Extrinsic and intrinsic mode of hydrogen occurrence in natural olivines: FTIR and TEM investigation

Olivine crystals from two mantle nodules in kimberlites (pipe Udachnaya and pipe Obnazennaya, Yakutiya, Siberia) were investigated using EMP, TEM, AEM and FTIR techniques to determine the mode of hydrogen occurrence in olivine. Olivine contains three types of nanometer-sized inclusions: “large” inclusions of hexagonal-like shape up to several hundred nm in size (1), lamellar defects (2) and small inclusions of hexagon-like shape up to several 10?nm in size (3). Lamellar defects and small inclusions are considered to be a “hydrous” olivine. All three types of inclusions contain OH^? or water, but they are different with respect to their phase composition. In “large” inclusions (1) hydrous magnesium silicates, such as serpentine?+?talc (“kerolite”?) and 10-Å phase?+?talc were identified. Lamellar defects (2) and small inclusions (3) are depleted in Mg and Fe compared to the olivine matrix, while the silica content is the same as that of olivine. Modulations in the periodicity of the olivine structure are observed in SAED patterns and HREM images of (2) and (3). The superperiodicity can be referred to OH^?-bearing point defect ordering in the olivine structure. If this is the case, the material of both lamellar defects and small inclusions can be assumed to be a “hydrous olivine” Mg_{2– x} v _x SiO₄H_{2 x} with a cation-deficient olivine crystal structure. Thus, both an extrinsic mode of hydrogen occurrence in olivine, such as nanometer-sized inclusions of OH^?-bearing magnesium silicates, and an intrinsic mode of hydrogen incorporation into the olivine structure, such as “hydrous olivine” in itself, were found. The data obtained here show that the OH absorption bands observed in olivine spectra at 3704(3717) and 3683(3688) cm^?1 can be unambiguously identified with serpentine; the band at 3677(3676) cm^?1 can be associated with talc. The absorption bands observed at 3591 and 3660?cm^?1 in olivine match those of the 10-Å phase at 3594, 3662 and 3666?cm^?1.     

The effect of silica activity on the incorporation mechanisms of water in synthetic forsterite: a polarised infrared spectroscopic study

Pure forsterite crystals were grown from hydrous melts using controlled cooling experiments at 2.0 GPa and varying the bulk Mg/Si ratio from 2.0 to 1.5. Oriented single crystals were then studied by polarised infrared spectroscopy. The spectra of the samples with the lowest silica activity (aSiO₂) contain the main OH bands in the range 3,620–3,450 cm^–1 only. In contrast, the spectra of the samples synthesised with the highest aSiO₂ contain additional pleochroic bands at 3,160, 3,220 and 3,600 cm^–1. The variations are interpreted in terms of protonated silicon vacancies being dominant at low aSiO₂ and Mg vacancies dominant at high aSiO₂. Xenolithic mantle olivines generally do not have the spectrum expected for orthopyroxene buffered conditions, suggesting that they re-equilibrated with their host melts during ascent, but mantle olivine from the Zabargad peridotite massif probably is in equilibrium with the coexisting orthopyroxene.Editorial responsibility: T.L. Grove     

Some constraints on the thermodynamic mixing properties of Fe-Mg orthopyroxenes and olivines

Existing data on the temperature and composition dependence of the Fe²⁺-Mg²⁺ distribution between Fe-Mg olivine and orthopyroxene, the intra-crystalline distribution of Fe²⁺ and Mg²⁺ between M1 and M2 sites in orthopyroxene, and macroscopic activity-composition relations in olivine and orthopyroxene are shown to be inconsistent with generally accepted thermodynamic formulations which assume that the non-configurational Gibbs energy of orthopyroxene is independent of the degree of long-range ordering of Fe²⁺ and Mg⁺ between M1 and M2 sites. These data are interpreted in terms of the constraints they provide on the size of Bragg-Williams type energy, entropy, and volume terms for olivine and orthopyroxene. The apparent equilibrium constant for Fe-Mg exchange between olivine and orthopyroxene is shown to be a potentially useful ‘geothermometer’ for olivine-orthopyroxene assemblages with olivines with mole fraction of Fe₂SiO₄ component less than 0.2 or greater than 0.6. A provisional calibration of this ‘geothermometer’ is presented.     

