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.     

The importance of defining chemical potentials,substitution mechanisms and solubility in trace element diffusion studies: the case of Zr and Hf in olivine

The diffusion, substitution mechanism and solubility limits of Zr and Hf in synthetic forsterite (Mg₂SiO₄) and San Carlos olivine (Mg_0.9Fe_0.1)₂SiO₄ have been investigated between 1,200 and 1,500 °C as a function of the chemical potentials of the components in the system MgO(FeO)–SiO₂–ZrO₂(HfO₂). The effect of oxygen fugacity and crystallographic orientation were also investigated. The solubilities of Zr in forsterite are highest and diffusion fastest when the coexisting three-phase source assemblage includes ZrSiO₄ (zircon) or HfSiO₄ (hafnon), and lower and slower, respectively, when the source assemblage includes MgO (periclase). This indicates that Zr and Hf substitute on the octahedral sites in olivine, charge balanced by magnesium vacancies. Diffusion is anisotropic, with rates along the crystal axes increasing in the order a < b < c. The generalized diffusion relationship as a function of chemical activity (as \(a_{{{\text{SiO}}_{2} }}\)), orientation and temperature is: \(logD_{\text{Zr}} = \frac{1}{4}loga_{{{\text{SiO}}_{2} }} + logD_{0} - \left( {\frac{{368 \pm 17\;{\text{kJ}}\;{\text{mol}}^{ - 1} }}{{2.303\;{\text{RT}}}}} \right)\) where the values of log D ₀ are ?3.8(±0.5), ?3.4(±0.5) and ?3.1(±0.5) along the a, b and c axes, respectively. Most experiments were conducted in air (fO₂ = 10^?0.68 bars), but one at fO₂ = 10^?11.2 bars at 1,400 °C shows no resolvable effect of oxygen fugacity on Zr diffusion. Hf is slightly more soluble in olivine than Zr, but diffuses slightly slower. Diffusivities of Zr in experiments in San Carlos olivine at 1,400 °C, fO₂ = 10^?6.6 bars are similar to those in forsterite at the same conditions, showing that the controls on diffusivities are adequately captured by the simple system (nominally iron-free) experiments. Diffusivities are in good agreement with those measured by Spandler and O’Neill (Contrib Miner Petrol 159:791–818, 2010) in San Carlos olivine using silicate melt as the source at 1,300 °C, and fall within the range of most measurements of Fe–Mg inter-diffusion in olivine at this temperature. Forsterite–melt partitioning experiments in the CaO–MgO–Al₂O₃–SiO₂–ZrO₂/HfO₂ show that the interface concentrations from the diffusion experiments represent true equilibrium solubilities. Another test of internal consistency is that the ratios of the interface concentrations between experiments buffered by Mg₂SiO₄ + Mg₂Si₂O₆ + ZrSiO₄ or Mg₂SiO₄ + ZrSiO₄ + ZrO₂ (high silica activity) to those buffered by Mg₂SiO₄ + MgO + ZrO₂ (low silica activity) agree well with the ratios calculated from thermodynamic data. This study highlights the importance of buffering chemical potentials in diffusion experiments to provide constraints on the interface diffusant concentrations and hence validate the assumption of interface equilibrium.     

Cation diffusion in olivine—II. Ni-Mg,Mn-Mg,Mg and Ca

Diffusivities of bivalent cations. Mg, Ni. Mn and Ca, in olivine were determined experimentally. The diffusivities of Ni and Mn in forsterite were determined by couple annealing between Ni₂SiO₄ and Mg₂SiO₄, and Mn₂SiO₄ and Mg₂SiO₄, respectively. The diffusivities of Mg and Ca in forsterite were determined by the use of ²⁶Mg and Ca tracers, respectively. Combined with other published results, the diffusion coefficients for bivalent cation diffusion in pure forsterite along the c crystallographic axis range from 2.45 × 10^?11 to 1.4 × 10^?13 cm² sec^?1 at 1200°C, in the order of Fe > Mn > Co > Ni > Mg > Ca. The results suggest that the diffusivity is governed by at least two factors, i.e. the size of the diffusing ionic species and the change of defect density in the crystal structure which is induced by substitution of diffusing ion for Mg ion.     

