Titanian chondrodite and clinohumite in marbles from the Ötztal crystalline basement

Summary Marble lenses within the polymetamorphic Ötztal crystalline complex frequently contain pockets of clinohumite and chondrodite and their titanium-rich varieties. Chondrodites contain up to 9.1 wt% TiO₂ and clinohumites about half that amount. The maximum amounts of Ti in both minerals do not exeed values of 0.4 in the formula. XTi and X_F are correlated by a slope of –1, indicating the efficiency of the TiO₂Mg_–1F_–2 substitution at constant OH (Evans andTrommsdorff, 1983). Clinohumites sometimes contain lamellae which have nonstoichiometric cation ratios reflecting a composition between clinohumite and olivine. In many cases Ti-rich clinohumites and chondrodites coexist with Mg-ilmenite. Ti-rich clinohumites and chondrodites often break down to a symplectite of Ti-poor clinohumite (or olivine) and Mg-ilmenite. Parts of the marbles, which are barren of Mg-ilmenite contain F-rich clinohumites. The latter do not show any signs of breakdown features. We conclude therefore that fluorine stabilizes the humite group minerals to a wide range of metamorphic conditions. Ti-rich humite-group minerals are not stable till amphibolite facies conditions, and below F-rich humite-group minerals and olivine are the more stable phases in a H₂O-rich, SiO₂-poor carbonate system.

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Titanreiche Chondrodite und Klinohumite in Marmoren des Ötztalkristallins.

Zusammenfassung In Marmorlinsen des polymetamorphen Ötztalkristaliins kommen häufig titanarme und titanreiche Clinohumite und Chondrodite vor. Die höchsten Titan-Gehalte in Chondrodit betragen 9.1 Gew.-% TiO₂ während Clinohumite nur etwa die Hälfte dieses Wertes enthalten. Dies entspricht einem Maximalgehalt an Titan von 0.4 in den Formeln von Chondrodit und Clinohumit. Eine negative Korrelation zwischen X_Ti, und X_F mit der Steigung von –1 bestätigt die Wirksamkeit der Substitution TiO₂Mg_–1F_–2 bei konstantem OH (Evans undTrommsdorff, 1983). In Clinohumiten konnten nichtstöchiometrische Lamellen nachgewiesen werden, die chemisch zwischen Clinohumit und Olivin zusammengesetzt sind. Ti-reiche Clinohumite und Chondrodite koexistieren immer mit Mg-Ilmenit und wandeln sich häufig an ihren Rändern in einen Symplektit von Ti-ärmerem Clinohumit oder Olivin und Mg-Ilmenit um. In den Mg-Ilmenit freien Bereichen der Marmore kommen stets Ti-arme aber F-reiche Clinohumite vor, die niemals randliche Umwandlungserscheinungen zeigen. Die grobkörnigen (mm-großen) Humitminerale werden der variszischen Metamorphose in Amphibolitfazies zugeschrieben, während die Symplektite als Produkte der eoalpinen grünschieferfaziellen Überprägung angesehen werden. Wir schließen daraus, daß die Humitminerale durch Fluor in einem großen Bereich metamorpher Bedingungen stabilisiert werden, während Ti-reiche Humitminerale bei Bedingungen der Grünschieferfazies instabil werden und F-reiche Humitminerale und Olivin die stabilen Phasen in einem H₂O-reichen, SiO₂-armen Karbonatsystem sind.

     

Experimental study of the influence of water on elastic wave velocities in dunite and serpentinite (on the nature of the low-velocity zone in the upper mantle of the Earth)

Longitudinal wave velocities (V _P ) in rocks were measured experimentally in dunite (olivinite) and serpentinite at a water pressure of 300 MPa and temperatures of 20–850°C. It is shown that the strong decrease in V _P in dunite (by ~3 km/s) observed within the range of 400–800°C results from penetration of water into rock along microfractures and from the formation of hydrous minerals (mostly serpentine) along the boundaries of mineral grains as a result of water–olivine interaction. It is suggested that serpentinization or the formation of similar hydrous minerals in olivine-rich mantle rocks under the influence of deep fluids may result in the formation of zones of low-velocity elastic waves in the upper mantle at great depths (~100 km).     