Experimental partitioning of halogens and other trace elements between olivine, pyroxenes, amphibole and aqueous fluid at 2 GPa and 900–1,300 °C

We present new partition coefficients for various trace elements including Cl between olivine, pyroxenes, amphibole and coexisting chlorine-bearing aqueous fluid in a series of high-pressure experiments at 2 GPa between 900 and 1,300 °C in natural and synthetic systems. Diamond aggregates were added to the experimental capsule set-up in order to separate the fluid from the solid residue and enable in situ analysis of the quenched solute by LA–ICP–MS. The chlorine and fluorine contents in mantle minerals were measured by electron microprobe, and the nature of OH defects was investigated by infrared spectroscopy. Furthermore, a fluorine-rich olivine from one selected sample was investigated by TEM. Results reveal average Cl concentrations in olivine and pyroxenes around 20 ppm and up to 900 ppm F in olivine, making olivine an important repository of halogens in the mantle. Chlorine is always incompatible with Cl partition coefficients D _Cl ^{olivine/fluid} varying between 10^?5 and 10^?3, whereas D _Cl ^{orthopyroxene/fluid} and D _Cl ^{clinopyroxene/fluid} are ~10^?4 and D _Cl ^{amphibole/fluid} is ~5 × 10^?3. Furthermore, partitioning results for incompatible trace element show that compatibilities of trace elements are generally ordered as D ^amph/fluid ≈ D ^cpx/fluid > D ^opx/fluid > D ^ol/fluid but that D ^{mineral/fluid} for Li and P is very similar for all observed silicate phases. Infrared spectra of olivine synthesized in a F-free Ti-bearing system show absorption bands at 3,525 and ~3,570 cm^?1. In F ± TiO₂-bearing systems, additional absorption bands appear at ~3,535, ~3,595, 3,640 and 3,670 cm^?1. Absorption bands at ~3,530 and ~3,570 cm^?1, previously assigned to humite-like point defects, profit from low synthesis temperatures and the presence of F. The presence of planar defects could not be proved by TEM investigations, but dislocations in the olivine lattice were observed and are suggested to be an important site for halogen incorporation in olivine.     

Infrared spectroscopic investigation of hydroxyl in β-(Mg,Fe)2SiO4 and coexisting olivine: Implications for mantle evolution and dynamics

Wadsleyite (β-(Mg,Fe)₂SiO₄) is a major constituent of the Earth's transition zone and is known to accommodate OH. The portion of the transition zone between 400–550 km could be an important source or sink for hydroxyl in plumes and slabs intersecting this region. Micro-infrared spectroscopy has been carried out on the β-phase and coexisting metastable olivine synthesized in a multianvil apparatus at 14 GPa and 1550–1650 K under hydrous conditions. Single-crystal and polycrystal specimens of both phases were analyzed in the 1800–8500 cm^?1 frequency region to determine the speciation, abundances, and partitioning behavior of the hydrous components in coexisting β-phase and olivine. β-phase spectra consistently show three distinct OH bands at 3329, 3580, and 3615 cm^?1. OH concentrations range from 10000–65000 H/10⁶ Si. A strong positive correlation of grain size and extent of transformation with OH concentration in the β-phase indicates that grain-growth and transformation rates are enhanced in a hydrous environment. Olivine spectra are variable, but consistently show a prominent broad-band absorbance representing molecular H₂O, consistent with the infrared signature of the starting material. OH concentrations in olivine range from <300–1400 H/10⁶ Si. The highest OH concentrations measured for olivine and the β-phase may represent solubility limits, in which case the OH solubility ratio between these two phases is approximately 1∶40. Where both phases coexist and are undersaturated with OH, the partitioning ratio of OH between them is about 1∶100. The large solubility contrast between olivine and the β-phase suggests a mechanism for hydrating the transition zone via olivine carried down in subducting slabs. Plumes impinging on an OH-rich upper transition region could cause H₂ or H₂O to be released upon transformation of the β-phase to olivine, resulting in initiation of secondary upwellings. If dissolution of OH weakens the β-phase, and if OH is present in the mantle, the region between 400–550 km could be a zone of low viscosity.     

