Structure and crystal chemistry of hydrous wadsleyite, Mg1.75SiH0.5O4: possible hydrous magnesium silicate in the mantle transition zone

The crystal structure of hydrous wadsleyite, Mg_1.75SiH_0.5O₄ synthesized in an MA 8-type apparatus at conditions of 1300°C and 15.5 GPa, has been analyzed and refined in space group Imma, using the X-ray intensities measured on a 60X60X10 μm single crystal. The composition (Z=8) and unit cell are Mg_1.74Si_0.97H_0.65O₄ by E.P.M.A. analysis and a=5.663(1) Å, b= 11.546(2) Å, c=8.247(4) Å, V=539.2(5) ų. The partial M-site occupancies were determined; vacancies associated with the incorporation of water are strongly concentrated on the Mg 3 site. The OH in the structure was confirmed by Raman and FTIR spectroscopies. The result of valence sum calculation based on the refined bond lengths indicates that O1 is a hydroxyl. The formula of hydrous wadsleyite can be expressed as Mg_2-xSiH_2xO₄, where 0≤x≤0.25. When x=0.25, all of the O1 site is hydroxyl and the maximum solubility of 3.3 wt% H₂O is realized. Structural relations to other dense hydrous phases are discussed.     

High-pressure Raman spectroscopic study of Fo90 hydrous wadsleyite

Raman spectra of monoclinic Fo₉₀ hydrous wadsleyite with 2.4 wt% H₂O have been measured in a diamond-anvil cell with helium as a pressure-transmitting medium to 58.4 GPa at room temperature. The most intense, characteristic wadsleyite modes, the Si–O–Si symmetric stretch at 721 cm⁻¹ and the symmetric stretch of the SiO₃ unit at 918 cm⁻¹, shift continuously to 58.4 GPa showing no evidence of a first order change in the crystal structure despite compression well beyond the stability field of wadsleyite in terms of pressure. The pressure dependence of these two modes is nearly identical for Fo₉₀ hydrous and Fo₁₀₀ anhydrous wadsleyite. A striking feature in the high-pressure Raman spectra of Fo₉₀ hydrous wadsleyite is the appearance of new Raman modes above 9 GPa in the mid-frequency range (300–650 cm⁻¹ at 1-bar and shifted to 500–850 cm⁻¹ at 58.4 GPa) accompanied by a significant growth in their intensities under further compression. In the OH stretching frequency range Fo₉₀ hydrous wadsleyite exhibits a larger number of modes than the Mg end-member phase. The higher number of modes may be due to either additional protonation sites or simply that we observe a different subset of all possible OH modes for each sample. The high-pressure behaviour of the OH stretching modes of Fo₉₀ and Fo₁₀₀ hydrous wadsleyite is consistent: OH stretching modes with frequencies <3,530 cm⁻¹ decrease with increasing pressure whereas the higher-frequency OH modes show a close to constant pressure dependence to at least 13.2 GPa. The approximately constant pressure dependence of the OH modes above 3,530 cm⁻¹ is consistent with protons being located at the O1···O edges around M3.     

Mg-vacant structural modules and dilution of the symmetry of hydrous wadsleyite, β-Mg2–xSiH2xO4 with 0.00≤x≤0.25

The crystal structures of the two hydrous wadsleyite crystals with formulae, Mg_1.75SiH_0.50O₄ (0.5H–β) and Mg_1.86SiH_0.28O₄ (0.3H–β) have been analyzed in this study. The single-crystal X-ray diffraction data showed that the unit cells of the 0.3H–β and the 0.5H–β are metrically monoclinic with a slight distortion from the orthorhombic cell but their intensity distributions conform to the orthorhombic symmetry within the limit of experimental errors. The Fourier and the difference Fourier syntheses were calculated. Small but significant Fourier peaks were found at the site, Si2, in a normally vacant tetrahedral void adjacent to Mg3 site as reported for the monoclinic hydrous wadsleyite by Smyth et al.. From the comparison of the hydrous and anhydrous wadsleyite structures, the Mg-vacant structural modules were found to be the building units for the structure of hydrous wadsleyite. The dilution of symmetry from orthorhombic to monoclinic in the hydrous wadsleyite structure is interpreted qualitatively due to lack of mirror perpendicular to the a axis in the module. The mode of arrangement of the Mg-vacant structural modules interprets the symmetry and hydrogen content of the hydrous wadsleyite and gives the structural relationship between hydrous wadsleyite and hydrous ringwoodite. Received: 8 May 1998 / Revised, accepted: 3 October 1998     