Xenon and Argon: A contrasting behavior in olivine at depth

Xenon in the atmospheres of the Earth and Mars is characterized by a low abundance compared to other noble gases and by a depletion in light isotopes. By means of combined chemical analysis, in situ X-ray diffraction and Raman spectroscopy, we propose that Xe reacts with olivine at the high pressures and temperatures found in the upper mantle and in pre-terrestrial bodies. That provides a mechanism for the incorporation of Xe at depth and consequent isotopic fractionation. The substitution mechanism of Xe to Si depends on the type of silicate framework, forming XeO₂ molecules in fully polymerized phases of silica, and XeO₄ molecules in the isolated tetrahedra structure of olivine. Consequently, Xe retention in (Mg,Fe)₂SiO₄ olivine is less thermodynamically favored than in SiO₂, implying lesser amounts of Xe trapped in olivine. This chemistry does not extend to the lighter noble gas Ar in the investigated pressure range. The incorporation of both Xe and Ar in olivine is correlated to its trace element content likely through the formation of vacancies, a pre-requisite for the retention of Xe on tetrahedral sites and Ar on octahedral sites.     

OH-bearing planar defects in olivine produced by the breakdown of Ti-rich humite minerals from Dabie Shan (China)

The partial breakdown of Ti-chondrodite and Ti-clinohumite during exhumation from ultra-high pressure to amphibolite facies conditions in garnet-pyroxenites from Dabie Shan (China) produces coronas of olivine coexisting with ilmenite blebs. Fourier transform infrared (FTIR) spectra of this newly formed olivine exhibit absorption bands in the hydroxyl-stretching region. Two intense peaks were observed at 3,564 and 3,394 cm⁻¹, identical in energy to peaks in Ti-clinohumite. Transmission electron microscopy (TEM) of the same olivine domains revealed the presence of a complex (001) planar intergrowth. These interlayers have a 1.35 nm repeat distance, which is characteristic of clinohumite. Such interlayers are also enriched in Ti with respect to the adjacent olivine as shown by energy dispersive spectrometry. The combined evidence from FTIR spectroscopy and TEM indicates that OH is incorporated along Ti-clinohumite planar defects. This study provides evidence that the nominally anhydrous phase olivine may contain OH as a humite-type defect beyond the breakdown of the hydrous humite minerals and confirms earlier suggestions that Ti plays a key role in OH incorporation in mantle olivine. We suggest that olivine containing Ti-clinohumite defects is an important phase for water transport in subduction zones and for the storage of water in cold subcontinental mantle. However, these defects are unlikely to be stable in hotter parts of the oceanic mantle such as where basaltic magmas are generated.     

俯冲带蛇纹岩的变质过程

俯冲带蛇纹岩是俯冲带流体的重要来源,特别是其深部脱水作用对地幔动力学影响深远,是研究俯冲带约80~200km深度范围的地球动力学的关键,因此研究蛇纹岩的变质作用过程及其相关特征矿物(组合)的温压稳定范围具有重要意义。蛇纹岩具有简单的矿物(组合):蛇纹石类、硅镁石类、磁铁矿、氢氧镁石、绿泥石、橄榄石、透辉石、角闪石、滑石等,并且这些矿物(组合)对温压变化不敏感从而很难用来判定蛇纹岩所经历的变质演化轨迹。近几十年来,研究者通过实验岩石学和野外地质观察,主要研究了蛇纹石类矿物和硅镁石类矿物的温压稳定范围,并且试图使用这些特征矿物(组合)来判定俯冲带蛇纹岩的峰期变质条件。本文总结了蛇纹岩中这些主要矿物的温压稳定范围和相关变质反应,并且以中国西南天山蛇纹岩为例,展示使用特征矿物(组合)和叶蛇纹石Al等值线判定蛇纹岩峰期温压条件在实际岩石中的应用。另外,早期对叶蛇纹石的研究表明:随着温压条件的变化,叶蛇纹石的晶体结构会发生相应的调整。表现为单位晶胞内硅氧四面体的个数(m值)发生变化:温度升高,m值变小;压力升高,m值变大,这个发现在高压实验和天然样品中得到了一定程度的验证。本文利用已知峰期温压范围的叶蛇纹石样品分别采用粉末制样法和离子减薄制样法,进行透射电镜测试(TEM)样品的m值,并通过统计的方法获得叶蛇纹石的m值的峰值。结果显示叶蛇纹石的m值的峰值在一定程度上可以用以指示温压条件。本文提出可以用矿物组合、叶蛇纹石Al等值线和叶蛇纹石m值峰值相结合的方法确定蛇纹岩的变质温压条件和P-T轨迹。     