Low differential stress and controlled chemical environment in multianvil high-pressure experiments

Studies of mass transport and kinetics in minerals at high pressure often require a sample environment in which the stress is near-hydrostatic and the chemical environment is carefully controlled. We report here details of a multianvil sample assembly in which these requirements are fulfilled and which has been used to study the effect of pressure on the kinetics of dislocation recovery in olivine up to 10 GPa. Annealing experiments have been performed on single crystals of San Carlos olivine at 8.5 GPa and 1400° C in a 1200 tonne split-sphere multianvil apparatus. The sample assembly consists of an 18 mm MgO octahedron with a LaCrO₃ heater of variable wall thickness to give a small temperature variation (20° C) along the 3 mm length of the sample capsule. To minimize the differential stress on the sample, the olivine single crystal is surrounded by NaCl and both pressurization and depressurization are performed slowly at a temperature of 600° C (to minimize the strength of the NaCl). The silica activity is buffered by orthopyroxene powder in contact with the olivine and the oxygen fugacity is buffered by Ni + NiO within the sample capsule. The H₂O-content of the sample assembly is minimized by drying all components at 230° C under vacuum. Olivine single crystals recovered after annealing at 1400° C and 8.5 GPa show no evidence of deformation, either ductile or brittle. Dislocation densities of 10⁹–10¹⁰ m^-2 are similar to those observed prior to high-pressure annealing and indicate differential stresses of <10 mpa.=" infrared=" spectroscopy=" indicates=" that=" the=" hydrogen=" content=" of=" a=" sample=" annealed=" at=" 10=" gpa,=" 1500°=" c=" for=" 21=" h=" is=">13 H/10⁶Si, which, although low, is higher than that of the crystals prior to high-pressure annealing. Finally, the effectiveness of the fO₂ buffer has been verified by estimating the fO₂ at the surface of the sample from the solubility of Fe in Pt metal in equilibrium with the olivine and orthopyroxene.     

Titanium solubility in olivine in the system TiO<Subscript>2</Subscript>–MgO–SiO<Subscript>2</Subscript>: no evidence for an ultra-deep origin of Ti-bearing olivine

The finding of ilmenite rods in olivine from orogenic peridotites has sparked a discussion about the processes of incorporation and exsolution of titanium in olivine. We have experimentally investigated the solubility of Ti in olivine as a function of composition, temperature and pressure in the synthetic TiO₂–MgO–SiO₂ system. Experiments at atmospheric pressure in the temperature range 1,200–1,500°C showed that the highest concentration of TiO₂ is obtained when olivine coexists with spinel (Mg₂TiO₄). The amount of TiO₂ in olivine in the assemblages olivine + spinel + periclase and olivine + spinel + ilmenite at 1,500°C was 1.25 wt.%. Changes in the coexisting phases and decreasing temperature result in a significant reduction of the Ti solubility. Olivine coexisting with pseudobrookite (MgTi₂O₅) and a Ti–Si-rich melt at 1,500°C displays a fourfold lower TiO₂ content than when buffered with spinel. A similar decrease in solubility is obtained by a decrease in temperature to 1,200°C. There is a negative correlation between Ti and Si and no correlation between Ti and Mg in Ti-bearing olivine. Together with the established phase relations this suggests that there is a direct substitution of Ti for Si at these temperatures, such that the substituting component has the stoichiometry Mg₂TiO₄. The unit cell volume of olivine increases systematically with increasing TiO₂ content demonstrating that the measured TiO₂ contents in olivine are not caused by micro-inclusions but by incorporation of Ti in the olivine structure. Least squares fitting of 20 olivine unit cell volumes against the Ti content yield the relation: V (ų)=290.12(1) + 23.67(85) N_Ti. The partial molar volume of end-member Mg₂TiO₄ olivine (N_Ti=1) is thus 47.24±0.13 cm³. The change of the Ti solubilty in olivine coexistent with rutile and orthopyroxene with pressure was investigated by piston cylinder experiments at 1,400°C from 15 to 55 kbar. There is no increase in TiO₂ contents with pressure and in all the experiments olivine contains ~0.2 wt.% TiO₂. Moreover, a thermodynamic analysis indicates that Ti contents of olivine coexisting with rutile and orthopyroxene should decrease rather than increase with increasing pressure. These data indicate that the ilmenite exsolution observed in some natural olivine does not signify an ultra-deep origin of peridotite massifs.     

