commercial differential scanning calorimeter (Netzsch DSC 404), modified to allow sample loading at liquid nitrogen temperature was used to heat the material from −150 to +200 °C at rates varying between 5 and 15 °C min⁻¹. The transformation started around −50 °C very gradually, and peaked at about 0 °C. To obtain a baseline correction, each sample was scanned under exactly the same conditions after the backtransformation was complete. Because of the relative sluggishness, onset and offset temperatures were not well defined as compared to fast (e.g., melting) reactions. To aid in integration, the resulting signals were successfully fitted using a generic asymmetric peak model. The enthalpy of backtransformation was determined to be ΔH =−10.37 ± 0.50 kJ mol⁻¹. From previous in situ X-ray diffraction experiments, the location of the direct transformation in P-T space has been constrained to 5.7 ± 0.4 GPa at 500 °C (Kunz et al. 1996). With the reaction volume known from the same study, and assuming that ΔC _p of the transformation remains negligible between the conditions of our measurements and 500 °C, our result gives an estimate of the entropy of transition and the P-T slope of the reaction curve. To a first approximation, the values ΔS = −16.00 ± 0.65 J(mol · K)⁻¹ and dP/dT = 0.0040 ± 0.0002 GPa/K have been determined. These results need to be refined by equation of state data for Ca(OH)₂-II. Received: 30 December 1999 / Accepted: 10 April 2000     

天水地震区深源岩石在1000MPa高压下的状态参数特征

本文重点介绍了天水地震区产出的深源岩石在１０００ＭＰａ高压下，测得的岩石的密度、纵横波速度和计算的波阻抗随压力的变化。发现不同时期产出的不同种类的深源岩石，它们的高压状态参数值变化范围很窄。压力上升到４００ＭＰａ以后，岩石的密度、纵横波速度的变化很小，几乎观测不到其变化。本文简单地讨论了岩石在４００ＭＰａ以上高压状态下，上述参数值变化不大的原因，并对４００ＭＰａ压力下取得的高压状态参数值做了实用误差分析，结果表明：在不考虑温度情况下，该压力下获得的状态参数值在实际应用中完全可以代替更高压力状态下（４００ＭＰａ－２０００ＭＰａ）的测量值。因此４００ＭＰａ特征压力下取得的岩石状态参数值对人工地震测深解释和重力解释仍是有参考意义的。