Serpentinites and their tectonic signature along the Northwest Zagros Thrust Zone, Kurdistan Region, Iraq

Two types of serpentinized peridotites are distinguished within the Northwest Zagros Thrust Zone (NW-ZTZ) in Kurdistan region of Iraq. One is found as lower members of ophiolite sequences, such as the Mawat and Penjwin ophiolites of the upper Cretaceous age. The other is represented by intraformational isolated serpentinite bodies in Betwat, Qaladeza, and Qalander areas within the Walash–Naopurdan volcano-sedimentary unit of the Paleocene to Eocene paleo-arc tectonic setting. Serpentinites within the NW-ZTZ consist mainly of lizardite and chrysotile, with subordinate amounts of syn-serpentinization magnetite, carbonates, chromium chlorite, tremolite, and talc as secondary minerals, and olivine, clinopyroxene, and chromian spinel as primary minerals. Minor antigorite is also found in the sheared serpentinites often found in ophiolite sequences. Petrological and geochemical studies of serpentinites from the NW-ZTZ show that, of the original protoliths of serpentinites, those associated with ophiolites are residual depleted harzburgite and dunite. The $ {\text{Cr}}\# \left( {{{ = {\text{ Cr}}} \mathord{\left/ {\vphantom {{ = {\text{ Cr}}} {\left( {{\text{Cr}} + {\text{Al}}} \right){\text{ atomic ratio}}}}} \right. \kern-0em} {\left( {{\text{Cr}} + {\text{Al}}} \right){\text{ atomic ratio}}}}} \right) $ of chromian spinel is more than 0.6, and the forsterite content of olivine is 91–92. On the other hand, the original protolith of isolated serpentinite bodies is less depleted harzburgite or depleted lherzolite, which has spinel with Cr# less than 0.6 and olivine with 90–91 forsterite contents. Whole rock chemistry of major, trace, and rare earth elements shows that the serpentinites of ophiolite sequences are depleted in CaO, Al₂O₃, and SiO₂, Sr, and Zr, and are enriched in MgO, Ni, and Cr, in comparison with the isolated serpentinites. Cr# of the disseminated unaltered chromian spinels indicates that the serpentinites of both types had been originated from the supra-subduction zone tectonic setting; the serpentinites of ophiolite sequences obducted and thrusted over the continental margin during the obduction of the Tethyth oceanic crust onto the Arabian continental margin during the upper Cretaceous period. Isolated serpentinite bodies represent serpentinized forearc mantle wedge peridotites emplaced by diapiric upwelling into non-accretionary forearc tectonic settings during the Paleocene to Eocene age.     

The effect of silica activity on the diffusion of Ni and Co in olivine

The diffusion of Ni and Co was measured at atmospheric pressure in synthetic monocrystalline forsterite (Mg₂SiO₄) from 1,200 to 1,500 °C at the oxygen fugacity of air, along [100], with the activities of SiO₂ and MgO defined by either forsterite + periclase (fo + per buffer) or forsterite + protoenstatite (fo + en buffer). Diffusion profiles were measured by three methods: laser-ablation inductively-coupled-plasma mass-spectrometry, nano-scale secondary ion mass spectrometry and electron microprobe, with good agreement between the methods. For both Ni and Co, the diffusion rates in protoenstatite-buffered experiments are an order of magnitude faster than in the periclase-buffered experiments at a given temperature. The diffusion coefficients D _M (M = Ni or Co) for the combined data set can be fitted to the equation:

$$\log \,D_{\text{M}} \,\left( {{\text{in}}\,{\text{m}}^{2} \,{\text{s}}^{ - 1} } \right) = - 6.77( \pm 0.33) + \Delta E_{\text{a}} (M)/RT + 2/3\log a_{{SiO_{2} }}$$

with E_a(Ni) = ? 284.3 kJ mol^?1 and E_a(Co) = ? 275.9 kJ mol^?1, with an uncertainty of ±10.2 kJ mol^?1. This equation fits the data (24 experiments) to ±0.1 in log D _M. The dependence of diffusion on \(a_{{{\text{SiO}}_{2} }}\) is in agreement with a point-defect model in which Mg-site vacancies are charge-balanced by Si interstitials. Comparative experiments with San Carlos olivine of composition Mg_1.8Fe_0.2SiO₄ at 1,300 °C give a slightly small dependence on \(a_{{{\text{SiO}}_{2} }}\), with D \(\propto\) (\(a_{{{\text{SiO}}_{2} }}^{0.5}\)), presumably because the Mg-site vacancies increase with incorporation of Fe³⁺ in the Fe-bearing olivines. However, the dependence on fO₂ is small, with D \(\propto\) (fO₂)^0.12±0.12. These results show the necessity of constraining the chemical potentials of all the stoichiometric components of a phase when designing diffusion experiments. Similarly, the chemical potentials of the major-element components must be taken into account when applying experimental data to natural minerals to constrain the rates of geological processes. For example, the diffusion of divalent elements in olivine from low SiO₂ magmas, such as kimberlites or carbonatites, will be an order of magnitude slower than in olivine from high SiO₂ magmas, such as tholeiitic basalts, at equal temperatures and fO₂.