Inter-mineral Fe isotope variations in mantle-derived rocks and implications for the Fe geochemical cycle

Iron isotope and major- and minor-element compositions of coexisting olivine, clinopyroxene, and orthopyroxene from eight spinel peridotite mantle xenoliths; olivine, magnetite, amphibole, and biotite from four andesitic volcanic rocks; and garnet and clinopyroxene from seven garnet peridotite and eclogites have been measured to evaluate if inter-mineral Fe isotope fractionation occurs in high-temperature igneous and metamorphic minerals and if isotopic fractionation is related to equilibrium Fe isotope partitioning or a result of open-system behavior. There is no measurable fractionation between silicate minerals and magnetite in andesitic volcanic rocks, nor between olivine and orthopyroxene in spinel peridotite mantle xenoliths. There are some inter-mineral differences (up to 0.2‰ in ⁵⁶Fe/⁵⁴Fe) in the Fe isotope composition of coexisting olivine and clinopyroxene in spinel peridotites. The Fe isotope fractionation observed between clinopyroxene and olivine appears to be a result of open-system behavior based on a positive correlation between the Δ⁵⁶Fe_{clinopyroxene-olivine} fractionation and the δ⁵⁶Fe value of clinopyroxene and olivine. There is also a significant difference in the isotopic compositions of garnet and clinopyroxene in garnet peridotites and eclogites, where the average Δ⁵⁶Fe_{clinopyroxene-garnet} fractionation is +0.32 ± 0.07‰ for six of the seven samples. The one sample that has a lower Δ⁵⁶Fe_{clinopyroxene-garnet} fractionation of 0.08‰ has a low Ca content in garnet, which may reflect some crystal chemical control on Fe isotope fractionation. The Fe isotope variability in mantle-derived minerals is interpreted to reflect subduction of isotopically variable oceanic crust, followed by transport through metasomatic fluids. Isotopic variability in the mantle might also occur during crystal fractionation of basaltic magmas within the mantle if garnet is a liquidus phase. The isotopic variations in the mantle are apparently homogenized during melting processes, producing homogenous Fe isotope compositions during crust formation.     

富铁橄榄石的水溶性实验研究SCIEI北大核心CSCD

地幔的力学性质主要受橄榄石流变性的控制,含水对橄榄石流变性质的影响很大,而橄榄石的水溶性受到温度和铁含量的影响,因此,本文进行了不同铁含量橄榄石在不同温度下的水溶性实验研究。实验使用的样品为天然橄榄石单晶Fa_(17)和Fa_(24.7)(Fe_(No.)=100×molar Fe/(Mg+Fe))以及人工合成的橄榄石单晶Fa_(22);橄榄石单晶的水溶性实验在300MPa围压和1273~1473K的温度条件下进行,每隔50K进行一组实验,氧逸度被控制在Ni NiO水平上。实验结束后,对橄榄石单晶沿b面进行双面研磨抛光,用电子探针分析确定橄榄石单晶成分,采用EBSD精确测量橄榄石的单晶方向,使用红外光谱仪(FTIR)的非偏振光路测试橄榄石单晶在b轴上的吸收光谱。对FTIR吸收光谱进行积分得到富铁橄榄石的水溶性实验结果:当温度由1273K升至1473K时,橄榄石单晶Fa_(17)的水溶性变化为600~1200H/10^(6) Si,橄榄石单晶Fa_(24.7)的水溶性变化为1000~1300H/10^(6) Si,人工合成的橄榄石单晶Fa_(22)的水溶性变化为500~900 H/10^(6) Si。因此,相同铁含量橄榄石单晶的水溶性随温度的增加而增加,相同温度条件下,天然形成的橄榄石的水溶性随着铁含量的增加而增加,百分之一的铁含量的增加,可以导致约百分之十的水溶性的增加。本文所研究的不同铁含量的橄榄石可以为更好地估算上地幔水溶性提供依据。     

Low-temperature evolution of OH bands in synthetic forsterite, implication for the nature of H defects at high pressure

