Pressure-induced coordination change of Ti in silicate glass: a XANES study

The effect of pressure on titanium coordination in glasses, with composition K₂TiSi₄O₁₁, quenched isobarically from liquids equilibrated at high pressure (5, 10, 15, 20, 25, 30 kbar respectively) and T=1600° C has been investigated by X-ray absorption spectroscopy (XAS). The XANES spectra collected at the Ti K-edge clearly show a variation with pressure that is related to changes in the geometrical environment around the Ti atoms. By comparison with spectra of standard materials, the XANES spectra of the glasses suggest a relatively low average coordination number (near 5) in samples quenched at low pressure and a higher coordination number (near 6) in samples quenched from the highest pressure. The combination of XANES data with density and compressibility measurements supports the idea that a mixture of 6- and lower coordinated (4- and/ or 5-coordinated) Ti geometries are present in the 1 bar glass, and an increasing proportion of 6-coordinated Ti occurs in the glasses synthesized at progressively higher pressures.     

Experimental study of polybaric REE partitioning between olivine, pyroxene and melt of the Yamato 980459 composition: Insights into the petrogenesis of depleted shergottites

A synthetic composition representing the Yamato 980459 martian basalt (shergottite) has been used to carry out phase relation, and rare earth element (REE) olivine and pyroxene partitioning experiments. Yamato 980459 is a sample of primitive basalt derived from a reduced end-member among martian mantle sources. Experiments carried out between 1-2 GPa and 1350-1650 °C simulate the estimated pressure-temperature conditions of basaltic melt generation in the martian mantle. Olivine-melt and orthopyroxene-melt partition coefficients for La, Nd, Sm, Eu, Gd and Yb (D_REE values) were determined by LA-ICPMS, and are similar to the published values for terrestrial basaltic systems. We have not detected significant variation in D-values with pressure over the range investigated, and by comparison with previous studies carried out at lower pressure.We apply the experimentally obtained olivine-melt and orthopyroxene-melt D_REE values to fractional crystallization and partial melting models to develop a three-stage geochemical model for the evolution of martian meteorites. In our model we propose two ancient (∼4.535 Ga) sources: the Nakhlite Source, located in the shallow mantle, and the Deep Mantle Source, located close to the martian core-mantle boundary. These two sources evolved distinctly on the ε¹⁴³Nd evolution curve due to their different Sm/Nd ratios. By partially melting the Nakhlite Source at ∼1.3 Ga, we are able to produce a slightly depleted residue (Nakhlite Residue). The Nakhlite Residue is left undisturbed until ∼500 Ma, at which point the depleted Deep Mantle Source is brought up by a plume mechanism carrying with it high heat flow, melts and isotopic signatures of the deep mantle (e.g., ε¹⁸²W, ε¹⁴²Nd, etc.). The plume-derived Deep Mantle Source combines with the Nakhlite Residue producing a mixture that becomes a mantle source (herein referred to as “the Y98 source”) for Yamato 980459 and the other depleted shergottites with the characteristic range of Sm/Nd ratios of these meteorites. The same hot plume provides a heat source for the formation of enriched and intermediate shergottites. Our model reproduces the REE patterns of nakhlites and depleted shergottites and can explain high ε¹⁴³Nd in depleted shergottites. Furthermore, the model results can be used to interpret whole rock Rb-Sr and Sm-Nd ages of shergottites.     

Comparative petrology, geochemistry, and petrogenesis of evolved, low-Ti lunar mare basalt meteorites from the LaPaz Icefield, Antarctica

