Olivine/Fe-metal equilibrium under high pressure: an ATEM investigation

San Carlos olivine samples enclosed in soft iron capsules were annealed in an uniaxial split-sphere apparatus, at pressures ranging from 4.6 to 9.0 GPa and temperature ranging from 1310o to 1595 oC. We estimated the annealing fO₂, theoretically controlled by the olivine/Fe-metal equilibrium, to be 1 to 2 log units above the fO₂ of the iron/wustite buffer. Samples were investigated by analytical transmission electron microscopy (ATEM) in order to verify that olivine and Fe capsule did equilibrate during the annealings. TEM imaging of the olivine bulk shows a and c dislocations confined in the (010) plane, and small (0.5 μm) spatially coupled precipitates of (1) Al-rich spinel and (2) enstatite (volumic proportion of precipitates ≃60 ppm). These coupled precipitates are surrounded by split c dislocation loops. Olivine composition profiles, determined by ATEM near the Fe-capsule/olivine contact, reveal a weak loss of Ni from the olivine matrix toward the capsule, as expected in such reducing conditions. These profiles also reveal a marked incorporation of Fe from the capsule into the olivine matrix. These observations, and their interpretation in terms of olivine point defect chemistry, lead to the following conclusions: (1) the starting olivine contained a high concentration of vacancies on octahedral sites (≥1000 ppm per site); such a high vacancy concentration is expected in San Carlos olivine which equilibrated in nature at relatively high fO₂; (2) the olivine/Fe-metal equilibrium did control fO₂ during the annealings, that resulted in a rapid re-equilibration of olivine at the beginning of the runs to the lower fO₂ imposed by the Fe capsule; this led to a strong decrease of the octahedral vacancy concentration in olivine. (3) Such a fO₂ decrease promoted in olivine the coupled precipitation of both types of Al-rich spinel and enstatite precipitates. These observations show that the use of Fe-capsule in high pressure experiments is an efficient method for controlling fO₂ when studying olivine, and more generally Fe-bearing silicates. Received: 5 November 1997 / Accepted: 5 May 1998     

Strength of solid pressure media and implications for high pressure apparatus

The stress-strain properties of talc, pyrophyllite, silver chloride, sodium chloride, boron nitride and graphite have been measured under confining pressures up to 8 or 10 kb at room temperature, and, in the case of talc, also at temperatures up to 900° C. The extrapolation and application of these results to solid medium high pressure apparatus of pistoncylinder type is discussed and a calculation made of the correction to nominal pressure (friction correction), taking into account the stress gradients in the medium and the shearing between the medium and the cylinder wall. Correction to the nominal differential stress measured in solid medium stress-strain apparatus is also discussed.     

FTIR Spectrum of Phenocryst Olivine as an Indicator of Silica Saturation in Magmas

Fourier Transform infrared (FTIR) absorption spectra of hydroxylwere measured on olivine phenocrysts from hydrous basaltic meltsthat originated in island-arc tectonic settings. The basalticmelts encompass a wide range of silica activities from orthopyroxene-saturatedhypersthene-normative to nepheline-normative compositions. Theintensities and wavenumber placement of hydroxyl absorptionbands correlate with the degree of silica saturation of theparent melt from which the olivine crystallized. Olivines fromsilica-undersaturated nepheline-normative melts absorb IR radiationin the wavenumber range 3430–3590 cm^–1 (Group 1).In contrast, olivines from orthopyroxene-saturated boniniticmelts exhibit hydroxyl absorption bands in the wavenumber range3285–3380 cm^–1 (Group 2). Olivines crystallizedat intermediate silica activities exhibit a combination of thetwo groups of hydroxyl IR bands, where the proportion of Group2 bands increases with increasing silica saturation of the parentmelt. The positions of hydroxyl absorption peaks observed herefor natural samples are consistent with previous measurementson experimentally annealed olivines. Thus protonation experimentscan be employed to make spectroscopically dry olivine structuresvisible by IR, yielding information on the silica saturationof the parental magmas. Hydroxyl concentrations in the studiedolivines were estimated to be 1–2 ppm, corresponding toan olivine–melt partition coefficient of (1·0 ±0·3) x 10^–4. KEY WORDS: nominally anhydrous minerals; olivine; water; mantle; silica activity; melt inclusions     