We performed in situ infrared spectroscopic measurements of OH bands in a forsterite single crystal between ?194 and 200 °C. The crystal was synthesized at 2 GPa from a cooling experiment performed between 1,400 and 1,275 °C at a rate of 1 °C per hour under high silica-activity conditions. Twenty-four individual bands were identified at low temperature. Three different groups can be distinguished: (1) Most of the OH bands between 3,300 and 3,650 cm^?1 display a small frequency lowering (<4 cm^?1) and a moderate broadening (<10 cm^?1) as temperature is increased from ?194 to 200 °C. The behaviour of these bands is compatible with weakly H-bonded OH groups associated with hydrogen substitution into silicon tetrahedra; (2) In the same frequency range, two bands at 3,617 and 3,566 cm^?1 display a significantly anharmonic behaviour with stronger frequency lowering (42 and 27 cm^?1 respectively) and broadening (~30 cm^?1) with increasing temperature. It is tentatively proposed that the defects responsible for these OH bands correspond to H atoms in interstitial position; (3) In the frequency region between 3,300 and 3,000 cm^?1, three broad bands are identified at 3,151, 3,178 and 3,217 cm^?1, at ?194 °C. They exhibit significant frequency increase (~20 cm^?1) and broadening (~70 cm^?1) with increasing temperature, indicating moderate H bonding. These bands are compatible with (2H)_Mg defects. A survey of published spectra of forsterite samples synthesized above 5 GPa shows that about 75 % of the incorporated hydrogen belongs to type (1) OH bands associated with Si substitution and 25 % to the broad band at 3,566 cm^?1 (type (2); 3,550 cm^?1 at room temperature). The contribution of OH bands of type (3), associated to (2H)_Mg defects, is negligible. Therefore, solubility of hydrogen in forsterite (and natural olivine compositions) cannot be described by a single solubility law, but by the combination of at least two laws, with different activation volumes and water fugacity exponents.     

FTIR spectroscopy of OH in olivine: A new tool in kimberlite exploration

Our study of olivines from Canadian kimberlites shows that the application of FTIR spectroscopy significantly improves the reliability of olivine as a kimberlite indicator mineral (KIM). We have developed an algorithm that yields the water concentration and the normalized intensity of the OH IR absorption band at 3572 cm⁻¹ from unpolished olivine grains of unknown thickness. For 80% of kimberlitic olivines these two parameters are significantly higher than those for olivines from non-kimberlitic magmas and consequently, olivines with water concentrations >60 ppm and a strong absorption band at 3572 cm⁻¹ can be reliably classified as being kimberlitic.We have identified two major spectral features in the OH absorption bands of kimberlitic olivines that allow for a more detailed classification: (a) the presence of three types of high-requency OH absorption bands (Group 1A, 1B and 1C) and (b) the proportion of low-frequency OH absorption bands (Group 2) relative to high-frequency bands (Group 1). Comparison of our results with experimental studies suggests that differences within Group 1 OH absorption bands are due to different pressures of crystallization or hydrogenation. The three identified types of Group 1 OH absorption bands approximately correspond to high (P > 2 GPa, Group 1A), moderate (2-1 GPa, Group 1B), and low (<1 GPa, Group 1C) pressures of hydrogenation. Group 2 OH IR absorption bands in olivines with NiO > 3500 ppm are interpreted to reflect olivine-orthopyroxene equilibria and hence are indicative of xenocrystic olivine derived from lherzolitic or harzburgitic mantle sources. Interaction of xenocrystic olivine with hydrous kimberlitic melts with low silica activity likely will cause a gradual increase in Group 1 absorption bands. Therefore, FTIR spectra of olivine can be used to obtain qualitative estimates of the duration of interaction between mantle material and a kimberlitic melt.In addition to applications in kimberlite and diamond exploration, FTIR spectra of olivine phenocrysts, combined with mineral chemical data, may also provide insights into kimberlite evolution. Our data suggest that in some instances the ascent of kimberlitic magmas could have been interrupted at or near the Moho, followed by olivine crystallization and exsolution of aqueous fluids.     

Development of corona textures around olivine in anorthosites of the Korosten’ pluton, Ukrainian Shield: Mineralogy, geochemistry, and fluid inclusions