     

Hydrogen incorporation into forsterite in Mg2SiO4–K2Mg(CO3)2–H2O and Mg2SiO4–H2O–C at 7.5–14.0 GPa

Experiments on water solubility in forsterite in the systems Mg₂SiO₄–K₂Mg(CO₃)₂–H₂O and Mg₂SiO₄–H₂O–C were conducted at 7.5–14.0 GPa and 1200–1600 °C. The resulting crystals contain 448 to 1480 ppm water, which is 40–70% less than in the forsterite–water system under the same conditions. This can be attributed to lower water activity in the carbonate-bearing melt. The water content of forsterite was found to vary systematically with temperature and pressure. For instance, at 14 GPa in the system forsterite–carbonate–H₂O the H₂O content of forsterite drops from 1140 ppm at 1200 °C to 450 ppm at 1600 °C, and at 8 GPa it remains constant or increases from 550 to 870 ppm at 1300–1600 °C. Preliminary data for D-H-bearing forsterite are reported. Considerable differences were found between IR spectra of D-H- and H-bearing forsterite. The results suggest that CO₂ can significantly affect the width of the olivine-wadsleyite transition, i.e., the 410-km seismic discontinuity, which is a function of the water content of olivine and wadsleyite.     

Breakdown of hydrous ringwoodite to pyroxene and spinelloid at high P and T and oxidizing conditions

To get deeper insight into the phase relations in the end-member system Fe₂SiO₄ and in the system (Fe, Mg)₂SiO₄ experiments were performed in a multi-anvil apparatus at 7 and 13 GPa and 1,000–1,200°C as a function of oxygen fugacity. The oxygen fugacity was varied using the solid oxygen buffer systems Fe/FeO, quartz–fayalite–magnetite, MtW and Ni/NiO. The run products were characterized by electron microprobe, Raman- and FTIR-spectroscopy, X-ray powder diffraction and transmission electron microscopy. At fO₂ corresponding to Ni/NiO Fe-ringwoodite transforms to ferrosilite and spinelloid according to the reaction: 9 Fe₂SiO₄ + O₂ = 6 FeSiO₃ + 5 Fe_2.40Si_0.60O₄. Refinement of site occupancies in combination with stoichiometric Fe³⁺ calculations show that 32% of the total Fe is incorporated as Fe³⁺ according to From the Rietveld refinement we identified spl as spinelloid III (isostructural with wadsleyite) and/or spinelloid V. As we used water in excess in the experiments the run products were also analyzed for structural water incorporation. Adding Mg to the system increases the stability field of ringwoodite to higher oxygen fugacity and the spinel structure seems to accept higher Fe³⁺ but also water concentrations that may be linked. At oxygen fugacity corresponding to MtW conditions similar phase relations in respect to the breakdown reaction in the Fe-end-member system were observed but with a strong fractionation of Fe into spl and Mg into coexisting cpx. Thus, through this strong fractionation it is possible to stabilize very Fe-rich wadsleyite with considerable Fe³⁺ concentrations even at an intermediate Fe–Mg bulk composition: assuming constant K _D independent on composition and a bulk composition of x _Fe = 0.44 this fractionation would stabilize spl with x _Fe = 0.72. Thus, spl could be a potential Fe³⁺ bearing phase at P–T conditions of the transition zone but because of the oxidizing conditions and the Fe-rich bulk composition needed one would expect it more in subduction zone environments than in the transition zone in senso stricto.