New data is presented for five evolved, low-Ti lunar mare basalt meteorites from the LaPaz Icefield, Antarctica, LAP 02205, LAP 02224, LAP 02226, LAP 02436, and LAP 03632. These basalts have nearly identical mineralogies, textures, and geochemical compositions, and are therefore considered to be paired. The LaPaz basalts contain olivine (Fo_64-2) and pyroxene (Fs₃₂Wo₈En₆₀ to Fs_84-86Wo₁₅En_2-0) crystals that record extreme chemical fractionation to Fe-enrichment at the rims, and evidence for silicate liquid immiscibility and incompatible element enrichment in the mesostasis. The basalts also contain FeNi metals with unusually high Co and Ni contents, similar to some Apollo 12 basalts, and a single-phase network of melt veins and fusion crusts. The fusion crust has similar chemical characteristics to the whole rock for the LaPaz basalts, whereas the melt veins represent localized melting of the basalt and have an endogenous origin. The crystallization conditions and evolved nature of the LaPaz basalts are consistent with fractionation of olivine and chromite from a parental liquid similar in composition to some olivine-phyric Apollo 12 and Apollo 15 basalts or lunar low-Ti pyroclastic glasses. However, the young reported ages for the LaPaz mare basalts (∼2.9 Ga) and their relative incompatible element enrichment compared to Apollo mare basalts and pyroclastic glasses indicate they cannot be directly related. Instead, the LaPaz mare basalts may represent fractionated melts from a magmatic system fed by similar degrees of partial melting of a mantle source similar to that of the low-Ti Apollo mare basalts or pyroclastic glasses, but which possessed greater incompatible element enrichment. Despite textural differences, the LaPaz basalts and mare basalt meteorite NWA 032 have similar ages and compositions and may originate from the same magmatic system on the Moon.     

Crystallization of titaniferous chromite,magnesian ilmenite and armalcolite in tholeiitic suites in the Karoo Igneous Province

Titaniferous chromite (up to 8 wt% TiO₂) and magnesian ilmenite (up to 10 wt% MgO) coexist at the base of the differentiated tholeiitic Mount Ayliff Intrusion in the Karoo Province of southern Africa, suggesting that the original magma was TiO₂-rich. Picritic lavas with 3% TiO₂ from the Lebombo monocline of the Karoo Province also contain microphenocrysts of magnesian ilmenite (up to 6 wt% mgO) and armalcolite (up to 7 wt% MgO). These oxide mineral associations and compositions are atypical of tholeiitic magmas, in which chromite usually has less than 1 wt% TiO₂, ilmenite less than 3 wt% MgO and armalcolite is rarely a primary mineral. Experiments have been conducted at one atmosphere pressure on a range of compositions to determine the effect of TiO₂ on the crystallization and composition of chromite, ilmenite and armalcolite. The results indicate that increasing the TiO₂ content of picritic magmas increases the TiO₂ content of the spinel, mainly at the expense of Al₂O₃, whereas Cr₂O₃ is not affected. Spinel compositions in the Mount Ayliff Intrusion (with over 45 wt% Cr₂O₃, less than 10 wt% Al₂O₃ and 8 wt% TiO₂) were duplicated in experiments on a picrite at temperatures of about 1,200°C at the Ni/NiO buffer. Increasing fO₂ from fayalite-magnetite-quartz to Ni/NiO buffer is shown to increase the crystallization temperature of armalcolite and to decrease that of ilmenite. The total FeO content of the liquid has little influence on the crystallization temperature of these phases. The TiO₂ content of the liquid, when either ilmenite or armalcolite crystallizes, varies inversely with SiO₂ content. The MgO content of the liquid at which ilmenite or armalcolite crystallizes depends upon the TiO₂ content of the starting composition, with naturally occurring and experimetally determined saturation being demonstrated for liquids with 5 wt% MgO and 5.5 wt% TiO₂. The partition coefficent for MgO between armalcolite or ilmenite and liquid is about 1.5. Observed magnesian armalcolite and ilmenite compositions in picrite lavas (both minerals) and in the Mount Ayliff Intrusion (ilmenite only) are consistent with crystallization from a TiO₂-rich magma with approximately 5 wt% MgO. The Fe ₂ ³⁺ TiO₅ component of armalcolite in the picrite lavas matches those formed experimentally at temperatures of 1,150–1,110°C and fO₂ of the Ni/NiO to Ni/NiO+1 log unit. Similarities also exist between the compositions of chromite, ilmenite and armalcolite and liquid fraction-ation trends of some Hawaiian high-TiO₂ lavas and the experimental studies presented here.     