New data on the composition of minerals in corona textures around olivine and crystal-fluid inclusions in olivine from anorthosites of the Korosten’ pluton (sampled in the Golovino quarry), Ukrainian Shield were obtained using electron and ion microprobe analyses, Raman spectroscopy, scanning electron microscopy, and cryo- and thermometry. The corona textures developed around olivine grains in contact with plagioclase and consist of inner orthopyroxene rims around olivine and outer rims of orthopyroxene-clinopyroxene-orthoclase-plagioclase symplectites. The symplectites and orthopyroxene rims most probably developed nearly simultaneously and grew in the opposite directions from the original contact of the magmatic olivine and plagioclase and replaced both olivine and plagioclase. The Al₂O₃ and CaO concentrations in the symplectitic orthopyroxene increase toward the contact with magmatic plagioclase, whereas the Al₂O₃ and CaO concentrations in the symplectitic plagioclase simultaneously decrease and its Na₂O and K₂O increase. Optically discernible crystalline and fluid phases of crystal-fluid inclusions in olivine were identified as pyroxenes (orthopyroxene and clinopyroxene), actinolite, Ca-and Fe, Mg-carbonates, and magnetite, along with practically pure highdensity CO₂. The mineral assemblages of corona texture in the Korsten’ anorthosites were produced by autometasomatic processes at a high CO₂ activity, and the local variations in the chemistry of corona minerals were likely controlled by the content and chemistry of the interstitial fluid and primary minerals. The coronas developed under subsolidus conditions, via the reaction interaction of olivine and plagioclase under the effect of an integranular fluid, with the dissolution of olivine and plagioclase at T = 980–860°C and P > 5 kbar. Inasmuch as corona textures do not occur ubiquitously in the rocks, the origin of the former was most probably controlled by the amount of the intergranular fluid.     

Olivines and olivine coronas in mesosiderites

Olivines and their surrounding coronas in mesosiderites have been studied texturally and compositionally by optical and microprobe methods. Most olivine is compositionally homogeneous but some is irregularly zoned. It ranges from Fo_58–92 and shows no consistent pattern of distribution within and between mesosiderites. Olivine occurs as large single crystals or as partially recrystallized mineral clasts, except for two lithic clasts. One is in Emery, the other in Vaca Muerta, and they are both shock-modified olivine orthopyroxenites. $\text{FeO}\text{MnO}$ ratios in olivine exhibit a variety of differing trends and range from 22–46, most commonly 35–40. These values are lower than those in olivine from diogenites sensu stricto (45–50) and have therefore experienced a different history. Some of the olivine clasts could have coexisted with some of the large orthopyroxene clasts as equilibrium assemblages, but some could not. Much of the olivine may be derived from mesosiderite olivine orthopyroxenites, which differ from diogenites sensu stricto. More magnesian olivine may be a residue from one or more source rocks, with varying degrees of melting. These events probably occurred in a highly evolved and differentiated parent body.Fine-grained coronas surround olivine, except for those in impact-melt group mesosiderites (Simondium, Hainholz, Pinnaroo) and those without tridymite in their matrices (Bondoc, Veramin). Coronas consist largely of orthopyroxene, plagioclase, clinopyroxene, chromite, merrillite and ilmenite and are similar to the matrix, but lack metal and tridymite. Coronas contain abundant orthopyroxene but are unusually rich in chromite (up to 7%) and merrillite (up to 20%). The outer parts of the corona grade into the matrix, but have little or no metal and tridymite. Texturally the innermost part of the corona can be divided into three stages of development: I Radiating acicular; II Intermediate; III Granular. Stage I is the result of the greatest disequilibrium between olivine and matrix orthopyroxene and Stage III has the least disequilibrium. Coronas are the result of the reaction olivine + tridymite = orthopyroxene, probably because FeO (and MgO) diffuse from olivine to tridymite in the matrix. Absence of metal and concentration of chromite in the corona are probably the result of an FeO potential gradient away from the olivine. Merrillite concentrations are a result of P₂O₅ migration into the corona but are controlled by the availability of calcic pyroxene, or possibly plagioclase. Although the coronas are texturally similar to terrestrial and lunar counterparts, they are unique and represent different kinds of reactions marked by a large degree of intra-corona diffusion under dry conditions. Opaque oxide-silicate-metal buffer assemblages yield apparent equilibration conditions of about 840°C and fO₂ near 10^?20. Poikiloblastic pyroxene textures in some coronas suggest a closing of reaction systems between 900 and 1000°C and such systems may record a higher temperature stage of development.     