Evaluation of the non-hydrostatic stress produced in a multi-anvil high pressure apparatus

Olivine single crystals have been deformed under high confining pressure (P=5?GPa) and temperature (T=1400?°C) conditions in a multi-anvil high pressure apparatus. NaCl, diamond and NaCl+diamond (2:1 by volume) powders were encapsulated along with the olivine single crystals in order to produce a range of stress states. The change of the non-hydrostatic stress transmitted to the olivine samples, enclosed within these three different media, during heating has been evaluated by observation of dislocation microstructure and density. A higher differential stress can be generated with diamond powder (0.1?GPa) than with NaCl powder (0.02?GPa). Although an intermediate differential stress between 0.1?GPa and 0.02?GPa had been expected to be generated using NaCl+diamond powder, the generation of non-hydrostatic stress in the olivine sample was unsuccessful. This may be caused by the fact that compaction (or sintering) proceeded in the capsule throughout the experiments. The most important finding of these experiments is that a constant non-hydrostatic stress can be applied to a sample under very high pressure and temperature conditions within the multi-anvil high pressure apparatus for the duration of the experiment. This approach is therefore suitable for investigating the steady-state rheological properties of mantle minerals at near-mantle conditions.     

Thermal expansion of alkali halides at high pressure: NaCl as an example

Thermal defects in ionic materials can have important effects on their thermal expansion at high temperatures. Earlier treatments of thermal expansion generally have neglected or not considered such effects. Here an analytical expression for the thermal defect contribution and its dependence on pressure is derived. We show that such contributions, which are significant at high temperature and atmospheric pressure, become negligible at pressures above approximately 0.25 to 0.35 of the bulk modulus at standard conditions. At very high pressure, based on Birch's (1968) relationship between high and low pressure thermal expansion, and assuming αK _Tis independent of pressure, NaCl thermal expansion can be calculated within the constraints of a semi-empirical quasi-harmonic perfect crystal model. The calculations are compared with available theoretical and experimental values over an extended temperature/pressure regime. The method should have broad applicability for other ionic crystals.     

侧装式弯曲元高压冻融试验装置研制与初步应用北大核心CSCD

研究深土冻融过程的声波响应特性,对于声波技术应用于深厚表土层人工冻结工程有重要意义。深土原位冻融始终处于高地应力环境下,但目前声波测试装置尚不具备高压冻融条件下的测试功能。为此本文结合弯曲元测试技术,研制了侧装式弯曲元高压冻融试验装置,以了解高应力条件下深土冻融过程的剪切波速。该试验装置主要由试样承压舱、加载系统、控温系统、数据采集系统和弯曲元测试系统构成。系统核心单元——试样承压舱采用双层筒结构,内筒为聚四氟乙烯筒,外筒为钢筒,弯曲元探头设置于内层筒侧壁。通过数值计算确定内筒壁厚8mm,外筒壁厚15mm,该结构可满足高应力下承压舱的抗变形、隔热和隔振要求。利用弯曲元测试系统研究了声波走时确定方法,以及激励波形和频率等测试参数。根据测试结果,本试验条件下声波走时采用初达波法确定,激励波形采用方波,高密度冻土和未冻土的激励频率分别选择4kHz和5kHz。最后,利用该装置测试了有载条件下深部黏土不同负温下的剪切波速,初步验证了装置的适用性。     

In situ observation of a phase transition in Fe2SiO4 at high pressure and high temperature

We used an in situ measurement method to investigate the phase transition of Fe₂SiO₄ polymorphs under high pressures and temperatures. A multi-anvil high-pressure apparatus combined with synchrotron X-ray radiation was used. The stability of each polymorph was identified by observing the X-ray diffraction data from the sample. In most experiments, the diffraction patterns were collected 10–30 min after reaching the desired pressure and temperature conditions. The transition boundary between the olivine and spinel phase at T = 1,000–1,500 K and P = 2–8 GPa was determined to occur at P (GPa) = 0.5 + 0.0034 × T (K). The transition pressure determined in this study was in general agreement with that observed in previous high-pressure experiments. However, the slope of the transition, dP/dT, determined in our study was significantly higher than that estimated by the previous study combined with the in situ X-ray method.     