Partial dehydration of brucite and its implications for water distribution in the subducting oceanic slab

Hydrous minerals within the subducting oceanic slab are important hosts for water. Clarification of the stability field of hydrous minerals helps to understand transport and distribution of water from the surface to the Earth’s interior. We investigated the stability of brucite, a prototype of hydrous minerals, by means of electrical conductivity measurements in both open and closed systems at 3 GPa and temperatures up to 1300 K. Dramatic increase of conductivity in association with characteristic impedance spectra suggests that partial dehydration of single-crystal brucite in the open system with a low water fugacity occurs at 950 K, which is about 300 K lower than those previously defined by phase equilibrium experiments in the closed system. By contrast, brucite completely dehydrates at 1300 K in the closed system, consistent with previous studies. Partial dehydration may generate a highly defective structure but does not lead to the breakdown of brucite to periclase and water immediately. Water activity plays a key role in the stability of hydrous minerals. Low water activity (aH₂O) caused by the high wetting behavior of the subducted oceanic slab at the transition zone depth may cause the partial dehydration of the dense hydrous magnesium silicates (DHMSs), which significantly reduces the temperature stability of DHMS (this mechanism has been confirmed by previous study on super hydrous phase B). As a result, the transition zone may serve as a ‘dead zone’ for DHMSs, and most water will be stored in wadsleyite and ringwoodite in the transition zone.     

Structural relation of hydrous ringwoodite to hydrous wadsleyite

The sequential displacement mechanism based on the oxygen-lattice cubic closest packing (c.c.p.) in the < 2 0 1 > direction was proposed in this study. All displacements of cations are within the OT and the O layers with the length of displacement vector being around 1.7 or 2.9 Å, contrary to displacement of around 5.0 Å for models proposed previously. The difference in atomic arrangement between hydrous wadsleyite and hydrous ringwoodite is small. The atomic arrangement of the O layer of hydrous wadsleyite is essentially the same as that of hydrous ringwoodite when Mg vacancies preferentially exist in the O layer. The partial occupancies of normally vacant tetrahedral sites reported in the hydrous-β and hydrous-γ structures may possibly be caused by the existence of Mg vacancies at the octahedral sites through phase transition from hydrous-β to hydrous-γ or from hydrous-γ to hydrous-β phases.     

Oxygen isotope fractionation between hydroxide minerals and water

The modified increment method has been applied to the calculation of oxygen isotope fractionation factors for hydroxide minerals. The results suggest the following sequence of ¹⁸O-enrichment in the common hydroxides: limonite > gibbsite > goethite > brucite > diaspore. The hydroxides are significantly enriched in ¹⁸O relative to the corresponding oxides. The sequence of ¹⁸O-enrichment in the hydroxides and oxides of trivalent cations is as follows: M(OH)₃ > MO(OH) > M₂O₃. There are also considerable fractionations within the polymorphos of Al(OH)₃. The internally consistent fractionation factors for hydroxide–water systems are obtained for the temperature range of 0 to 1200 °C, which are comparable with the data derived from synthesis experiments and natural samples at surficial temperatures. Temperature dependence of oxygen isotope fractionations between goethite, gibbsite, boehmite and diaspore and water are significant enough for the purpose of geothermometry. Thus the hydroxide–water pairs hold great promise of serving as reliable paleothermometers in surficial geological environments. Received: 22 January 1997 / Revised, accepted: 2 June 1997     

Thermodynamic properties and phase stability of wadsleyite II

The thermodynamical stability of a newly observed wadsleyite II phase in the Mg₂SiO₄ system is studied by the density functional theory. The wadsleyite II equation of state has been derived. The phase boundaries of Mg₂SiO₄ polymorphs: wadsleyite, wadsleyite II and ringwoodite are studied using the quasi-harmonic approximation at high external pressures. Clapeyron slopes determined for wadsleyite II–ringwoodite and wadsleyite–wadsleyite II boundaries are 0.0047 and 0.0058 GPa/K, respectively. It is shown that the wadsleyite II phase is not thermodynamically preferred in the pure Mg₂SiO₄ system and will probably not occur between wadsleyite and ringwoodite phases.     