Water incorporation in synthetic and natural MgAl2O4 spinel

The solubility and incorporation mechanisms of water in synthetic and natural MgAl₂O₄ spinel have been investigated in a series of high-pressure/temperature annealing experiments. In contrast to most other nominally anhydrous minerals, natural spinel appears to be completely anhydrous. On the other hand, non-stoichiometric Al-rich synthetic (defect) spinel can accommodate several hundred ppm water in the form of structurally-incorporated hydrogen. Infrared (IR) spectra of hydrated defect spinel contain one main O-H stretching band at 3343-3352 cm⁻¹ and a doublet consisting of two distinct O-H bands at 3505-3517 cm⁻¹ and 3557-3566 cm⁻¹. IR spectra and structural refinements based on single-crystal X-ray data are consistent with hydrogen incorporation in defect spinel onto both octahedral and tetrahedral O-O edges. Fine structure of O-H bands in IR spectra can be explained by partial coupling of interstitial hydrogen with cation vacancies, or by the effects of Mg-Al disorder on the tetrahedral site. The concentration of cation vacancies in defect spinel is a major control on hydrogen affinity. The commercial availability of large single crystals of defect spinel coupled with high water solubility and similarities in water incorporation mechanisms between hydrous defect spinel and hydrous ringwoodite (Mg₂SiO₄) suggests that synthetic defect spinel may be a useful low-pressure analogue material for investigating the causes and consequences of water incorporation in the lower part of Earth’s mantle transition zone.     

Harzburgite found in the Hegenshan ophiolite,southeastern Central Asian Orogenic Belt: Petrogenesis and geological implications

This paper reports detailed studies on harzburgite and serpentinite in the Hegenshan ophiolitic mélange. Harzburgite consists mainly of olivine and orthopyroxene with trace amounts of clinopyroxene and chromian spinel. Clinopyroxene occurs as isolated crystals or in the intergrowth of chromian spinel–clinopyroxene–orthopyroxene. Harzburgite is moderately to highly depleted, displaying high Fo contents in olivine (90.8–92.2), moderate Al₂O₃ contents in orthopyroxene (1.59–2.79 wt%), low heavy REE abundances in clinopyroxene, and moderate Cr# values of spinel (0.50–0.62). The modal proportions of olivine and orthopyroxene pseudomorph grains imply that the parent of the Hegenshan serpentinite should be harzburgite. Whole-rock compositions of the harzburgite and serpentinite samples are characterized by depletions in Al₂O₃ and CaO and enrichments in light REE, Sr, and U. Geochemical modeling suggests that the Hegenshan harzburgite represents residues after 17–18% partial melting of the primitive mantle. The melt in equilibrium with clinopyroxene is more depleted than typical forearc basalt and boninite. Various pyroxene thermobarometers yield equilibrated temperatures of 945–1067 °C and pressures of 4.8–8.0 kbar for the Hegenshan harzburgite. The oxygen barometer yields results of +0.4 to +1.7 log units above the fayalite–magnetite–quartz buffer for the Hegenshan harzburgite. These petrological and geochemical characteristics, as well as the estimated P–T–fO₂ conditions support a back-arc setting for the Hegenshan ophiolitic mélange.     

Development of orthopyroxene-Fe/Mg ferrite symplectites by continuous olivine oxidation

The development of orthopyroxene-Fe/Mg ferrite symplectites associated with olivine is discussed with respect to the chemical reactions by which they form. Previously proposed reactions are presented graphically and the differences between them are reviewed. With the exception of exsolution, these are all discontinuous reactions in the sense that olivine is replaced by the two-phase symplectite assemblage.Olivine-hosted symplectites developed in the margins of lherzolite xenoliths from Kauai, Hawaii, demonstrate a reaction mechanism which has not been previously documented from natural samples. Original Fo₉₀ olivine in these samples oxidized to a new assemblage consisting of orthopyroxene (En_92–95)-Fe/Mg ferrite (Mf_35–50) symplectites developed within more magnesian olivine (Fo_92–96) hosts. Thus, by this mechanism, olivine of a different composition persists as part of a final three-phase assemblage. As oxidation advanced, the compositions of all three product phases became continuously more magnesian and the stoichiometric coefficients of the orthopyroxene and Fe/Mg ferrite continuously increased, whereas those of the product olivine decreased in the mass-balance equations. These characteristics demonstrate that the reaction was controlled by oxygen diffusion into the xenoliths from the highly oxidized alkali picrite melt in which they were entrained. Thermodynamic calculations suggest that a gradient in oxygen fugacity of 10^0.9 bars existed across the xenolith rims and resulted in compositional gradients of 4 mol% fayalite and ferrosilite and 15 mol% magnetite.     