The natural occurrence of hydroxide in olivine

Polarized infrared (IR) spectra of olivine single crystals from 17 different localities show a tremendous variability in both mode and abundance of hydroxide (OH) incorporation. Kimberlitic olivines contain the most total OH at an estimated concentration level of 976 H/10⁶Si, whereas olivines from basalts contain the least at 3 H/10⁶Si. Olivines of metamorphic and hydrothermal origin have widely varying concentration levels intermediate between those of basalts and kimberlites. Over 30 distinct OH absorption bands have been identified. Most of these bands are not unique to individual localities but may be found in samples from several different localities. Pleochroism is consistent among localities, but relative band intensities vary. No evidence is found for molecular H₂ in olivine. Hydrous minerals have been identified in olivine by their characteristic OH absorption bands. Serpentine is commonly found and is clearly distinguishable from intrinsic OH. Talc is present in one sample. Prominent OH bands at 3572 and 3525 cm^?1 are attributed to humite group minerals. San Carlos, Arizona, olivines annealed in the presence of H₂O develop absorption bands which are found in natural samples, however the OH absorption spectra of these annealed olivines are not identical to those of any single natural crystal. Sharp-band OH abundances in annealed samples are an order of magnitude lower than the maximum measured in natural specimens. The mechanical properties determined from these annealed olivines may not be directly applicable to mantle olivine because both the OH sites and concentrations are different.     

Petrological constraints on seismic properties of the Slave upper mantle (Northern Canada)

Modes and compositions of minerals in Slave mantle xenoliths, together with their pressures and temperatures of equilibrium were used to derive model depth profiles of P- and S-wave velocities (Vp, Vs) for composites equivalent to peridotite, pyroxenite and eclogite. The rocks were modeled as isotropic aggregates with uniform distribution of crystal orientations, based on single-crystal elastic moduli and volume fractions of constituent minerals. Calculated seismic wave velocities are adjusted for in situ pressure and temperature conditions using (1) experimental P- and T- derivatives for bulk rocks' Vp and Vs, and (2) calculated P- and T- derivatives for bulk rocks' elastic moduli and densities. The peridotite seismic profiles match well with the globally averaged IASP91 model and with seismic tomography results for the Slave mantle. In peridotite, an observed increase of seismic wave velocities with depth is controlled by lower degrees of chemical depletion in the deeper upper mantle. In eclogite, seismic velocities increase more rapidly with depth than in peridotite. This follows from contrasting first-order pressure derivatives of bulk isotropic moduli for eclogite and peridotite, and from the lower compressibility of eclogite at high pressures. Our calculations suggest that depletion in cratonic mantle has a distinct seismic signature compared to non-cratonic mantle. Depleted mantle on cratons should have slower Vp, faster Vs and should show lower Poisson's ratios due to an orthopyroxene enrichment. For the modelled Slave craton xenoliths, the predicted effect on seismic wave velocities would be up to 0.05 km/s.     