Oxygen fugacity and geochemical variations in the martian basalts: implications for martian basalt petrogenesis and the oxidation state of the upper mantle of Mars

The oxygen fugacity of the Dar al Gani 476 martian basalt is determined to be quartz-fayalite-magnetite (QFM) −2.3 ± 0.4 through analysis of olivine, low-Ca pyroxene, and Cr-spinel and is in good agreement with revised results from Fe-Ti oxides that yield QFM −2.5 ± 0.7. This estimate falls within the range of oxygen fugacity for the other martian basalts, QFM −3 to QFM −1. Oxygen fugacity in martian basalts correlates with ⁸⁷Sr/⁸⁶Sr, ¹⁴³Nd/¹⁴⁴Nd, and La/Yb ratios, indicating that the mantle source of the basalts is reduced and that assimilation of crust-like material controls the oxygen fugacity. This allows constraints to be placed on the oxidation state of the martian mantle and on the nature of assimilated crustal material. The assimilated material may be the product of early and extensive hydrothermal alteration of the martian crust, or it may be amphibole- or phlogopite-bearing basaltic rock within the crust. In either case, water may play a significant role in the oxidation of basaltic magmas on Mars, although it may be secondary to assimilation of ferric iron-rich material.     

Experimental study on the effects of temperature cycling on coarsening of plagioclase and olivine in an alkali basalt

We conducted experiments on an alkali basalt at 1-atmosphere in order to investigate the effects of temperature cycling on crystal coarsening. Experiments at 1,150 °C near the Ni–NiO buffer indicate that coarsening of plagioclase and olivine crystals is greatly accentuated by temperature cycling. For a given experiment duration, crystal number density decreases with temperature cycle amplitude and average crystal size increases with increasing amplitude. We observed little correlation between cycle period and crystal number density or average crystal size. We suggest that dissolution and size-proportional crystal growth during repeated heating and cooling decrease crystal number density and increase average crystal size. These experiments indicate that the texture of silicate minerals can be modified by temperature cycling and that phenocrysts may develop quicker in silicate magmas when the magma temperature is cycled.     

Osmium mass balance in peridotite and the effects of mantle-derived sulphides on basalt petrogenesis

Analyses of enriched mantle (EM)-basalts, using lithophile element-based isotope systems, have long provided evidence for discrete mantle reservoirs with variable composition. Upon partial melting, the mantle reservoir imparts its isotopic fingerprint upon the partial melt produced. However, it has increasingly been recognised that it may not be simple to delimit these previously well-defined mantle reservoirs; the “mantle zoo” may contain more reservoirs than previously envisaged.Here we demonstrate that a simple model with varying contributions from two populations of compositionally distinct mantle sulphides can readily account for the observed heterogeneities in Os isotope systematics of such basalts without additional mantle reservoirs. Osmium elemental and isotopic analyses of individual sulphide grains separated from spinel lherzolites from Kilbourne Hole, New Mexico, USA demonstrate that two discrete populations of mantle sulphide exist in terms of both Re-Os systematics and textural relationship with co-existing silicates. One population, with a rounded morphology, is preserved in silicate grains and typically possesses high [Os] and low [Re] with unradiogenic, typically sub-chondritic ¹⁸⁷Os/¹⁸⁸Os attributable to long term isolation in a low-Re environment. By contrast, irregular-shaped sulphides, preserved along silicate grain boundaries, possess low [Os], higher [Re] and a wider range of, but generally supra-chondritic ¹⁸⁷Os/¹⁸⁸Os ([Os] typically ? 1-2 ppm, ¹⁸⁷Os/¹⁸⁸Os ? 0.3729; this study). This population is thought to represent metasomatic sulphide.Uncontaminated silicate phases contain negligible Os (<100 ppt) therefore the Os elemental and isotope composition of basalts is dominated by volumetrically insignificant sulphide ([Os] ? 37 ppm; this study). During the early stages of partial melting, supra-chondritic interstitial sulphides are mobilised and incorporated into the melt, adding their radiogenic ¹⁸⁷Os/¹⁸⁸Os signature. Only when sulphides armoured within silicates are exposed to the melt through continued partial melting will enclosed sulphides add their high [Os] and unradiogenic ¹⁸⁷Os/¹⁸⁸Os to the aggregate melt. Platinum-group element data for whole rocks are also consistent with this scenario. The sequence of (i) addition of all of the metasomatic sulphide, followed by (ii) the incorporation of small amounts of armoured sulphide can thus account for the range of both [Os] and ¹⁸⁷Os/¹⁸⁸Os of EM-basalts worldwide without the need for contributions from additional silicate mantle reservoirs.     

