Oxygen isotope fractionations involving pyroxenes: The calibration of mineral-pair geothermometers

Oxygen isotope fractionations between wollastonite, diopside, jadeite, hedenbergite and water have been experimentally studied at high pressures (1<- PH₂O ≥ 24 kbar) and temperatures (400/dg ≤ T <- 800/dgC) using the three-isotope method (Matsuhisa et al., 1978). Initial ${}^{18}\text{O}{}^{16}\text{O}$ fractionations were made close to equilibrium and initial ${}^{17}\text{O}{}^{16}\text{O}$ ratios were well removed from equilibrium, allowing accurate determinations of the equilibrium ${}^{18}\text{O}{}^{16}\text{O}$ fractionations and of the extent of isotopic exchange. Scanning electron microscope and rate studies show that the wollastonite-water and diopside-water exchange reactions occur largely by solution-precipitation (Ostwald Ripening) mechanisms. Equilibrium ${}^{18}\text{O}{}^{16}\text{O}$ fractionations between water and the minerals wollastonite, diopside, and hedenbergite are in close agreement with one another, whereas significantly more positive fractionations are found for jadeite-water. These isotopic substitution effects can be ascribed to replacement of SiOM bonds (M is a divalent metal cation in octahedral coordination) by higher frequency SiOAl bonds. The fractionations determined in this study can be combined with quartz- and feldspar-water data of Matsuhisa et al. (1979) and revised magnetite-water data of O'NEIL (1963), to provide a coherent set of mineral-pair fractionations satisfactorily represented by straight lines through the origin on a conventional graph of In /ga versus T^?2. Mineral-water data, on the other hand, cannot readily be fitted to the simple relationship suggested by Bottinga and Javoy (1973). Coefficients “A” for the mineral-pair fractionations 1000 ln α = A × 10⁶T^?2 are:

     

2.

高温高压岩石流变仪的围压标定方法     

党嘉祥  周永胜  何昌荣  闫小兵 《地学前缘》2008,15(3):287-291

高温高压岩石流变仪围压标定的主要方法为氯化盐类的部分熔融法和矿物相变法。利用氯化盐类进行压力标定时,不仅可以利用单一盐类,也可以使用多种盐类的混合物;常用的压力标定矿物相变及其适用温压范围如下:石英-柯石英,500~1200℃、2.5~3.2GPa;钠长石-硬玉+石英,600~1200℃、1.6~3.2GPa;铁橄榄石+石英-铁辉石,600~1200℃、1~1.7GPa;磷镁石-Mg3(PO4)2-Ⅱ,565~825℃、0.6~0.9GPa;方解石-文石,600~1200℃、0.5~2.5GPa。不同的标定方法具有不同的特征,文中将进行详细介绍。     

3.

Sulphur isotope effects in the high temperature oxidation of troilite     

C.E McEwing  C.E Rees  H.G Thode 《Geochimica et cosmochimica acta》1983,47(11):2059-2061

Troilite oxidation in air at 1200°C gives sulphur dioxide which is slightly enriched (~0.3%.) in ³⁴S. No systematic variations were seen of the isotopic compositions of product sulphur dioxide or residual troilite with extent of conversion. We speculate that the oxidation reaction takes place at the surface of the molten troilite in such a way as to inhibit mixing between the reacting outer layers and the unreacted liquid substrate so that Rayleigh behaviour with extent of reaction is not observed.     

4.

Empirical calibration of oxygen isotope fractionation in zircon   总被引：2，自引：0，他引：2  

John W. Valley  Ilya N. Bindeman 《Geochimica et cosmochimica acta》2003,67(17):3257-3266

New empirical calibrations for the fractionation of oxygen isotopes among zircon, almandine-rich garnet, titanite, and quartz are combined with experimental values for quartz-grossular. The resulting A-coefficients (‰K²) are:

	Ab	Jd	An	Di	Wo	Mt
Q	0.50	1.09	1.59	2.08	2.20	6.11
Ab		0.59	1.09	1.58	1.70	5.61
Jd			0.50	0.99	1.11	5.02
An				0.49	0.61	4.52
Di					0.12	4.03
Wo						3.91