Pressure-induced structural modifications in Mg2GeO4-olivine: A Raman spectroscopic study

Raman spectra of Mg₂GeO₄-olivine were obtained from ambient pressure up to 34 GPa at ambient temperature. Under quasi-hydrostatic pressure conditions, the following modifications in the Raman spectra occur as pressure increases: 1) near 11 GPa, two sharp extra bands appear in the 600–700 cm^?1 frequency range, and increase in intensity with respect to the olivine bands; 2) above 22 GPa, these two bands become very intense, and the number, position and relative intensity of the other vibrational bands drastically change; 3) the intensity of sharp bands progressively decreases above 25 GPa. The transformation occurs at lower pressures under non-hydrostatic conditions. During decompression to atmospheric pressure, the high-pressure phase partially reverts to olivine. These observations can be interpreted as the progressive metastable transformation from the olivine structure to a crystalline phase with four-fold coordinated Ge, in which the GeO₄ tetrahedra are polymerized. We propose that the metastable high-pressure phase is a structurally disordered spinelloid close to the hypothethical ω- or ?^*-phase, and forms by a shear mechanism assisted by the development of a dynamical instability in the olivine structure. Implications for the transformations undergone by olivines under far-from-equilibrium conditions (e.g. in subducting lithospheric slabs and in shocks) are discussed.     

High-temperature thermal expansion and elasticity of calcium-rich garnets

We present new high temperature elasticity data on two grossular garnet specimens. One specimen is single-crystal, of nearly endmember grossular, the other is polycrystalline with about 22% molar andradite. Our data extend the high temperature regime for which any garnet elasticity data are available from 1000 to 1350 K and the compositional range of temperature data to near endmember grossular. We also present new data on the thermal expansivity of calcium-rich garnet. We find virtually no discernable differences in the temperatureT derivatives at ambient conditions of the isotropic bulkK _S and shearμ moduli when comparing our results between these two specimens. These calcium-rich garnets have the lowest values of ¦(?K _S /?T) _P ¦ = (1.47,1.49) x 10^-2GPa/K, and among the highest values of ¦(?μ/?T) _P ¦ = 1.25 x 10^-2GPa/K, when compared with other garnets. Small, but measurable, nonlinear temperature dependences of most of the elastic moduli are observed. Several dimensionless parameters are computed with the new data and used to illustrate the effects of different assumptions on elastic equations of state extra-polated to high temperatures. We discuss how dimensionless parameters and other systematic considerations can be useful in estimating the temperature dependence of some properties of garnet phases for which temperature data are not yet available. While we believe it is premature to quantitatively predict the temperature variation ofK _S andμ for majorite garnets, our results have bearing on the amount of diopside required to explain the shear velocity gradients in Earth's transition zone.     

A model of the OH positions in olivine,derived from infrared-spectroscopic investigations

Polarized infrared (IR) spectroscopy of olivine crystals from Zabargad, Red Sea shows the existence of four pleochroic absorption bands at 3,590, 3,570, 3,520 and 3,230 cm^?1, and of one non pleochroic band at 3,400 cm^?1. The bands are assigned to OH stretching frequencies. Transmission electron microscopy (TEM) shows no oriented intergrowths in this olivine; it is concluded that OH is structural. On the basis of the pleochroic scheme of the absorption spectra it is proposed that [□O(OH)₃] and [□O₂(OH)₂] tetrahedra occur as structural elements, assuming that the vacancies are on Si sites. If M2 site vacancies were assumed [SiO₃(OH)] and [SiO₂(OH)₂] tetrahedra occur as structural elements.     

The cubic-tetragonal phase transition in the system majorite (Mg4Si4O12) – pyrope (Mg3Al2Si3O12), and garnet symmetry in the Earth's transition zone

 Garnets along the join Mg₄Si₄O₁₂ (majorite end member) – Mg₃Al₂Si₃O₁₂ (pyrope) synthesized at 2000 °C, 19 GPa are, after quench, tetragonal in the compositional range up to 20 mol% pyrope, but cubic at higher Al contents. Lattice constants a _tet and a _tet in the tetragonal compositional range converge with increasing pyrope contents towards the lattice constant of the cubic garnets. The elastic strain and the intensity of the (222) reflection as a function of composition indicate a second-order phase transition near 20 mol% pyrope. From the wedge-like shape of pseudomerohedral twins and their interaction near 90° twin-boundary corners, as well as from the absence of growth-induced dislocations, it is concluded that the Al-poor garnets are also cubic at synthesis conditions but invert by (Mg,Si) ordering on the octahedral sites into tetragonal phases of space group I4₁/a upon quench. This implies that the cubic-to-tetragonal phase transition in Mg₄Si₄O₁₂ garnet occurs below 2000 °C at 19 GPa and at even lower temperatures in more aluminous compositions. A composition-dependent Landau model is consistent with a direct transformation from Ia3d to I4₁/a. Comparison of the T-X stability field of majorite-pyrope garnets with the chemistry of majorite-rich garnets expected to occur in the Earth's transition zone shows that the latter will be cubic under all conditions. Softening of elastic constants, which commonly accompanies ferroelastic phase transitions, may affect the seismic velocities of garnets in the deeper transition zone where majorite contents are highest. Received July 5, 1996 / Revised, accepted September 24, 1996     