Systematic study of hydrogen incorporation into Fe-free wadsleyite

The H₂O content of wadsleyite were measured in a wide pressure (13–20 GPa) and temperature range (1,200–1,900°C) using FTIR method. We confirmed significant decrease of the H₂O content of wadsleyite with increasing temperature and reported first systematic data for temperature interval of 1,400–1,900°C. Wadsleyite contains 0.37–0.55 wt% H₂O at 1,600°C, which may be close to its water storage capacity along average mantle geotherm in the transition zone. Accordingly, water storage capacity of the average mantle in the transition zone may be estimated as 0.2–0.3 wt% H₂O. The H₂O contents of wadsleyite at 1,800–1,900°C are 0.22–0.39 wt%, indicating that it can store significant amount of water even under the hot mantle environments. Temperature dependence of the H₂O content of wadsleyite can be described by exponential equation C_{\textH2 \textO} = 6 3 7.0 7 \texte ^{- 0.00 4 8T} , C_{{{\text{H}}_{2} {\text{O}}}} = 6 3 7.0 7 {\text{e}}^{ - 0.00 4 8T} , where T is in °C. This equation is valid for temperature range 1,200–2,100°C with the coefficient of determination R ² = 0.954. Temperature dependence of H₂O partition coefficient between wadsleyite and forsterite (D _wd/fo) is complex. According to our data apparent D_wd/fo decreases with increasing temperature from D _wd/fo = 4–5 at 1,200°C, reaches a minimum of D _wd/fo = 2.0 at 1,400–1,500°C, and then again increases to D _wd/fo = 4–6 at 1,700–1,900°C.     

Compositions of aqueous fluids in equilibrium with pyroxenes and olivines at mantle pressures and temperatures

Solubility experiments were performed at 30 kbars in the system Mg₂SiO₄-SiO₂-H₂O, and at 20 and 30 kbars on omphacitic pyroxene-water mixtures. They confirm that the solubility of the forsterite component in aqueous fluids remains rather low (up to 5 wt.%), whereas the solubility of the SiO₂ component from solids of appropriate SiO₂-rich compositions in the system Mg₂SiO₄-SiO₂-H₂O increases with temperature up to some 75% at 1,100° C. At this temperature a simplified harzburgite consisting of forsterite and enstatite coexists with a fluid containing about 35% (MgO+SiO₂). Hydrous fluids coexisting with omphacitic clinopyroxenes leach sodium silicate component from the solid leaving less jadeitic pyroxenes behind. Most interestingly, the amount of sodium leached at constant temperature increases with decreasing pressure.Comparison of the results with previous solubility studies in the system K₂O-MgO-Al₂O₃-SiO₂-H₂O indicates that hydrous fluids in the mantle must be alkaline rather than silicanormative. Alkali metasomatism caused by such fluids would lead to potassium enrichment in deeper portions of the upper mantle and to sodium enrichment at shallower levels, where amphiboles become stable. This K/Na fractionation in the upper mantle may explain the generation of K-rich or of Na-rich magmas through partial melting at different depths.     

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     

Ultra-depleted peridotite xenoliths in the Northern Taihang Mountains: Implications for the nature of the lithospheric mantle beneath the North China Craton

We report the finding of peridotite xenoliths in the Early Cretaceous Longmengou olivine-bearing diabase (138 Ma) in the Northern Taihang Mountains in the central North China Craton. Based on the modal proportions of olivine, clinopyroxene, amphibole and anorthite, these peridotite xenoliths can be divided into three zones: clinopyroxene-bearing olivine zone (COZ), olivine-clinopyroxene zone (OCZ), and amphibole-bearing anorthite-clinopyroxene zone (AACZ). The core of olivine grains in clinopyroxene-bearing olivine zone have higher Mg^# (> 95), SiO₂ (41.80–42.53 wt%) and lower CaO (< 0.07 wt%), FeO (3.91–4.54 wt%) than the rim (Mg^# = 92.5–93.4, SiO₂ = 41.27–41.98 wt%, CaO = 0.20–0.34 wt%, and FeO = 7.02–8.87 wt%), suggesting that rim is reaction product. The core of olivine grains with higher Mg^# (> 95) and lower NiO content (< 0.04 wt%) in the clinopyroxene-bearing olivine zone was derived from ultra-depleted mantle subsequently altered by high Mg^# melts/magma with low Ni. Two generations of olivine grains occur in the OCZ where the first generation shows exsolution of ilmenite and magnetite rods containing up to 0.35 wt% TiO₂, and was likely derived from garnet peridotite hydrated by water. The second generation shows high Mg^# (96.2–97.1) and cataclastic texture, and was possibly formed by decomposition of the COZ. The occurrence of aluminous spinel suggests the role of melts with extremely high Al and Mg. Clinopyroxene in the AACZ shows systematic core-rim compositional variation with CaO and SiO₂ contents increasing towards the rim, and MgO and Fe₂O₃ concentrations decreasing from the core to the rim, indicating that the amphibole-bearing anorthite-clinopyroxene zone is a product of the reaction between mantle xenoliths and mafic magma. Plagioclase with high An value (92.0–99.95, average 97.79) indicates that the metasomatic melts have high Ca/Na and Al/Si ratios, possibly produced by the partial melting of ultra-depleted mantle under “wet” conditions. Combined with the data on other mantle xenoliths discovered in the NCC, our results suggest that the Mesozoic lithospheric mantle beneath the North Taihang Mountains within the central NCC is composed of ultra-depleted Archean and Paleoproterozoic peridotites and dunites modified by complex melts. We also propose that the destruction of eastern part of the NCC mainly occurred during Early Cretaceous, and that the boundary of the lithospheric destruction coincides with the Taihang Mountains.     