The effect of dissolved water on the oxidation state of iron in natural silicate liquids

Ferric-ferrous ratios have been measured in 22 experiments on three natural compositions equilibrated at known temperature (950°–1100° C) and oxygen fugacity, and at water-saturated conditions over a pressure range from 0.05 to 0.2 GPa. There does not appear to be any reaction between the melt and the capsule material that affects the redox state of the iron in the melt. An empirical expression for the anhydrous behavior of the redox state of iron in each of these compositions has also been determined at 1 bar as a function of temperature and oxygen fugacity. A direct comparison of the hydrous ferric-ferrous values with the calculated anhydrous values shows that the dissolution of water in a per-alkaline rhyolite, andesite, and an augite minette has no effect on the redox state of the iron in these melts. This result parallels the effect of water on sulfide speciation in basaltic melts, and confirms published results on experimental hydrous basalts.     

The oxidation state of Ti in hornblende and biotite determined by electron energy-loss spectroscopy,with inferences regarding the Ti substitution

Structural formulae of many Ti-rich hornblendes and biotites exhibit cation deficiencies that increase with Ti content. These deficiencies may be caused by the presence of trivalent instead of tetravalent Ti, of oxygen replacing hydroxyl, or of vacancies on octahedral cation sites. In order to determine the oxidation state of their Ti, electron energy-loss spectra of natural, Ti-rich hornblende and biotites are compared with spectra of natural and synthetic Ti-bearing oxides and silicates. Spectra of Ti₂O₃ and TiO₂ demonstrate that the Ti L _2,3 edge for Ti³⁺ is shifted by ca. 2 eV to lower energy relative to the edge for Ti⁴⁺. Oxidation states of Ti determined by energy-loss spectroscopy for several minerals agree with data from other techniques: tetravalent for Ti-omphacite, perovskite, ilmenite and titanite; trivalent for NaTi³⁺Si₂O₆ pyroxene and fassaite from the Allende meteorite. The energy-loss spectra of the hornblende and biotite show that their Ti is tetravalent and cannot be the cause of the cation deficiencies. The relations between Ti contents and the number of deficiencies differ for hornblende and biotite. Hornblende shows a 2:1 relation between Ti content and deficiencies, suggesting Ti is coupled to an oxygen that is replacing hydroxyl (Ti-oxyhornblende substitution). Biotite shows a 1:1 relation, consistent with coupling of Ti to a vacant octahedral cation site (Ti-vacancy substitution) or to a variable combination of such vacancies and two oxygens replacing hydroxyls (Ti-oxybiotite substitution).     

Occurrence,chemistry, and origin of immiscible silicate glasses in a tholeiitic basalt: A TEM/AEM study

The occurrence and chemistry of immiscible silicate glasses in a tholeiite mesostasis from the Umtanum formation, Washington, were investigated with transmission electron microscopy and analytical electron microscopy (TEM/AEM). TEM observation reveals isolated, dark globules (2.1 micron or less in diameter) randomly distributed in a transparent matrix glass interstitial to plagioclase laths. The globules less than 0.3 micron and larger than 0.8 micron fall beyond the linear relationship defined by the 0.3–0.8 micron globules in a plot of the logarithm of number versus size. Large globules (0.7 micron or larger in diameter) range from homogeneous to heterogeneous in optical properties and chemistry. Homogeneous globules are completely glassy, whereas heterogeneous globules contain crystalline domains. AEM analyses show that the globules have high Si, Fe, Ca, and Ti with subordinate Mg, Al, P, S, Cl, K, and Mn, which gives high normative fa, px, il, and ap. The matrix glass consists dominantly of Si with low Al and minor Na and K, yielding a high normative qz, or, ab, and an.It is proposed that the silicate liquid immiscibility occurs by reaction of network-modifying cations (NMCs) with dominantly chain-like anionic units in the parental melt to form less polymerized, NMC-bearing units and highly polymerized, Si-rich units. The globules nucleated metastably under supercooled conditions, and medium-size globules become either larger or smaller at lower temperatures. Internal nucleation of NMC-rich phases occurred in some larger globules upon cooling.     