	Zrc	Alm	Grs	Ttn
Qtz	2.64	2.71	3.03	3.66
Zrc		0.07	0.39	1.02
Alm			0.32	0.95
Grs				0.63

Full-size table

     

高温高压岩石流变仪的围压标定方法

高温高压岩石流变仪围压标定的主要方法为氯化盐类的部分熔融法和矿物相变法。利用氯化盐类进行压力标定时,不仅可以利用单一盐类,也可以使用多种盐类的混合物;常用的压力标定矿物相变及其适用温压范围如下:石英-柯石英,500~1200℃、2.5~3.2GPa;钠长石-硬玉+石英,600~1200℃、1.6~3.2GPa;铁橄榄石+石英-铁辉石,600~1200℃、1~1.7GPa;磷镁石-Mg3(PO4)2-Ⅱ,565~825℃、0.6~0.9GPa;方解石-文石,600~1200℃、0.5~2.5GPa。不同的标定方法具有不同的特征,文中将进行详细介绍。     

Sulphur isotope effects in the high temperature oxidation of troilite

Troilite oxidation in air at 1200°C gives sulphur dioxide which is slightly enriched (~0.3%.) in ³⁴S. No systematic variations were seen of the isotopic compositions of product sulphur dioxide or residual troilite with extent of conversion. We speculate that the oxidation reaction takes place at the surface of the molten troilite in such a way as to inhibit mixing between the reacting outer layers and the unreacted liquid substrate so that Rayleigh behaviour with extent of reaction is not observed.     

Empirical calibration of oxygen isotope fractionation in zircon

New empirical calibrations for the fractionation of oxygen isotopes among zircon, almandine-rich garnet, titanite, and quartz are combined with experimental values for quartz-grossular. The resulting A-coefficients (‰K²) are:

Viscosity of albite melt at high pressure and high temperature

 The viscosity of albite (NaAlSi₃O₈) melt was measured at high pressure by the in situ falling-sphere method using a high-resolution X-ray CCD camera and a large-volume multianvil apparatus installed at SPring-8. This system enabled us to conduct in situ viscosity measurements more accurately than that using the conventional technique at pressures of up to several gigapascals and viscosity in the order of 10⁰ Pa s. The viscosity of albite melt is 5.8 Pa s at 2.6 GPa and 2.2 Pa s at 5.3 GPa and 1973 K. Experiments at 1873 and 1973 K show that the decrease in viscosity continues to 5.3 GPa. The activation energy for viscosity is estimated to be 316(8) kJ mol⁻¹ at 3.3 GPa. Molecular dynamics simulations suggest that a gradual decrease in viscosity of albite melt at high pressure may be explained by structural changes such as an increase in the coordination number of aluminum in the melt. Received: 6 January 2001 / Accepted: 27 August 2001     

Electrical conductivity of K-feldspar at high temperature and high pressure

Electrical conductivity measurements on dry polycrystalline K-feldspar were performed at 1.0 to 3.0 GPa and 873 to 1,173 K with a multi-anvil high-pressure apparatus and the Solartron-1260 Impedance/Gain Phase Analyzer in the frequency range of 10^?1 to 10⁶ Hz. At each temperature the complex impedance displays a perfect semi-circular arc that represents the grain-interior conduction. Under the experimental conditions, electrical conductivity exponentially increases with increasing temperature and slightly decreases with increasing pressure; however, the effect of pressure on the conductivity is less pronounced than that of temperature. The activation enthalpy decreases slightly from 0.99 to 1.02 eV with increasing pressure, and the activation energy and activation volume for K-feldspar are 0.98 eV and 1.46?±?0.17 cm³/mol, respectively. According to these Arrhenius parameters, ionic conduction is proposed to be the dominant conduction mechanism in K-feldspar at high temperatures and pressures, and potassium ions are the charge carriers transporting by an interstitial mechanism. The diffusion coefficient of potassium at high temperatures was calculated from our conductivity data on K-feldspar using Nernst–Einstein equation, and the results were compared with the previous experimental results.     