Development of an apparatus to measure groundwater qualities in situ and to sample groundwater using boreholes

 To accurately measure the pH, Eh, EC and temperature of groundwater retrieved from boreholes, a deep groundwater sampling apparatus was developed which provided sensory measurements both in situ and in a flow-through cell at ground level. Under a pressure of 1×10⁶ Pa the in situ accuracy of the apparatus sensor was within the following limits: pH ±0.2, temperature ±0.1°C, Eh ±10 mV, and EC ±2.4%. The measuring and sampling of deep groundwater from a borehole of more than 1000 m in depth was performed continuously for 30 days. Values of pH were the same for the in situ sensor, the flow-through cell sensor and the laboratory measurements of the sampled water. At the beginning of the sampling period, Eh values of the in situ sensor indicated deep groundwater conditions. The apparatus is particularly useful for Eh measurement. Chemical composition and stable isotope ratios indicated that the groundwater sampled from more than 1000 m depth was a connate water with a chemical composition slightly different from seawater of the present time, and the groundwater retrieved from 800 m depth was a meteoric water. Natural radioactive elements are thought to be the origin of the tritium in the groundwater retrieved from the 1000 m depth. Received: 6 August 1996 / Accepted: 22 October 1996     

测量岩体应力波的压电应力计

本文介绍一种用于岩体爆炸测量的新型压电应力计--RS 型应力计.它利用压电晶体的压电效应直接测量应力。由于外壳采用爆炸现场测点处的岩芯材料制成,避开了应力测量中难以解决的匹配问题.实践表明:只要保证 RS 型应力计按规定工艺要求制作,并进行系统的标定和回填,对中硬和坚硬岩体中自由场和毛洞周边的爆炸应力测量是可行的。     

A piezometer for Stress Wave Measurement in Rock Mass

A new type of stress piezometer, RS stress gage, is presented in this paper. This new type of stress gage make use of piezoelectricity of piezocrystal to measure dynamic stress and read the magnitude directly. To avoid the bad matching of the gage and rock mass in situ, the shell of the gage is made of rock core from in situ. It has been proved that the new stress gage can work well during the measuring of the stress of blast wave in rock mass as long as it was made fine, calibrated accurately, and inserted carefully.     

Problems of pressure estimation in high temperature experiments using solid media apparatus with particular reference to piston-cylinder and anvil-with-hole apparatus (Part I)

The high albite (Ab)⇄jadeite (Jd)+quartz(Q) reaction (1) and the quartz(Q)⇄coesite (Cs) transformation (2) have been determined within the temperature range of 1000–1100°C and 1000–1400°C respectively under variable pressures using an anvil-with-hole apparatus. The equilibrium curves for the two reactions as a function ofP andT are as follows: P=−1·33+0·0296T (reaction 1);P=18·949+0·0111T(reaction 2). These two lines intersect at 31·1±0·5kb and 1096°C. The possibility of using an anvil-with-hole apparatus for conducting current investigations is discussed in this paper.     