Chemical evolution, petrogenesis, and regional chemical correlations of the flood basalt sequence in the central Deccan Traps, India

The lava sequence of the central-western Deccan Traps (from Jalgaon towards Mumbai) is formed by basalts and basaltic andesites having a significant variation in TiO₂ (from 1.2 to 3.3 wt%), Zr (from 84 to 253 ppm), Nb (from 5 to 16ppm) and Ba (from 63 to 407 ppm), at MgO ranging from 10 to 4.2 wt%. Most of these basalts follow a liquid line of descent dominated by low pressure fractionation of clinopyroxene, plagioclase and olivine, starting from the most mafic compositions, in a temperature range from 1220° to 1125°C. These rocks resemble those belonging to the lower-most formations of the Deccan Traps in the Western Ghats (Jawhar, Igatpuri and Thakurvadi) as well as those of the Poladpur formation. Samples analyzed for⁸⁷Sr/⁸⁶Sr give a range of initial ratios from 0.70558 to 0.70621. A group of flows of the Dhule area has low TiO₂ (1.2–1.5 wt%) and Zr (84–105 ppm) at moderate MgO (5.2–6.2 wt%), matching the composition of low-Ti basalts of Gujarat, low-Ti dykes of the Tapti swarm and Toranmal basalts, just north of the study area. This allows chemical correlations between the lavas of central Deccan, the Tapti dykes and the north-western outcrops. The mildly enriched high field strength element contents of the samples with TiO₂ > 1.5 wt% make them products of mantle sources broadly similar to those which generated the Ambenali basalts, but their high La/Nb and Ba/Nb, negative Nb anomalies in the mantle normalized diagrams, and relatively high⁸⁷Sr/⁸⁶Sr, make evident a crustal input with crustally derived materials at less differentiated stages than those represented in this sample set, or even within the sub-Indian lithospheric mantle.     

Deformation microstructures of olivine and pyroxene in mantle xenoliths in Shanwang,eastern China,near the convergent plate margin,and implications for seismic anisotropy

Deformation microstructures, including lattice-preferred orientations (LPOs) of olivine, enstatite, and diopside, in mantle xenoliths at Shanwang, eastern China, were studied to understand the deformation mechanism and seismic anisotropy of the upper mantle. The Shanwang is located across the Tan-Lu fault zone, which was formed due to the collision between the Sino-Korean and South China cratons. All samples are spinel lherzolites and wehrlites, and LPOs of minerals were determined using scanning electron microscope/electron backscattered diffraction. We found two types of olivine LPO: type-B in spinel lherzolites and type-E in wehrlites. Enstatite showed two types of LPO (types BC and AC), and diopside showed four different types of LPO. Observations of strong LPOs and numerous dislocations in olivine suggest that samples showing both type-B and -E LPOs were deformed in dislocation creep. The seismic anisotropy of the P-wave was in the range of 2.2–11.6% for olivine, 1.2–2.3% for enstatite, and 2.1–6.4% for diopside. The maximum seismic anisotropy of the shear wave was in the range 1.93–7.53% for olivine, 1.53–2.46% for enstatite, and 1.81–6.57% for diopside. Furthermore, the thickness of the anisotropic layer was calculated for four geodynamic models to understand the origin of seismic anisotropy under the study area by using delay time from shear wave splitting, and S-wave velocity and anisotropy from mineral LPOs. We suggest that the seismic anisotropy under the study area can be most likely explained by two deformation modes that might have occurred at different times: one of deformed lherzolites with a type-B olivine LPO by lateral shear during/after the period of the Mesozoic continental collision between the Sino-Korean and South China cratons; and the other deformed the wehrlites with a type-E olivine LPO by horizontal extension during the period of change in absolute plate motion in relation to the westward-subducting Pacific plate.     