H<Subscript>2</Subscript>O storage capacity of MgSiO<Subscript>3</Subscript> clinoenstatite at 8–13 GPa, 1,100–1,400°C

We present H₂O analyses of MgSiO₃ pyroxene crystals quenched from hydrous conditions in the presence of olivine or wadsleyite at 8–13.4 GPa and 1,100–1,400°C. Raman spectroscopy shows that all pyroxenes have low clinoenstatite structure, which we infer to indicate that the crystals were high clinoenstatite (C2/c) during conditions of synthesis. H₂O analyses were performed by secondary ion mass spectrometry and confirmed by unpolarized Fourier transform infrared spectroscopy on randomly oriented crystals. Measured H₂O concentrations increase with pressure and range from 0.08 wt.% H₂O at 8 GPa and 1,300°C up to 0.67 wt.% at 13.4 GPa and 1,300°C. At fixed pressure, H₂O storage capacity diminishes with increasing temperature and the magnitude of this effect increases with pressure. This trend, which we attribute to diminishing activity of H₂O in coexisting fluids as the proportion of dissolved silicate increases, is opposite to that observed previously at low pressure. We observe clinoenstatite 1.4 GPa below the pressure stability of clinoenstatite under nominally dry conditions. This stabilization of clinoenstatite relative to orthoenstatite under hydrous conditions is likely owing to preferential substitution of H₂O into the high clinoenstatite polymorph. At 8–11 GPa and 1,200–1,400°C, observed H₂O partitioning between olivine and clinoenstatite gives values of D ^ol/CEn between 0.65 and 0.87. At 13 GPa and 1,300°C, partitioning between wadsleyite and clinoenstatite, D ^wd/CEn, gives a value of 2.8 ± 0.4.     

Crystal chemistry of wadsleyite II and water in the Earth’s interior

Wadsleyite II is a variably hydrous magnesium-iron silicate phase similar to spinelloid IV and a potential host for H in the Transition Zone of the Earths mantle. Two separate samples of wadsleyite II synthesized at 17.5 GPa and 1400°C and at 18 GPa and 1350°C have been characterized by electron microprobe, single-crystal X-ray diffraction, visible, IR, Raman, and Mössbauer spectroscopies, and transmission electron microscopy including electron energy-loss spectroscopy. The two samples have the following chemical formulae: Mg_1.71Fe_0.18Al_0.01H_0.33Si_0.96O₄ and Mg_1.60Fe_0.22Al_0.01 H_0.44Si_0.97O₄. Mössbauer spectroscopy and electron energy loss spectroscopy (EELS) indicate that about half of the iron present is ferric. Refinement of the structures shows them to be essentially the same as spinelloid IV. Calculated X-ray powder diffraction patterns show only subtle differences between wadsleyite and wadsleyite II. The hydration mechanism appears to be protonation of the non-silicate oxygen (O2) and possibly the oxygens surrounding the partially vacant tetrahedral site Si2, charge-balanced by cation vacancies in Si2, M5 and M6. The unit cell volume of this phase and its synthesis conditions indicate that it may be an intermediate phase occurring between the fields of wadsleyite and ringwoodite, if sufficient trivalent cations are available. The unit cell parameters have been refined at pressures up to 10.6 GPa by single-crystal X-ray diffraction in the diamond anvil cell. The refined bulk modulus for the sample containing 2.8 wt% H₂O is 145.6 ± 2.8 GPa with a K of 6.1 ± 0.7. Similar to wadsleyite and ringwoodite, hydration has a large effect on the bulk modulus. The presence of this phase in the mantle could serve to obscure the seismic expression of the phase boundary between wadsleyite and ringwoodite near 525 km. The large apparent effect of hydration on bulk modulus is consistent with hydration having a larger effect on seismic velocities than temperature in the Transition Zone.     

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.     