Olivine xenocrysts in picritic magmas

Experimental partial melting of plagioclase lherzolite at 0.7 MPa confining pressure has produced euhedral olivine crystals by corrosion and overgrowth during cooling. The particular conditions of this experiment allow observation of both processes recorded in the crystal shape: corrosion boundaries are rounded, or straight when parallel to [001] intersection of {110} planes; (010) and {110} facets are developed by fast overgrowth during quenching. These observations support the contention that phenocrysts in basaltic or picritic magmas are, in part, xenocrysts. The possible mantle origin of olivine crystals in two natural occurrences of ultramafic magmas; the picritic pillow lavas of the Troodos, and a wehrlitic intrusion of the oman ophiolite, is investigated. In both cases discriminant characteristics are deduced from detailed microstructural study. The mantle origin of olivine megacrysts in the investigated picrites raises the question about the existence of picritic magmas in the mantle.     

Estimating the hydraulic properties of an aquitard from in situ pore pressure measurements

A workflow is described to estimate specific storage (S _s) and hydraulic conductivity (K) from a profile of vibrating wire piezometers embedded into a regional aquitard in Australia. The loading efficiency, compressibility and S _s were estimated from pore pressure response to atmospheric pressure changes, and K was estimated from the earliest part of the measurement record following grouting. Results indicate that S _s and K were, respectively, 8.8?×?10^?6 to 1.2?×?10^?5 m^?1 and 2?×?10^?12 m s^?1 for a claystone/siltstone, and 4.3?×?10^?6 to 9.6?×?10^?6 m^?1 and 1?×?10^?12 to 5?×?10^?12 m s^?1 for a thick mudstone. K estimates from the pore pressure response are within one order of magnitude when compared to direct measurement in a laboratory and inverse modelled flux rates determined from natural tracer profiles. Further analysis of the evolution and longevity of the properties of borehole grout (e.g. thermal and chemical effects) may help refine the estimation of formation hydraulic properties using this workflow. However, the convergence of K values illustrates the benefit of multiple lines of evidence to support aquitard characterization. An additional benefit of in situ pore pressure measurement is the generation of long-term data to constrain groundwater flow models, which provides a link between laboratory scale data and the formation scale.     

Olivine dissolution in basaltic melt

The main purpose of this work is to understand and quantify diffusive and convective olivine dissolution in basaltic melt. Crystal dissolution and growth in a magma chamber is often accompanied by the descent or ascent of the crystal in the chamber due to gravity. The motion induces convection that enhances mass transport. Such convective dissolution and growth rates have not been quantified before. MgO diffusivity in the melt (D_MgO), MgO concentration of the interface melt (C₀) and the effective thickness of the compositional boundary layer (δ) are necessary parameters to model the convective dissolution. Experiments of non-convective olivine dissolution in a basaltic melt were conducted at 1271-1480 °C and 0.47-1.42 GPa in a piston-cylinder apparatus. At specific temperature and pressure conditions, multiple experiments of different durations show that the interface melt reaches near-saturation within 2 min. Therefore, diffusion, not interface reaction, is the rate-controlling step for non-convective olivine dissolution in basaltic melt. The compositional profile length and olivine dissolution distance are proportional to the square root of experimental duration, consistent with diffusive dissolution. D_MgO and C₀ are obtained from the experimental results. D_MgO displays Arrhenian dependence on temperature, but the pressure dependence is small and not resolved. C₀ increases with increasing temperature and decreases with increasing pressure. Comparison with literature data shows that D_MgO depends strongly on the initial melt composition, while C₀ does not. δ is estimated from fluid dynamics. D_MgO/δ, which characterizes the kinetic and dynamic aspects of convective crystal dissolution, is parameterized as a function of temperature, pressure, and olivine composition. Convective olivine dissolution rate in basaltic melt can be conveniently calculated from the model results. Application to convective crystal growth and xenolith digestion is discussed.     