Experimental study of liquid immiscibility in the fluid-magmatic silicate systems containing Ti,Nb, Sr,REE, and Zr

Aluminosilicate alkaline systems containing Ti, REE (La, Ce), Y, Sr, and Nb were studied experimentally at T = 1200 and 1250°C and P = 2 kbar in the presence of aqueous and alkaline fluid. In the fluid-absent experiments with systems containing the same elements, loparite crystals in a silicate matrix were obtained. These systems in the presence of aqueous and alkaline fluid pressure conditions demonstrate an immiscible splitting into two liquids: (1) aluminosilicate matrix and (2) droplets enriched in Ti, REE (La, Ce), Y, Sr, and Nb, which contain silicate admixture and are compositionally close to loparites. According to approximate estimates, the partition coefficients between the melts of the droplets and aluminosilicate matrix (K = C _dr/C _sil) are more than 5 for TiO₂, < 0.35 for SiO₂, 10–20 for Nb₂O₅, > 15 for REE, and from 2.3 to 7.6 for SrO. Obtained unmixing may be of great significance for explaining the genesis of REE-Nb (loparite) deposits. In addition, the experiments demonstrate that Zr may be accumulated together with Ti and REE due to liquid immiscibility of this type. The partition coefficient of ZrO₂ between the melts of droplets and aluminosilicate matrix (K = C _dr/C _sil) according to approximate estimates varies from ∼ 3.5 to 9.     

黔西威宁地区玄武岩风化壳稀土赋存状态与浸出实验

选取贵州西部威宁地区峨眉山玄武岩风化壳中稀土作为研究对象,进行稀土的浸出实验,讨论稀土元素的赋存状态。实验结果显示,哲觉、海外剖面的样品稀土含量∑REY(∑REE+Y)平均为1086.66×10-6,是潜在的风化壳型稀土资源,但其浸出率平均值为7.14%,且在粘土岩中的浸出率较高,粉砂岩和凝灰质粘土岩次之,表明离子吸附型稀土占的比例很低,稀土在玄武岩风化壳中的赋存状态主要不是以离子吸附型存在。基于目前技术,离子吸附相稀土才是稀土利用的基础,威宁地区峨眉山玄武岩风化壳中稀土难以作为离子吸附型稀土资源来进行综合利用。     

贵州西南部峨眉山玄武岩分布区架底和大麦地金矿床金的赋存状态

贵州西南部峨眉山玄武岩分布区位于滇黔桂"金三角"北段,区内成矿地质条件优越、找矿前景较好.贵州省地矿局一0五地质大队根据黔西南地区金矿找矿建立的成矿模式,理论指导找矿,近年来成功新发现了赋存于峨眉山玄武岩中的架底大型金矿床和大麦地中型金矿床,在贵州西南部峨眉山玄武岩分布区乃至全国玄武岩分布区实现了原生金矿的重大找矿突破,架底、大麦地两个金矿床地质特征基本一致.通过详实的岩相学研究,并结合扫描电镜(SEM)、电子探针(EPMA)、激光剥蚀-等离子体质谱(LA-ICP-MS)和金物相分析研究,认为金主要以"不可见金"形式赋存于含砷黄铁矿和毒砂中.架底金矿床赋存于峨眉山玄武岩组中的金矿体(Ⅱ矿体)中的金主要以包裹金形式存在于硫化物中,其平均占有率达73.8％,其次为硅酸盐矿物中的金和游离金,其平均占有率分别为15.4％、8.8％;而赋存于构造蚀变体(SBT)中的金矿体(Ⅰ矿体)中的金主要以游离金形式存在,其平均占有率达90.6％,其次以包裹金形式存在于硫化物、硅酸盐矿物和碳酸盐矿物中,可能与样品受后期风化-氧化作用有关.大麦地金矿床赋存于峨眉山玄武岩组中的金矿体(Ⅱ矿体)中的金与赋存于构造蚀变体(SBT)中的金矿体(Ⅰ矿体)中的金的存在形式基本一致,主要以包裹金形式存在于硅酸盐矿物和硫化物中,其平均占有率分别为41.2％、35.6％,其次为游离金,其平均占有率为16.4％.     