High pressure elasticity and phase transformation in brucite, Mg(OH)2

The first pressure derivatives of the second-order elastic constants have been calculated for brucite, Mg(OH)₂ from the second- and third-order elastic constants. The deformation theory and finite strain elasticity theory have been used to obtain the second- and third-order elastic constants of Mg(OH)₂ from the strain energy of the lattice. The strain energy ϕ is calculated by taking into account the interactions up to third nearest neighbors in the Mg(OH)₂ lattice. ϕ is then compared with the strain dependent lattice energy from continuum model approximation to obtain the expressions of elastic constants. The complete set of six second-order elastic constants C _IJ of brucite exhibits large anisotropy. Since C ₃₃ (= 21.6 GPa), which corresponds to the strength of the material along the c-axis direction, is less than the longitudinal mode C ₁₁ (= 156.7 GPa), the interlayer binding forces are weaker than the binding forces along the basal plane of Mg(OH)₂. The 14 nonvanishing components of the third-order elastic constants, C _IJK , of brucite have been obtained. All the C _IJK of brucite are negative except the values of C ₁₁₄ (= 230.36 GPa), C ₁₂₄ (= 75.45 GPa) and C ₁₃₄ (= 36.98 GPa). The absolute values of the C _IJK are, in general, one order of magnitude greater than the C _IJ ’s in the Mg(OH)₂ system as usually expected for a crystalline material. To our knowledge, no previous data are available to compare the pressure derivatives of brucite. The pressure derivatives of the two components viz., C ₁₄ and C ₃₃ become negative indicating an elastic instability in brucite while under pressure. This may be related to the phase transition of brucite largely involving rearrangements of H atoms revealed in the Raman spectroscopic, powder neutron diffraction and synchrotron X-ray diffraction studies.     

Compression mechanism and amorphization of portlandite, Ca(OH)2: structural refinement under pressure

In order to investigate compression mechanism and the pressure-induced amorphization of portlandite, Ca(OH)₂, the crystal structure has been refined up to 9.7?GPa using Rietveld analysis. Angular-dispersive synchrotron X-ray powder diffraction experiments were performed using a diamond anvil cell and an imaging plate at BL-18C in the Photon Factory at KEK, Japan. Compression behavior is highly anisotropic and the c axis is approximately 2.5 times as compressible as the a axis (β_a=0.004, β_c=0.011?GPa^?1). Because the refined fractional coordinate, z, of the O atom increases linearly with pressure, compression along the c axis is due to the shortening of the interlayer spacing. The compression mechanism shows no change up to the amorphization pressure and is basically the same as that of brucite, Mg(OH)₂, observed below 10 GPa. The octahedral regularity of CaO₆ approaches a regular configuration with pressure. The interlayer O…O distance is expected to be about 2.75 Å at the amorphization pressure and should affect hydrogen bonding.     

The effect of γ-irradiation on the structure and subsequent thermal decomposition of brucite

The effect of γ-irradiation on the structure, phase composition and kinetics of isothermal decomposition of natural textural brucite Mg(OH)₂ has been investigated by Mn²⁺ electron paramagnetic resonance (EPR), proton magnetic resonance (PMR), X-ray diffraction (XRD) and weight loss methods. Starting from a 10⁶-Gy dose, γ-irradiation (⁶⁰Co, 13.8 Gys^?1) is found to stimulate the formation of a new phase in the brucite structure, namely basic magnesium carbonate. The carbonate phase is assumed to form in brucite under γ-irradiation accordingly to the scheme \(\) (in the brucite structure). There is also a possibility that γ-irradiation forms particles with high reaction ability, CO^?₂ radicals and/or CO molecules, which can react with the brucite structure. Preliminary γ-irradiation (9.75 × 10⁷ Gy) slows down the subsequent isothermal dehydroxylation of natural brucite, which can be explained by the formation of the new carbonate phase in the Mg(OH)₂ structure. Dehydroxylation kinetics of both original and irradiated samples are interpreted by a two-stage nucleation model at 623, 648, 673, 698 and 723 K. The reaction rate is limited by the first nucleation stage rate (proton transition from an OH group near the reaction interface on a freed vacant orbital of an oxygen ion of the OH group in the nearest elementary cell, i.e., formation of a structured water molecule). The second-stage rate (water molecule removal from the structure and proton migration from the residual hydroxyl inside the structure) is about 1 order of magnitude higher. The activation energy of the limiting stage is 194 and 163 kJ mol^?1 for the original and irradiated samples, respectively. Non-linear Arrhenius dependencies for the first-stage rate constants are related to the potential barrier reduction due to thermal fluctuations of large structural zones (with radii of about 20 and 81 Å in original and irradiated samples, respectively), whose ions form this barrier.     