Experimental calibration of oxygen isotope fractionation between quartz and zircon

We report the results of an experimental calibration of oxygen isotope fractionation between quartz and zircon. Data were collected from 700 to 1000 °C, 10–20 kbar, and in some experiments the oxygen fugacity was buffered at the fayalite–magnetite–quartz equilibrium. Oxygen isotope fractionation shows no clear dependence on oxygen fugacity or pressure. Unexpectedly, some high-temperature data (900–1000 °C) show evidence for disequilibrium oxygen isotope partitioning. This is based in part on ion microprobe data from these samples that indicate some high-temperature quartz grains may be isotopically zoned. Excluding data that probably represent non-equilibrium conditions, our preferred calibration for oxygen isotope fractionation between quartz and zircon can be described by:

This relationship can be used to calculate fractionation factors between zircon and other minerals. In addition, results have been used to calculate WR/melt–zircon fractionations during magma differentiation. Modeling demonstrates that silicic magmas show relatively small changes in δ¹⁸O values during differentiation, though late-stage mafic residuals capable of zircon saturation contain elevated δ¹⁸O values. However, residuals also have larger predicted melt–zircon fractionations meaning zircons will not record enriched δ¹⁸O values generally attributed to a granitic protolith. These results agree with data from natural samples if the zircon fractionation factor presented here or from natural studies is applied.     

X-ray diffraction study of magnesite at high pressure and high temperature

 P–V–T measurements on magnesite MgCO₃ have been carried out at high pressure and high temperature up to 8.6 GPa and 1285 K, using a DIA-type, cubic-anvil apparatus (SAM-85) in conjunction with in situ synchrotron X-ray powder diffraction. Precise volumes are obtained by the use of data collected above 873 K on heating and in the entire cooling cycle to minimize non-hydrostatic stress. From these data, the equation-of-state parameters are derived from various approaches based on the Birch-Murnaghan equation of state and on the relevant thermodynamic relations. With K′₀ fixed at 4, we obtain K₀=103(1) GPa, α(K⁻¹)=3.15(17)×10⁻⁵ +2.32(28)×10⁻⁸ T, (∂K_T/∂T)_P=−0.021(2) GPaK⁻¹, (dα/∂P)_T=−1.81×10⁻⁶ GPa⁻¹K⁻¹ and (∂K_T/∂T)_V= −0.007(1) GPaK⁻¹; whereas the third-order Birch-Murnaghan equation of state with K′₀ as an adjustable parameter yields the following values: K₀=108(3) GPa, K′₀=2.33(94), α(K⁻¹)=3.08(16)×10⁻⁵+2.05(27) ×10⁻⁸ T, (∂K_T/∂T)_P=−0.017(1) GPaK⁻¹, (dα/∂P)_T= −1.41×10⁻⁶ GPa⁻¹K⁻¹ and (∂K_T/∂T)_V=−0.008(1) GPaK⁻¹. Within the investigated P–T range, thermal pressure for magnesite increases linearly with temperature and is pressure (or volume) dependent. The present measurements of room-temperature bulk modulus, of its pressure derivative, and of the extrapolated zero-pressure volumes at high temperatures, are in agreement with previous single-crystal study and ultrasonic measurements, whereas (∂K_T/∂T)_P, (∂α/∂P)_T and (∂K_T/∂T)_V are determined for the first time in this compound. Using this new equation of state, thermodynamic calculations for the reactions (1) magnesite=periclase+CO₂ and (2) magnesite+enstatite=forsterite+CO₂ are consistent with existing experimental phase equilibrium data. Received September 28, 1995/Revised, accepted May 22, 1996     

The Electrical Conductivity of Gabbro at High Temperature and High Pressure

The electric conductivity of gabbro has been measured at 1.0 - 2.0 GPa and 320-700℃, and the conduction mechanism has been analyzed in terms of the impedance spectra.Experimental results indicated that the electric conductivity depends on the frequency of alternative current. Impedance arcs representing the conduction mechanism of grain interiors are displayed in the complex impedance plane, and the mechanism is dominated at high pressure.These arcs occur over the range of 102 - k× 105 Hz (k is the positive integer from 1 to 9). On the basis of our results and previous work, it is concluded that gabbro cannot form any high conductivity layer (HCL) in the middle-lower crust.     