An experimental study of Ostwald ripening of olivine and plagioclase in silicate melts: implications for the growth and size of crystals in magmas

We carried out an experimental study to characterize the kinetics of Ostwald ripening in the forsterite-basalt system and in the plagioclase (An₆₅)-andesite system. Eight experiments were done in each system to monitor the evolution of mean grain size and crystal size distribution (CSD) with time t; the experiments were performed in a 1-atmosphere quench furnace, at 1,250°C for plagioclase and 1,300°C for olivine. Very contrasted coarsening kinetics were observed in the two series. In the plagioclase series, the mean grain size increased as log(t), from ≈3 μm to only 8.7 μm in 336 h. The kinetic law in log(t) means that Ostwald ripening was rate-limited by surface nucleation at plagioclase-liquid interfaces. In the olivine series, the mean grain size increased as t ^1/3, from ≈3 μm to 23.2 μm in 496 h. A kinetic law in t ^1/3 is expected when Ostwald ripening is rate-limited either by diffusion in the liquid or by grain growth/dissolution controlled by a screw dislocation mechanism. The shape of olivine CSDs, in particular their positive skewness, indicates that grain coarsening in the olivine experiments was controlled by a screw dislocation mechanism, not by diffusion. As the degrees of undercooling ΔT (or supersaturation) involved in Ostwald ripening are essentially <1°C, the mechanisms of crystal growth identified in our experiments are expected to be those prevailing during the slow crystallisation of large magma chambers. We extrapolated our experimental data to geological time scales to estimate the effect of Ostwald ripening on the size of crystals in magmas. In the case of plagioclase, Ostwald ripening is only efficient for mean grain sizes of a few microns to 20 μm, even for a time scale of 10⁵ years. It can, however, result in a significant decrease of the number of small crystals per unit volume, and contribute to the development of convex upwards CSDs. For olivine, the mean grain size increases from 2–3 μm to ≈70 μm in 1 year and 700 μm in 10³ years; a mean grain size of 3 mm is reached in 10⁵ years. Accordingly, the rate of grain size-dependent processes, such as compaction of olivine-rich cumulates or melt extraction from partially molten peridotites, may significantly be enhanced by textural coarsening.     

Thermodynamic and kinetic constraints on reaction rates among minerals and aqueous solutions. III. Activated complexes and the pH-dependence of the rates of feldspar,pyroxene, wollastonite,and olivine hydrolysis

The stoichiometries of activated complexes responsible for controlling the kinetics of mineral dissolution can be inferred from experimental rate data. Constraints are provided by adsorption equilibria, surface ion exchange reactions, and the pH-dependence of the steady-state rates of surface detachment. Adsorption equilibria may lead to accelerated or decelerated rates of hydrolysis due to formation of surface species. They may also result in pH-independent dissolution rates at low pH as a consequence of hydrogen ion surface saturation. Surface exchange reactions of H⁺ or H₃O⁺ for M(2) site cations in pyroxenes, Ca²⁺ in wollastonite, and alkali cations in feldspars go essentially to completion for dissolution in solutions that are appreciably undersaturated with respect to the reactant mineral. The rate of surface exchange is proportional to the fraction of exchangeable cations on the reacting surface, which leads to an integrated exponential relation for mass transfer as a function of time. The independence of detachment rates on the degree of surface exchange indicates approximately equivalent formation of activated complexes at both exchanged and unexchanged sites. The degree of hydration or protonation of activated complexes formed from surface species at active sites can be inferred from the dependence of the steady-state hydrolysis rates on pH.     

Experimental Study on the Solubility of Cr^2 in Olivine,Orthopyroxene and Spinel Solid Solutions

Experiments have been performed on the system MgO-SiO2-Cr-O at 0-2.88 GPa and 1100-1450℃,focusing on the stability of Cr^2 in olivine(O1),orthopyroxene(Opx) and spinel(Sp) and its partitioning between these phases.Analytical reagent grade chemicals,MgO,SiO2,Cr2O3.and Cr were used to make starting mixtures.Excess Cr(50%) was then added in these mixtures to ensure that the resultant phases were in equilibrium with the metal Cr.Flux of BaO B2O3(%) was added for facilitating experimental equilibrium and crystal growth.Cr was used as capsule material.All phases in the product were identified by X-ray and analyzed by electron microprobe,The contents of CrO in the different phases(O1,Opx and Sp)were calculated according to stoichiometry.The obtained results of calculation indicate that Cr^3 in Ol and Opx is negligible.The experimental results show;(a) with increasing temperature and decreasing pressure,Cr^2 solubility in Ol,Opx and Sp increases;(b) with in creasing temperature,the partitioning coefficient of Mg and Cr^2 between Ol and Opx decreases,that between Opx and Sp increases,and that between Ol and Sp remains almost unchanged;(c) the effect of pressure on all partitioning coefficients is negligible.