Elasticity of superhydrous B

The adiabatic single-crystal elastic moduli of superhydrous B, Mg₁₀Si₃O₁₄(OH)₄, have been measured at ambient conditions using Brillouin spectroscopy. This material is the first hydrous phase found to be stable at the extreme conditions of 20 GPa and 1400 °C. The single-crystal moduli, in GPa, are: C ₁₁=280.0±1.5, C ₂₂=307.4±1.6, C ₃₃=293.4±1.4, C ₄₄=90.0±1.1, C ₅₅=99.2±0.8, C ₆₆=89.6±0.6, C ₁₂=66.1±2.2, C ₁₃=105.6±2.6, C ₂₃=81.8±2.6. With aggregate elastic properties of K _VRH =154.0±4.2 and μ _VRH =97.0±0.7 GPa, superhydrous B is approximately 16% suffer than forsterite and 20% softer than magnesium silicate spinel; it is also considerably more elastically isotropic than forsterite. The single-crystal moduli are compared to those of forsterite, magnesium silicate spinel and periclase, materials that are both structurally and compositionally similar to superhydrous B. The longitudinal moduli of superhydrous B and forsterite follow similar trends and appear to be dominated by the incompressibility and rotation of silicon tetrahedra. The shear and off-diagonal moduli more closely resemble those of periclase and spinel and may reflect the properties inherent to layers of magnesium octahedra.     

Statistical approaches to the discrimination of mantle- and crust-derived low-Cr garnets using major and trace element data

Diamond exploration focuses on geochemical analysis of indicator minerals that are more abundant than diamond itself. Among such indicators, low-Cr (Cr₂O₃ < 1 wt%) garnets from mantle eclogites are problematic since they overlap compositionally with many lower-crust-derived garnets also transported by kimberlite. Misclassification of these garnets may create “false positive” mantle signatures and possible misdirection of exploration efforts. Statistical solutions using major elements in low-Cr garnet (Hardman et al. in J Geochem Explor 186:24–35, 2018) provide improved error rates for the discrimination of low-Cr crustal and mantle garnets recovered from kimberlite. In this study we analysed a large suite of garnets (n = 571) from both crustal and mantle settings, already characterised for major elements, for a wide range of trace elements by laser ablation inductively-coupled plasma mass spectrometry and use these new data along with literature data (n = 169) to evaluate the effectiveness of adding trace elements to garnet-based diamond exploration programs. A new garnet classification scheme, initially using a major-element based filter, uses garnet Sr contents and Eu anomalies to help identify low-Cr garnets that are misclassified using major element methods. Combined with existing methods, our new trace element classifiers offer improvement in classification error rates for low-Cr, crustal and mantle garnets to as low as 4.7% for calibration data.

     

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.     

The extrapolation of elastic moduli to high pressure and temperature

The elastic constants of a crystal under stress, defined as the second derivative of the crystal free energy with respect to strain, require a correction related to the static pressure at non-zero pressures. The corrections required for the elastic constants calculated by the free energy minimisation code PARAPOCS are described and tested by comparison with the elastic constants calculated numerically by applying small stresses in the appropriate orientations to simulated crystals of fluorite, forsterite, α-quartz and albite. The corrected elastic constants are then used to investigate the extrapolation of the bulk and shear moduli (and hence also the seismic wave velocities V _p and V _s) of β-spinel and forsterite to upper mantle pressures. A Murnaghan equation, thirdorder Eulerian finite strain equation, second order polynomial equation and a logistic equation were all fitted to the simulated bulk and shear moduli between 0 and 3 GPa pressure. The parameters derived for these equations are used to extrapolate the bulk and shear moduli to 14 GPa and the results are compared to the simulated high pressure moduli. Over this pressure range, the second order polynomial provides the best extrapolation of the bulk modulus, but the use of the logistic equation results in the best extrapolation of the shear modulus.     