Experimental and computational study of trace element distribution between orthopyroxene and anhydrous silicate melt: substitution mechanisms and the effect of iron

Although orthopyroxene (Opx) is present during a wide range of magmatic differentiation processes in the terrestrial and lunar mantle, its effect on melt trace element contents is not well quantified. We present results of a combined experimental and computational study of trace element partitioning between Opx and anhydrous silicate melts. Experiments were performed in air at atmospheric pressure and temperatures ranging from 1,326 to 1,420°C in the system CaO–MgO–Al₂O₃–SiO₂ and subsystem CaO–MgO–SiO₂. We provide experimental partition coefficients for a wide range of trace elements (large ion lithophile: Li, Be, B, K, Rb, Sr, Cs, Ba, Th, U; rare earth elements, REE: La, Ce, Nd, Sm, Y, Yb, Lu; high field strength: Zr, Nb, Hf, Ta, Ti; transition metals: Sc, V, Cr, Co) for use in petrogenetic modelling. REE partition coefficients increase from $ D_{\text{La}}^{{\text{Opx}} {\hbox{-}} {\text{melt}}} \sim 0.0005 Although orthopyroxene (Opx) is present during a wide range of magmatic differentiation processes in the terrestrial and lunar mantle, its effect on melt trace element contents is not well quantified. We present results of a combined experimental and computational study of trace element partitioning between Opx and anhydrous silicate melts. Experiments were performed in air at atmospheric pressure and temperatures ranging from 1,326 to 1,420°C in the system CaO–MgO–Al₂O₃–SiO₂ and subsystem CaO–MgO–SiO₂. We provide experimental partition coefficients for a wide range of trace elements (large ion lithophile: Li, Be, B, K, Rb, Sr, Cs, Ba, Th, U; rare earth elements, REE: La, Ce, Nd, Sm, Y, Yb, Lu; high field strength: Zr, Nb, Hf, Ta, Ti; transition metals: Sc, V, Cr, Co) for use in petrogenetic modelling. REE partition coefficients increase from $ D_{\text{La}}^{{\text{Opx}} {\hbox{-}} {\text{melt}}} \sim 0.0005 $ D_{\text{La}}^{{\text{Opx}} {\hbox{-}} {\text{melt}}} \sim 0.0005 to $ D_{\text{Lu}}^{{{\text{Opx}} {\hbox{-}} {\text{melt}}}} \sim 0.109 $ D_{\text{Lu}}^{{{\text{Opx}} {\hbox{-}} {\text{melt}}}} \sim 0.109 , D values for highly charged elements vary from $ D_{\text{Th}}^{{{\text{Opx}} {\hbox{-}} {\text{melt}}}} \sim 0.0026 $ D_{\text{Th}}^{{{\text{Opx}} {\hbox{-}} {\text{melt}}}} \sim 0.0026 through $ D_{\text{Nb}}^{{{\text{Opx}} {\hbox{-}} {\text{melt}}}} \sim 0.0033 $ D_{\text{Nb}}^{{{\text{Opx}} {\hbox{-}} {\text{melt}}}} \sim 0.0033 and $ D_{\text{U}}^{{{\text{Opx}} {\hbox{-}} {\text{melt}}}} \sim 0.0066 $ D_{\text{U}}^{{{\text{Opx}} {\hbox{-}} {\text{melt}}}} \sim 0.0066 to $ D_{\text{Ti}}^{{\text{Opx}} {\hbox{-}} {\text{melt}}} \sim 0.058 $ D_{\text{Ti}}^{{\text{Opx}} {\hbox{-}} {\text{melt}}} \sim 0.058 , and are all virtually independent of temperature. Cr and Co are the only compatible trace elements at the studied conditions. To elucidate charge-balancing mechanisms for incorporation of REE into Opx and to assess the possible influence of Fe on Opx-melt partitioning, we compare our experimental results with computer simulations. In these simulations, we examine major and minor trace element incorporation into the end-members enstatite (Mg₂Si₂O₆) and ferrosilite (Fe₂Si₂O₆). Calculated solution energies show that R²⁺ cations are more soluble in Opx than R³⁺ cations of similar size, consistent with experimental partitioning data. In addition, simulations show charge balancing of R³⁺ cations by coupled substitution with Li⁺ on the M1 site that is energetically favoured over coupled substitution involving Al–Si exchange on the tetrahedrally coordinated site. We derived best-fit values for ideal ionic radii r ₀, maximum partition coefficients D ₀, and apparent Young’s moduli E for substitutions onto the Opx M1 and M2 sites. Experimental r ₀ values for R³⁺ substitutions are 0.66–0.67 ? for M1 and 0.82–0.87 ? for M2. Simulations for enstatite result in r ₀ = 0.71–0.73 ? for M1 and ~0.79–0.87 ? for M2. Ferrosilite r ₀ values are systematically larger by ~0.05 ? for both M1 and M2. The latter is opposite to experimental literature data, which appear to show a slight decrease in $ r_{0}^{{{\text{M}}2}} $ r_{0}^{{{\text{M}}2}} in the presence of Fe. Additional systematic studies in Fe-bearing systems are required to resolve this inconsistency and to develop predictive Opx-melt partitioning models for use in terrestrial and lunar magmatic differentiation models.     