Friction in faulted rock at high temperature and pressure

Two hundred observations of frictional behavior of seven low-porosity silicate rocks were made at temperatures to 700°C and pressures from 2.5 to 6 kbar. For all rocks except one, peridotite, stick-slip occurred at low temperature and gave way to stable sliding at some high temperature, different for each rock. These differences could be related to the presence or absence of minerals such as amphibole, mica, or serpentine. Up to some temperature, depending on rock type, the friction stress was relatively unaffected by temperature. The shear stress decreased at higher temperature, and in some cases such decrease was related to the coincidence of fracture and friction strength. While somewhat dependent on rock type, the friction stress for the seven rocks studied was about the same, within 10–15%. Up to 265°C, water had little effect on the frictional behavior of faulted granite at 3 kbar effective pressure. The frictional stresses measured in the laboratory were significantly higher than estimated for natural faults. This difference could be accounted for by high pore pressure or weak alteration materials in the natural fault zone.     

Thermodynamic properties of San Carlos olivine at high temperature and high pressure

In this study, the thermal expansion and heat capacity of San Carlos olivine under high temperature and high pressure are reported. Combining accurate sound velocity data under different P–T conditions with density and heat capacity data at ambient pressure, the density, adiabatic bulk modulus, shear modulus, and most importantly, thermal expansion and heat capacity, of San Carlos are extracted to 14 GPa by a numerical procedure using classic thermodynamic relationships. These data are in agreement with published findings. To estimate the temperature gradient in the upper mantle, we also report the fitting equations of thermal expansion and heat capacity of San Carlos olivine as a function of both temperature and pressure to the P–T condition of the 410 km discontinuity, which provide the thermodynamic properties with increasing depth in the Earth’s interior.     

高温高压和控制氧逸度条件下透辉石电导率的各向异性实验研究

在1.0～4.0GPa 和1073～1373K 及控制氧分压条件下,借助于 YJ-3000t 紧装式六面顶固体高压设备和1260阻抗/增益-相位分析仪,就位测定了沿着不同晶轴方向的透辉石的电导率。氧逸度控制是由 Ni+NiO 固体缓冲剂完成的。实验结果表明:(1)在选择的频率范围,无论从复阻抗的模与频率还是从相角与频率关系上,部可以看出复阻抗对频率具有很强的依赖性;(2)随着温度升高,阻抗降低,电导率增大,Logo 与1/T 之间符合 Arrenhius 线性关系式;(3)随着压力升高,[001]方向的透辉石电导率降低,活化焓和指前因子亦随之减小,并首次获得了透辉石中主要载流子的活化能和活化体积分别为1.80±0.04eV 和0.035±0.015cm~3/mol;(4)在2.0GPa 下按照[001]、[100]、[010]的顺序,样品的电导率和指前因子降低,活化焓依次升高,高压下的透辉石电学性质存在各向异性;(5)小极化子导电机制可为透辉石在高温高压下的导电行为提供合理的解释。     

高温高压下石膏脱水相变的原位拉曼光谱研究

本文运用激光拉曼光谱仪,利用水热金刚石压腔装置对高温高压条件下石膏-水体系中的石膏脱水相变进行拉曼光谱研究.在压力0.1 MPa～837.9 MPa和温度16～200 ℃条件下通过系列实验对相变的过程进行了原位光谱分析.与人们已知的无水条件下石膏分两步脱水的过程不同,高压下石膏在饱和水环境下倾向于一次性的脱去所有结晶水而形成无水石膏,实验中没有观察到半水石膏的出现.通过实验数据得到石膏和无水石膏的转折温度和平衡压力间的关系式为P(MPa)=19.56·T(℃)-2926.5.     