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.     

The stability of hydrous phases beyond antigorite breakdown for a magnetite-bearing natural serpentinite between 6.5 and 11 GPa

Phase relations for a natural serpentinite containing 5 wt% of magnetite have been investigated using a multi-anvil apparatus between 6.5 and 11 GPa and 400–850 °C. Post-antigorite hydrous phase assemblages comprise the dense hydrous magnesium silicates (DHMSs) phase A (11.3 wt% H₂O) and the aluminous phase E (Al-PhE, 11.9 wt% H₂O). In addition, a ferromagnesian hydrous silicate (11.1 wt% H₂O) identified as balangeroite (Mg,Fe)₄₂Si₁₆O₅₄(OH)₄₀, typically described in low pressure natural serpentinite, was found coexisting with Al-PhE between 650 and 700 °C at 8 GPa. In the natural antigorite system, phase E stability is extended to lower pressures (8 GPa) than previously reported in simple chemical systems. The reaction Al-phase E?=?garnet?+?olivine?+?H₂O is constrained between 750 and 800 °C between 8 and 11 GPa as the terminal boundary between hydrous mineral assemblages and nominally anhydrous assemblages, hence restricting water transfer into the deep mantle to the coldest slabs. The water storage capacity of the assemblage Al-PhE?+?enstatite (high-clinoenstatite)?+?olivine, relevant for realistic hydrated slab composition along a relatively cold temperature path is estimated to be ca. 2 wt% H₂O. Attempts to mass balance run products emphasizes the role of magnetite in phase equilibria, and suggests the importance of ferric iron in the stabilization of hydrous phases such as balangeroite and aluminous phase E.     

Peridotite–eclogite–carbonatite systems at 7.0–8.5 GPa: concentration barrier of diamond nucleation and syngenesis of its silicate and carbonate inclusions

Diamond crystallization in multicomponent melts of variable composition is studied. The melt carbonates are K₂CO₃, CaCO₃?MgCO₃, and K-Na-Ca-Mg-Fe-carbonatites, and the melt silicates are model peridotite (60 wt.% olivine, 16 wt.% orthopyroxene, 12 wt.% clinopyroxene, and 12 wt.% garnet) and eclogite (50 wt.% garnet and 50 wt.% clinopyroxene). In the experiments carried out under the PT-conditions of diamond stability, the carbonate-silicate melts behave like completely miscible liquid phases. The concentration barriers of diamond nucleation (CBDN) in the melts with variable proportions of silicates and carbonates have been determined at 8.5 GPa. In the system peridotite–K₂CO₃–CaCO₃?MgCO₃–carbonatite they correspond to 30, 25, and 30 wt.% silicates, respectively, and in the analogous eclogite–carbonate system, 45, 30, and 35 wt.%. In the silicate-carbonate melts with higher silicate contents seed diamond growth occurs, which is accompanied by the crystallization of thermodynamically unstable graphite phase. In the experiments with melts compositionally corresponding to the CBDN at 7.0 GPa and 1200–1700 °C, a full set of silicate minerals of peridotite (olivine, orthopyroxene, clinopyroxene, garnet) and eclogite (garnet, clinopyroxene) parageneses was obtained. The minerals occur as syngenetic inclusions in natural diamonds; moreover, the garnets contain an impurity of Na, and the pyroxenes, K. The experimental data indicate that peridotite-carbonate and eclogite-carbonate melts are highly effective for the formation of diamond (or unstable graphite) together with syngenetic minerals and melts, which agrees with the carbonate-silicate (carbonatite) model for the mantle diamond formation.