A suggested origin of MARID xenoliths in kimberlites by high pressure crystallization of an ultrapotassic rock such as lamproite

Chemical, mineralogical and isotopic studies have been made on nodules of the MARID (Mica-Amphibole-Rutile-Ilmenite-Diopside) xenolith suite in southern African kimberlites. All are ultramafic and ultrapotassic (MgO= 20–25%, K₂O=4–9%), with bulk compositions reflecting the wide variation in relative proportions of the five minerals amongst the nodules. They are comparable in major element compositions to magnesian lamproites, in particular the ultrabasic olivine-lamproites of Western Australia. In a number of high pressure experimental studies on ultra-potassic rocks, the phases produced between 25–30 kbar from compositions comparable to those of MARID rocks (in the presence of additional water), were predominantly phlogopite and diopside (±K-richterite, ±ilmenite, ±rutile). Furthermore the compositions of experimental minerals produced in the synthetic-biotite-mafurite-H₂O system by Edgar et al. (1976) are similar to those in MARID rocks.It is suggested on the basis of these observations and the textural appearance of MARID rocks that they are magmatic compositional equivalents of MgO-rich lamproites that crystallized at high pressures. While lamproites have higher average concentrations of incompatible elements, (including REE), some MARID rocks have comparable abundances. It is suggested that late stage vapour-rich melts carrying substantial REE and other incompatible elements escaped from crystallizing MARID magmas into surrounding subcontinental lithosphere, thus resulting in lower levels of these elements in most MARID rocks. In contrast faster crystallization of lamproitic rocks under volcanic/ hypabyssal conditions would prevent similar losses.The MARID proto-magmas are thought to be either partial melts of metasomatised phlogopite peridotite, or small volume asthenospheric melts which are modified and further enriched by incorporation of small partial melts of enriched subcontinental lithosphere during magma ascent.     

地幔橄榄岩中橄榄石的指示意义

橄榄石是地幔橄榄岩和辉石岩的主要组成矿物,但也经常以斑晶和捕虏晶的形式出现在玄武质岩石中。结合近年来在地幔橄榄岩的主要元素（如Mg和Fe）组成特征以及Li、Mg和Fe稳定同位素地球化学方面的研究成果,重点对橄榄石的地球化学特征与华北克拉通岩石圈地幔演化过程之间的联系进行了讨论,旨在加深对华北克拉通岩石圈地幔演化过程的理解。现有研究表明：地幔橄榄岩中橄榄石的矿物学特征、元素和同位素地球化学组成能够很好地指示岩石圈地幔的特征及其演化过程,因而具有重要的意义。对于克拉通地区的地幔橄榄岩来说,橄榄石的Mg#通常可以指示岩石圈地幔的属性,古老、难熔的地幔橄榄岩中的橄榄石一般具有较高的Mg#（〉92）,而新生的岩石圈地幔橄榄岩中的橄榄石则具有较低的Mg#（〈91）。因此,地幔橄榄岩中橄榄石的Mg#在一定程度上具有年龄意义。橄榄岩中橄榄石的Li、Mg和Fe同位素组成也可以明确指示岩石圈地幔的属性及其所经历的演化过程,正常地幔的δ7Li、δ26Mg和δ57Fe组成相对均一,如果上述同位素组成偏离正常地幔值,则说明岩石圈地幔经历了熔体/流体的交代作用。华北克拉通地区地幔橄榄岩捕虏体中橄榄石的Li、Mg和Fe同位素组成研究表明：该区的岩石圈地幔经历了多个阶段、不同来源的熔体/流体的改造过程。     

High pressure generation in Kawai-type multianvil apparatus using nano-polycrystalline diamond anvils

Nano-polycrystalline diamond cubes with an edge length of 6 mm have been used as anvils for Kawai-type multianvil apparatus. The maximum pressure of ∼88 GPa was confirmed based on in situ X-ray diffraction measurements using nano-polycrystalline diamond anvils with a truncation of 1.0 mm, which is more than 50% higher than the pressure (∼56 GPa) achieved at the same press load using sintered-diamond anvils. The X-ray transparency of the nano-polycrystalline diamond anvil was found to be about 10–100 times as high as that of sintered-diamond anvils for a wide range of photon energies (∼30–130 keV), leading to high-quality X-ray imaging and diffraction profiles of the sample under pressure, even through the anvils. It is expected that further optimization of the pressure medium and gasket would lead to pressures far higher than 100 GPa without sacrificing the advantages of the multianvil apparatus over diamond anvil cells.     