Stability of various hydrous phases in CMAS pyrolite-H<Subscript>2</Subscript>O system up to 25 GPa

 We carried out a series of melting experiments with hydrous primitive mantle compositions to determine the stability of dense hydrous phases under high pressures. Phase relations in the CaO–MgO–Al₂O₃–SiO₂ pyrolite with ˜2 wt% of water have been determined in the pressure range of 10–25 GPa and in the temperature range between 800 and 1400 °C. We have found that phase E coexisting with olivine is stable at 10–12 GPa and below 1050 °C. Phase E coexisting with wadsleyite is stable at 14–16 GPa and below 900 °C. A superhydrous phase B is stable in pyrolite below 1100 °C at 18.5 GPa and below 1300 °C at 25 GPa. No hydrous phases other than wadsleyite are stable in pyrolite at 14–17 GPa and 900–1100 °C, suggesting a gap in the stability of dense hydrous magnesium silicates (DHMS). We detected an expansion in the stability field of wadsleyite to lower pressures (12 GPa and 1000 °C). The H₂O content of wadsleyite was found to decrease not only with increasing temperature but also with increasing pressure. The DHMS phases could exist in a pyrolitic composition only under the conditions present in the subducting slabs descending into the lower mantle. Under the normal mantle and hot plume conditions, wadsleyite and ringwoodite are the major H₂O-bearing phases. The top of the transition zone could be enriched in H₂O in accordance with the observed increase in water solubility in wadsleyite with decreasing pressure. As a consequence of the thermal equilibration between the subducting slabs and the ambient mantle, the uppermost lower mantle could be an important zone of dehydration, providing fluid for the rising plumes. Received: 9 September 2002 / Accepted: 11 January 2003 Acknowledgements The authors are thankful to Y. Ito for the assistance with the EPMA measurement, A. Suzuki, T. Kubo and T. Kondo for technical help with the high-pressure experiments and Raman and X-ray diffraction measurements and C.R. Menako for technical support. K. Litasov thanks H. Taniguchi for his continuous encouragement and the Center for Northeast Asian Studies of Tohoku University and the Japanese Society for the Promotion of Science for the research fellowships. This work was partially supported by the Grant-in-Aid of Scientific Research of the Priority Area (B) of the Ministry of Education, Science, Sport, and Culture of the Japanese government (no. 12126201) to E. Ohtani.     

Coalingite from kimberlite breccia of the Manchary pipe,Central Yakutia

Coalingite, Mg₁₀Fe₂(CO₃)(OH)₂₄ · 2H₂O, rare Mg–Fe hydrous carbonate, has been found in the course of the mineralogical study of a disintegrated kimberlite breccia from the Manchary pipe of the Khompu–May field located in the Tamma Basin, Central Yakutia, 100 km south of Yakutsk. Coalingite occurs as small reddish brown platelets, up to 0.2 mm in size. It is associated with lizardite, chrysotile and brucite, which are typical kimberlitic assemblage. Coalingite is a supergene mineral, but in this case, it is produced by the interaction of brucite-bearing kimberlite and underground water circulating through a vertical or oblique fault zone.     