大别山东南部高压—超高压变质岩的氢氧同位素地球化学

本文报道了大别山东南部安徽石马地区柯石英榴辉岩组合和黄镇地区石英榴辉岩组合的全岩及单矿物的氢氧同位素特征。石马榴辉岩的δ18O值在1.0‰～7.4‰之间,云母δD值为-76‰～-61‰;黄镇榴辉岩的全岩δ18O值为-1.1‰～-2.1‰,云母δD值为-89‰～-77‰。矿物之间的氢氧同位素分馏既有处于平衡状态者,也有处于不平衡状态者,反映这些岩石除继承变质前母体的18O亏损特征外,还经历了显著的同位素退化交换作用。石马和黄镇榴辉岩的矿物对氧同位素温度均给出两个峰值380～430℃与绿片岩相变质条件一致,600～640℃与高角闪岩相变质条件一致;给不出峰变质温度(750～800℃)是由于岩石经历了退变质流体的强烈改造作用。大别东南部高压-超高压榴辉岩的南部边界为石英榴辉岩与花岗片麻岩的界线,但氧同位素研究指示两者为原位接触关系。     

矿物氧同位素模式温度计算

根据对现遥氧扩散模型的解析分析,通过模拟矿物之间的氧同位素交换轨迹进行模式温度计算,改进了常规矿物对氧同位素地质温度计方法。将模式温度计算与矿物氧－扩散封闭次上结合,建立了一个系统独立的同位素温度计算方法,因此所得到的同位素温度能够更好地反映矿物在高温岩石冷却过程中,的氧同位素交换行为;模式温度计算有如下优点：（１）考虑到了矿物之间扩散引起的同位素交换;（２）遵循质量守恒原理,更严格地适用于有限封     

Reaction of forsterite with hydrogen molecules at high pressure and temperature

High pressure and temperature reactions of a mixture of forsterite and hydrogen molecules have been carried out using a laser heated diamond anvil cell at 9.8–13.2 GPa and ~1,000 K. In situ X-ray diffraction measurements showed no sign of decomposition or phase transitions of the forsterite under these experimental conditions, indicating that the olivine structure was maintained throughout all runs. However, a substantial expansion of the unit cell volume of the forsterite was observed for samples down to ~3 GPa upon quenching to ambient pressure at room temperature. The Raman spectroscopy measurements under pressure showed significant shifts of the Raman peaks of the Si–O vibration modes for forsterite and of the intramolecular vibration mode for H₂ molecules toward a lower frequency after heating. Additionally, no OH vibration modes were observed by Raman and FT-IR spectroscopic measurements. These lines of evidence show that the observed volume expansion in forsterite is not explained by the incorporation of hydrogen atoms as hydroxyl, but suggest the presence of hydrogen as molecules in the forsterite structure under these high pressure and temperature conditions.     

Oxygen and hydrogen isotope geochemistry of gneisses associated with ultrahigh pressure eclogites at Shuanghe in the Dabie Mountains