Preferential dissolution of SiO<Subscript>2</Subscript> from enstatite to H<Subscript>2</Subscript> fluid under high pressure and temperature

Stability and phase relations of coexisting enstatite and H₂ fluid were investigated in the pressure and temperature regions of 3.1–13.9 GPa and 1500–2000 K using laser-heated diamond-anvil cells. XRD measurements showed decomposition of enstatite upon heating to form forsterite, periclase, and coesite/stishovite. In the recovered samples, SiO₂ grains were found at the margin of the heating hot spot, suggesting that the SiO₂ component dissolved in the H₂ fluid during heating, then precipitated when its solubility decreased with decreasing temperature. Raman and infrared spectra of the coexisting fluid phase revealed that SiH₄ and H₂O molecules formed through the reaction between dissolved SiO₂ and H₂. In contrast, forsterite and periclase crystals were found within the hot spot, which were assumed to have replaced the initial orthoenstatite crystals without dissolution. Preferential dissolution of SiO₂ components of enstatite in H₂ fluid, as well as that observed in the forsterite H₂ system and the quartz H₂ system, implies that H₂-rich fluid enhances Mg/Si fractionation between the fluid and solid phases of mantle minerals.     

Fe–Mg interdiffusion rates in clinopyroxene: experimental data and implications for Fe–Mg exchange geothermometers

Chemical interdiffusion of Fe–Mg along the c-axis [001] in natural diopside crystals (X _Di = 0.93) was experimentally studied at ambient pressure, at temperatures ranging from 800 to 1,200 °C and oxygen fugacities from 10^?11 to 10^?17 bar. Diffusion couples were prepared by ablating an olivine (X _Fo = 0.3) target to deposit a thin film (20–100 nm) onto a polished surface of a natural, oriented diopside crystal using the pulsed laser deposition technique. After diffusion anneals, compositional depth profiles at the near surface region (~400 nm) were measured using Rutherford backscattering spectroscopy. In the experimental temperature and compositional range, no strong dependence of D ^Fe–Mg on composition of clinopyroxene (Fe/Mg ratio between Di₉₃–Di₆₅) or oxygen fugacity could be detected within the resolution of the study. The lack of fO₂-dependence may be related to the relatively high Al content of the crystals used in this study. Diffusion coefficients, D ^Fe–Mg, can be described by a single Arrhenius relation with $$D^{{{\text{Fe}} - {\text{Mg}}}} = 2. 7 7\pm 4. 2 7\times 10^{ - 7} {\text{exp(}}-3 20. 7\pm 1 6.0{\text{ kJ}}/{\text{mol}}/{\text{RT)m}}^{ 2} /{\text{s}}.$$ D ^Fe–Mg in clinopyroxene appears to be faster than diffusion involving Ca-species (e.g., D ^Ca–Mg) while it is slower than D ^Fe–Mg in other common mafic minerals (spinel, olivine, garnet, and orthopyroxene). As a consequence, diffusion in clinopyroxene may be the rate-limiting process for the freezing of many geothermometers, and compositional zoning in clinopyroxene may preserve records of a higher (compared to that preserved in other coexisting mafic minerals) temperature segment of the thermal history of a rock. In the absence of pervasive recrystallization, clinopyroxene grains will retain compositions from peak temperatures at their cores in most geological and planetary settings where peak temperatures did not exceed ~1,100 °C (e.g., resetting may be expected in slowly cooled mantle rocks, many plutonic mafic rocks, or ultra-high temperature metamorphic rocks).     