High-pressure neutron diffraction study on H–D isotope effects in brucite

A neutron powder diffraction study of hydrogenated and deuterated brucite was conducted at ambient temperature and at pressures up to 9 GPa, using a Paris–Edinburgh high-pressure cell at the WAND instrument of the ORNL High Flux Isotope Reactor. The two materials were synthesized by the same method and companion measurements of neutron diffraction were conducted under the same conditions. Our refinement results show that the lattice-parameters of the a axis, parallel to the sheets of Mg–O octahedra, decrease only slightly with pressure with no effect of H–D substitution. However, the c axis of Mg(OD)₂ is shorter and may exhibit greater compressibility with pressure than that of Mg(OH)₂. Consequently, the unit-cell volume of deuterated brucite is slightly, but systematically smaller than that of hydrogenated brucite. When fitted to a third-order Birch–Murnaghan equation in terms of the normalized unit-cell volume, values of the bulk modulus for hydrogenated and deuterated brucite (K ₀ = 39.0 ± 2.8 and 40.4 ± 1.3 GPa, respectively) are, however, indistinguishable from each other within the experimental errors. The measured effect of H–D substitution on the unit-cell volume also demonstrates that brucite (and other hydrous minerals) preferentially incorporate deuterium over hydrogen under pressure, suggesting that the distribution of hydrogen isotopes in deep-earth conditions may differ significantly from that in near-surface environments.     

Thermal expansion of Mg(OH)<Subscript>2</Subscript> brucite under high pressure and pressure dependence of entropy

An equation of state for Mg(OH)₂ brucite under high-pressure and high-temperature conditions has been obtained by measuring temperature dependence of volume up to 600 K at ambient pressure and pressure dependence of volume up to 16 GPa at 300, 473, 673, and 873 K with in situ X-ray diffraction. Pressure dependence of entropy of brucite has been calculated with thermal expansion coefficient and volume which are derived from the present EoS. This dependence indicates that generation of secondary OH dipoles affects entropy. The OH dipoles probably appear around 2 GPa and the number seems not to change over 8 GPa at 300 K.     

X射线衍射法分析水镁石煅烧制备的镁砂物相组成

研究了离子色谱法同时测定砂岩型铀矿浸出液中阳离子的方法。采用Ionpac CS12A阳离子分离柱,以20 mmol/L甲基磺酸(MSA)为淋洗液,直接电导检测-离子色谱法分离测定铀矿石浸出液中常见的阳离子(Li+、Na+、K+、NH4+、Ca2+、Mg2+),方法检出限为0.012 7~0.194 mg/L,相对标准偏差(RSD,n=5)为1.04%~4.50%,加标回收率为91.5%~106.0%。该方法用于铀矿石浸出液中的阳离子同时测定,具有很好的实用性。     

Hydrogen sites in the dense hydrous magnesian silicate phase E: a pulsed neutron powder diffraction study

Hydrogen site positions and occupancy in the crystal structure of dense hydrous magnesium silicate (DHMS) phase E were determined for the first time by pulsed neutron powder diffraction. A fully deuterated pure phase E powder sample, which had space group \(R\overline{3} m\) and lattice parameters of a = 2.97065(8) Å and c = 13.9033(4) Å, was synthesized at 15 GPa and 1100 °C. Through quantitative evaluation of refined structure parameters obtained with sufficient spatial resolution and very high signal-to-background ratio, we conclude that the O–D dipoles in the refined phase E structure are tilted by 24° from the direction normal to the layers of edge-shared MgO₆ octahedra (octahedral layers). The tilted dipole structure of phase E is in remarkable contrast to that of brucite, Mg(OH)₂, which has dipoles exactly normal to the octahedral layer. This contrast exists because the O–Si–O bonding unique in the phase E structure connects two adjacent octahedral layers and thereby reduces the interlayer O···O distance. This shrinkage of the interlayer distance induces the tilting of the O–D dipole and also generates unique O–D···O hydrogen bonding connecting all the layers in the phase E structure.     

A new hydrous phase δ-AlOOH synthesized at 21 GPa and 1000 °C

A new phase of AlOOH (tentatively called δ-AlOOH) was synthesized at 21?GPa and 1000?°C and its crystal structure was identified by a powder X-ray diffraction method. Rietveld refinement revealed that this aluminum oxide hydroxide has an orthorhombic unit cell, a?=?4.7134(1) Å, b?=?4.2241(1) Å, c?=?2.83252(8) Å, V?=?56.395 (5) ų, and Z?=?2 in the space group of P2₁?nm. A calculated density is 3.533?g?cm^?3, which is about 4.48 and 15.04% denser than that of diaspore and boehmite, respectively. The δ-[Al_0.86Mg_0.07Si_0.07]OOH is also stable at 21?GPa and 1000?°C, coexisting with majorite and phase egg, and its cell parameters are a?=?4.710(1) Å, b?=?4.215(1) Å, c?=?2.839(1) Å, and V?=?56.37(1) ų.     