Kaolinite as an in situ dosimeter for past radionuclide migration at the Earth's surface

The origin of 3 types of point defects (A-, A′- and B-centers) in kaolinite, due to natural irradiation and detected by electron paramagnetic resonance spectroscopy (EPR), has been demonstrated by artificial irradiation. The potential use of tracing the dynamics of the transfer of radionuclides through A-centers (i.e. the most stable centers) was qualitatively tested on different low-temperature alteration systems, some associated with U-concentrations. This paper proposes a quantitative approach to the reconstruction of the past migration of radionuclides by dosimetry of A-centers. With this aim in mind, the efficiency of α- and γ-radiations to produce A-centers was determined by experimental irradiation. Parameters extracted from A-center growth curves, together with their relationship with a parameter describing the degree of order of kaolinite, permitted (i) a definition to be made of the dose range in which a given kaolinite could be used as a dosimeter and (ii) the quantitative derivation of U-concentration from the cumulative dose (paleodose) of kaolinites. This was achieved by a formalism that accounted for the contribution of natural radiosources to the production of A-centers. The formalism was applied to the Nopal I U-deposit (Chihuhua, Mexico), considered as a natural analogue of a high level nuclear waste repository. Irrespective of the scenario considered, in terms of kaolinite age and of degree of isotopic disequilibrium in the system, A-center dosimetry permitted the determination of past occurrences of U which were several orders of magnitude higher than the present-day measured U-concentrations. Furthermore, this approach also provided evidence for several previous episodes of U-migration. EPR spectroscopy is thus a unique tool for the quantitative, indirect assessment of past radionuclide migration in the geosphere and kaolinite is a reliable in-situ dosimeter.     

Problems of pressure estimation in high temperature experiments using solid media apparatus; pressure calibration with reference to breakdown of albite and quartz-coesite transformation (Part II)

The high albite (Ab)?jadeite (Jd)+quartz(Q) reaction (1) and the quartz(Q)?coesite (Cs) transformation (2) have been determined within the temperature range of 1000–1100°C and 1000–1400°C respectively under variable pressures using an anvil-with-hole apparatus. The equilibrium curves for the two reactions as a function ofP andT are as follows: P=?1·33+0·0296T (reaction 1);P=18·949+0·0111T(reaction 2). These two lines intersect at 31·1±0·5kb and 1096°C. The possibility of using an anvil-with-hole apparatus for conducting current investigations is discussed in this paper.     

In situ neutron diffraction study of deuterated portlandite Ca(OD)2 at high pressure and temperature

The structure of deuterated portlandite, Ca(OD)₂, has been investigated using time-of-flight neutron diffraction at pressures up to ∼4.5 GPa and temperatures up to ∼823 K. Rietveld analysis of the data reveals that with increasing pressure, unit-cell parameter c decreases at a rate about 4.5 times larger than that for a, which is largely due to rapid contraction of the interlayer spacing in this pressure range. Fitting of the determined cell volumes to the third-order Birch–Murnaghan equation of state yields a bulk modulus (K ₀) of 32.2 ± 1.0 GPa and its first derivative (K ₀′) of 4.4 ± 0.6. Moreover, on compression, hydrogen-mediated interatomic interactions within the interlayer become strengthened, as reflected by decreases in interlayer D···O and D···D distances with increasing pressure. Correspondingly, D–D, the distance between the three equivalent sites over which D is disordered, increases, suggesting a pressure-induced hydrogen disorder. This behavior is similar to that reported in brucite at elevated pressure. On heating at ∼2.1 GPa, cell parameter c increases more rapidly than a, as expected. However, because of the pressure effect, the thermal expansion coefficients, particularly along c, are much smaller than those at ambient pressure. With increasing temperature, the three partially occupied D sites become further apart, and the D-mediated interactions, mainly the interlayer D···D repulsion, become weakened.