The oxygen and hydrogen isotope compositions of minerals and whole rock were determined for two types of gneiss (biotite gneiss and granitic gneiss) associated with ultrahigh pressure (UHP) eclogites in the Shuanghe district of the eastern Dabie Mountains. There are significant differences in δ¹⁸O between the two gneisses: the UHP biotite gneiss varying from −4.3‰ to 10.6‰ similar to the associated eclogites, whereas the non-UHP granitic gneiss ranges only from −3.8‰ to 1.2‰. The δD values are similar in the two gneisses with −37 to −64‰ for epidote/zoisite, −92 to −83‰ for amphibole, and −63 to −109‰ for biotite/phengite. Hydrogen isotope disequilibrium among the coexisting hydroxyl-bearing minerals is ascribed to retrograde exchange subsequent to amphibolite-facies metamorphism. Oxygen isotopic equilibrium has been preserved among various minerals in both gneisses regardless of the large variation in rock δ¹⁸O. Oxygen isotopic geothermometers yield different but regular temperatures corresponding to the closure temperatures of oxygen diffusion in the minerals. The metamorphic temperatures of both eclogite facies and amphibolite facies have been recovered in mineral pairs from the biotite gneiss. The isotopic temperatures for the granitic gneiss are mostly in accordance with amphibolite-facies metamorphism. However, high temperatures of 550 to 650 °C are obtained from those minerals resistant to retrograde oxygen isotope exchange, implying that the granitic gneiss may have experienced higher temperature metamorphism than expected from petrologic thermometers. The ¹⁸O-depletion of both gneisses is interpreted to result from meteoric-hydrothermal exchange before/during plate subduction. Therefore, the measured δ¹⁸O values of the gneisses reflect the oxygen isotope compositions of their protoliths prior to the UHP metamorphism. It is inferred that the UHP unit is in foreign contact with the non-UHP unit like a tectonic melange, but both of them experienced the two common stages of geodynamic evolution: (1) ¹⁸O-depletion prior to the UHP metamorphism, (2) uplifting since the amphibolite-facies metamorphism. Received: 5 May 1998 / Accepted: 27 August 1998     

Carrara大理岩高温高压变形实验研究

利用高精度的Paterson高温高压流变仪对Carrara大理岩在高温(873~1173K)高压(~300MPa)以及约10-6~10-3s-1应变速率下进行了三轴压缩变形实验。结果表明,在等应变速率条件下,其强度随着温度的升高而降低;在等温和等压条件下,其强度随着应变速率的增加先快速增加而后缓慢增加。在应变速率对差应力的双对数投图中,我们发现随着温度的升高拟合直线的斜率减小,并且在873K和高应变速率时973K温度下Carrara大理岩的流变本构方程服从指数律变化关系;而在高温(1073K和1173K)和973K低应变速率条件下Carrara大理岩的应力指数n为5.3~7.7,且服从幂次律变化关系。因此,Carrara大理岩在本研究的实验条件下主要有两种变形机制,一种是用指数律表示的高应力变形机制;另一种是用幂次律表示的中等应力变形机制。     

Quasi-harmonic computer simulations of the structural behaviour and EOS of pyrope at high pressure and high temperature

Numerical simulations, using empirical interatomic potentials within the framework of lattice dynamics and quasi-harmonic approximation, have been carried out to model the behaviour of the structure and of some thermoelastic properties of pyrope at high pressure and high temperature conditions (0–50 GPa, 300–1500 K). Comparison with observed data, available as a function either of P or of T, suggests that the pressure effects are satisfactorily modelled, whilst the effect of T on the simulations is underestimated. The cell edge, bond lengths and polyhedral volumes have been studied as a function of P along five isotherms, spaced by 300 K steps. These isotherms tend to converge at high pressure, which demonstrates that the pressure effects become dominant compared to those of thermal origin in affecting the structural properties far from ambient conditions. The cell parameter, bond distances, and other structural and thermoelastic quantities determined through simulations have been parametrised as a function of P and T by polynomial expansions. Bulk modulus and thermal expansion have been discussed in the light of the high-temperature-Birch-Murnaghan and of the Vinet P – V – T equations of state. The predictions of the bulk modulus versus P and T from the present calculations and from the Vinet-EOS agree up to 10 GPa, but they differ at higher pressure. Received: 23 October, 1998 / Revised, accepted: 23 April, 1999     

冲绳海槽浮岩的高温高压纵波速度

对采自冲绳海槽中部海底的浮岩样品和邻近陆地樱岛火山的安山岩样品进行了温度 (常温 - 15 0 0℃ )与压力 (常压 - 2 .4 GPa)实验 ,测得在较低温度 -压力条件下 (<1GPa,<80 0℃ )浮岩样品的纵波速度小于安山岩样品的纵波速度 ,在较高温度 -压力条件下 (>1GPa,>80 0℃ )二者的纵波速度接近一致 (5 .9km /s)。 1GPa/80 0℃是浮岩样品和安山岩样品的热动力相变点 ,推测该点的深度大于 18km。