Thermodynamics, structure, dynamics, and freezing of Mg2SiO4 liquid at high pressure

We perform first principles molecular dynamics simulations of Mg₂SiO₄ liquid and crystalline forsterite. On compression by a factor of two, we find that the Grüneisen parameter of the liquid increases linearly from 0.6 to 1.2. Comparison of liquid and forsterite equations of state reveals a temperature-dependent density crossover at pressures of ∼12-17 GPa. Along the melting curve, which we calculate by integration of the Clapeyron equation, the density crossover occurs within the forsterite stability field at P = 13 GPa and T = 2550 K. The melting curve obtained from the root mean-square atomic displacement in forsterite using the Lindemann law fails to match experimental or calculated melting curves. We attribute this failure to the liquid structure that differs significantly from that of forsterite, and which changes markedly upon compression, with increases in the degree of polymerization and coordination. The mean Si coordination increases from 4 in the uncompressed system to 6 upon twofold compression. The self-diffusion coefficients increase with temperature and decrease monotonically with pressure, and are well described by the Arrhenian relation. We compare our equation of state to the available highpressure shock wave data for forsterite and wadsleyite. Our theoretical liquid Hugoniot is consistent with partial melting along the forsterite Hugoniot at pressures 150-170 GPa, and complete melting at 170 GPa. The wadsleyite Hugoniot is likely sub-liquidus at the highest experimental pressure to date (200 GPa).     

An experimental study of Fe–Ni exchange between sulfide melt and olivine at upper mantle conditions: implications for mantle sulfide compositions and phase equilibria

The behavior of nickel in the Earth’s mantle is controlled by sulfide melt–olivine reaction. Prior to this study, experiments were carried out at low pressures with narrow range of Ni/Fe in sulfide melt. As the mantle becomes more reduced with depth, experiments at comparable conditions provide an assessment of the effect of pressure at low-oxygen fugacity conditions. In this study, we constrain the Fe–Ni composition of molten sulfide in the Earth’s upper mantle via sulfide melt–olivine reaction experiments at 2 GPa, 1200 and 1400 °C, with sulfide melt \(X_{{{\text{Ni}}}}^{{{\text{Sulfide}}}}=\frac{{{\text{Ni}}}}{{{\text{Ni}}+{\text{Fe}}}}\) (atomic ratio) ranging from 0 to 0.94. To verify the approach to equilibrium and to explore the effect of \({f_{{{\text{O}}_{\text{2}}}}}\) on Fe–Ni exchange between phases, four different suites of experiments were conducted, varying in their experimental geometry and initial composition. Effects of Ni secondary fluorescence on olivine analyses were corrected using the PENELOPE algorithm (Baró et al., Nucl Instrum Methods Phys Res B 100:31–46, 1995), “zero time” experiments, and measurements before and after dissolution of surrounding sulfides. Oxygen fugacities in the experiments, estimated from the measured O contents of sulfide melts and from the compositions of coexisting olivines, were 3.0?±?1.0 log units more reduced than the fayalite–magnetite-quartz (FMQ) buffer (suite 1, 2 and 3), and FMQ ??1 or more oxidized (suite 4). For the reduced (suites 1–3) experiments, Fe–Ni distribution coefficients \(K_{{\text{D}}}^{{}}=\frac{{(X_{{{\text{Ni}}}}^{{{\text{sulfide}}}}/X_{{{\text{Fe}}}}^{{{\text{sulfide}}}})}}{{(X_{{{\text{Ni}}}}^{{{\text{olivine}}}}/X_{{{\text{Fe}}}}^{{{\text{olivine}}}})}}\) are small, averaging 10.0?±?5.7, with little variation as a function of total Ni content. More oxidized experiments (suite 4) give larger values of K_D (21.1–25.2). Compared to previous determinations at 100 kPa, values of K_D from this study are chiefly lower, in large part owing to the more reduced conditions of the experiments. The observed difference does not seem attributable to differences in temperature and pressure between experimental studies. It may be related in part to the effects of metal/sulfur ratio in sulfide melt. Application of these results to the composition of molten sulfide in peridotite indicates that compositions are intermediate in composition (\(X_{{{\text{Ni}}}}^{{{\text{sulfide}}}}\)?~?0.4–0.6) in the shallow mantle at 50 km, becomes more Ni rich with depth as the O content of the melt diminishes, reaching a maximum (0.6–0.7) at depths near 80–120 km, and then becomes more Fe rich in the deeper mantle where conditions are more reduced, approaching (\(X_{{{\text{Ni}}}}^{{{\text{sulfide}}}}\)?~?0.28)?>?140 km depth. Because Ni-rich sulfide in the shallow upper mantle melts at lower temperature than more Fe-rich compositions, mantle sulfide is likely molten in much of the deep continental lithosphere, including regions of diamond formation.