OH point defects in olivine from Pakistan

The infrared (IR) spectra of gem-quality olivine crystals from Pakistan, formed in serpentinised dunitic rocks, are characterised by strongly pleochroic absorption bands at 3,613, 3,597, 3,580 and 3,566 cm^?1. These bands are assigned to O-H stretching vibrations of OH point defects corresponding to H₂O concentrations of about 35 wt ppm. Unlike other olivine spectra, the dominating bands are strongly polarised parallel to the b-axis. The unusual spectra type, excludes the presence of planar defects. This finding is supported by transmission electron microscopy. The 3,613 cm^?1 band is related to vacant Si sites, the slightly lower energetic bands preferentially to vacant M2 sites. The exclusive presence of these bands is not only a characteristic feature of olivines treated under high P,T conditions equivalent to mantle environment, the presence of these bands in untreated natural olivine also indicates formation conditions equivalent to crustal rocks.     

Solubility of water in the α, β and γ phases of (Mg,Fe)2SiO4

 The solubility of hydroxyl in the α, β and γ phases of (Mg,Fe)₂SiO₄ was investigated by hydrothermally annealing single crystals of San Carlos olivine. Experiments were performed at a temperature of 1000° or 1100 °C under a confining pressure of 2.5 to 19.5 GPa in a multianvil apparatus with the oxygen fugacity buffered by the Ni:NiO solid-state reaction. Hydroxyl solubilities were determined from infrared spectra obtained of polished thin sections in crack-free regions ≤100 μm in diameter. In the α-stability field, hydroxyl solubility increases systematically with increasing confining pressure, reaching a value of ∼20,000 H/10⁶Si (1200 wt ppm H₂O) at the α-β phase boundary near 13 GPa and 1100 °C. In the β field, the hydroxyl content is ∼400,000 H/10⁶Si (24,000 wt ppm H₂O) at 14–15 GPa and 1100 °C. In the γ field, the solubility is ∼450,000 H/10⁶Si (27,000 wt ppm H₂O) at 19.5 GPa and 1100 °C. The observed dependence of hydroxyl solubility with increasing confining pressure in the α phase reflects an increase in water fugacity with increasing pressure moderated by a molar volume term associated with the incorporation of hydroxyl ions into the olivine structure. Combined with published results on the dependence of hydroxyl solubility on water fugacity, the present results for the α phase can be summarized by the relation C _OH = A(T)f nH₂Oexp(−PΔV/RT), where A(T) = 1.1 H/10⁶Si/MPa at 1100 °C, n = 1, and ΔV = 10.6×10^–6 m³/mol. These data demonstrate that the entire present-day water content of the upper mantle could be incorporated in the mineral olivine alone; therefore, a free hydrous fluid phase cannot be stable in those regions of the upper mantle with a normal concentration of hydrogen. Free hydrous fluids are restricted to special tectonic environments, such as the mantle wedge above a subduction zone. Received: 10 February 1995 / Accepted: 23 October 1995     

Mechanisms of hydrogen incorporation and diffusion in iron-bearing olivine

The incorporation and diffusion of hydrogen in San Carlos olivine (Fo₉₀) single crystals were studied by performing experiments under hydrothermal conditions. The experiments were carried out either at 1.5 GPa, 1,000°C for 1.5 h in a piston cylinder apparatus or at 0.2 GPa, 900°C for 1 or 20 h in a cold-seal vessel. The oxygen fugacity was buffered using Ni–NiO, and the silica activity was buffered by adding San Carlos orthopyroxene powders. Polarized Fourier transform infrared (FTIR) spectroscopy was utilized to quantify the hydroxyl distributions in the samples after the experiments. The resulting infrared spectra reproduce the features of FTIR spectra that are observed in olivine from common mantle peridotite xenoliths. The hydrogen concentration at the edges of the hydrogenated olivine crystals corresponds to concentration levels calculated from published water solubility laws. Hydrogen diffusivities were determined for the three crystallographic axes from profiles of water content as a function of position. The chemical diffusion coefficients are comparable to those previously reported for natural iron-bearing olivine. At high temperature, hydrogenation is dominated by coupled diffusion of protons and octahedrally coordinated metal vacancies where the vacancy diffusion rate limits the process. From the experimental data, we determined the following diffusion laws (diffusivity in m² s⁻¹, activation energies in kJ mol⁻¹): for diffusion along [100] and [010]; for diffusion along [001]. These diffusion rates are fast enough to modify significantly water contents within olivine grains in xenoliths ascending from the mantle.