Simulation of screw dislocations in wadsleyite

The structure and energies of the cores of [100] and [001] screw dislocations in wadsleyite (β-Mg₂SiO₄) are calculated using a cluster-based combined elastic-atomistic method and a new parameterized interatomic potential model. For a core radius of 10 Å, core energies are found to be 2.5 and 4.4 eV/Å for the [100] and [001] dislocations, respectively. Both dislocations are associated with significant non-elastic displacement fields extending beyond the core with a radial component toward the dislocation line. The core of the [100] dislocation contains tetrahedrally coordinated magnesium, has a simple 2D structure and is spread parallel to (011) in a manner that suggests high mobility. In contrast, the core of the [001] dislocation has an extended and complex 3D structure involving the formation a large Si₆O₁₉ unit twisted around the dislocation line. This implies that movement of the [001] dislocation will be inhibited by the need to cleave Si–O bonds. These observations, combined with the anomalously low core energy of the [100] dislocation, explain the regular occurrence of [100] dislocations and very rare observation of [001] dislocations in experimentally deformed wadsleyite samples.     

Stability of dense hydrous magnesium silicate phases in the systems Mg2SiO4-H2O and MgSiO3-H2O at pressures up to 27 GPa

We conducted high-pressure phase equilibrium experiments in the systems MgSiO₃ with 15 wt% H₂O and Mg₂SiO₄ with 5 wt% and 11 wt% H₂O at 20 ∼ 27 GPa. Based on the phase relations in these systems, together with the previous works on the related systems, we have clarified the stability relations of dense hydrous magnesium silicates in the system MgO-SiO₂-H₂O in the pressure range from 10 to 27 GPa. The results show that the stability field of phase G, which is identical to phase D and phase F, expands with increasing water contents. Water stored in serpentine in the descending cold slabs is transported into depths greater than 200 km, where serpentine decomposes to a mixture of phase A, enstatite, and fluid. Reaction sequences of the hydrous phases which appear at higher pressures vary with water content. In the slabs with a water content less than about 2 wt%, phase A carries water to a depth of 450 km. Hydrous wadsleyite, hydrous ringwoodite, and ilmenite are the main water reservoirs in the transition zone from 450 to 660 km. Superhydrous phase B is the water reservoir in the uppermost part of the lower mantle from 670 to 800 km, whereas phase G appears in the lower mantle only at depths greater than 800 km. In cold slabs with local water enrichment greater than 2 wt%, the following hydrous phases appear with increasing depths; phase A to 450 km, phase A and phase G from 450 km to 550 km, brucite, superhydrous phase B, and phase G from 550 km to 800 km, and phase G at depths greater than 800 km. Received: 4 August 1999 / Accepted: 1 March 2000     

On Silica Activity and Serpentinization

Serpentinites have the lowest silica activity of common crustalrocks. At the serpentinization front, where olivine, serpentine,and brucite are present, silica activities (relative to quartz)are of the order of 10^–2·5 to 10^–5, dependingon the temperature. Here we argue that this low silica activityis the critical property that produces the unusual geochemicalenvironments characteristic of serpentinization. The formationof magnetite is driven by the extraction of silica from theFe₃Si₂O₅(OH)₄ component of serpentine, producing extremely reducingconditions as evinced by the rare iron alloys that partiallyserpentinized peridotites contain. The incongruent dissolutionof diopside to form Ca²⁺, serpentine, and silica becomes increasinglyfavored at lower T, producing the alkalic fluids characteristicof serpentinites. The interaction of these fluids with adjacentrocks produces rodingites, and we argue that desilication isalso part of the rodingite-forming process. The low silica activityalso explains the occurrence of low-silica minerals such ashydrogrossular, andradite, jadeite, diaspore, and corundum inserpentinites or rocks adjacent to serpentinites. The tendencyfor silica activity to decrease with decreasing temperaturemeans that the presence of certain minerals in serpentinitescan be used as indicators of the temperature of serpentinization.These include, with decreasing temperature, diopside, andraditeand diaspore. Because the assemblage serpentine + brucite marksthe lowest silica activity reached in most serpentinites, thepresence and distribution of brucite, which commonly is a crypticphase in serpentinites, is critical to interpreting the processesthat lead to the hydration of any given serpentinite. KEY WORDS: serpentinization; serpentinites; silica activity; oxygen fugacity; rodingites; magnetization of serpentinites