Olivine dissolution in basaltic melt

The main purpose of this work is to understand and quantify diffusive and convective olivine dissolution in basaltic melt. Crystal dissolution and growth in a magma chamber is often accompanied by the descent or ascent of the crystal in the chamber due to gravity. The motion induces convection that enhances mass transport. Such convective dissolution and growth rates have not been quantified before. MgO diffusivity in the melt (D_MgO), MgO concentration of the interface melt (C₀) and the effective thickness of the compositional boundary layer (δ) are necessary parameters to model the convective dissolution. Experiments of non-convective olivine dissolution in a basaltic melt were conducted at 1271-1480 °C and 0.47-1.42 GPa in a piston-cylinder apparatus. At specific temperature and pressure conditions, multiple experiments of different durations show that the interface melt reaches near-saturation within 2 min. Therefore, diffusion, not interface reaction, is the rate-controlling step for non-convective olivine dissolution in basaltic melt. The compositional profile length and olivine dissolution distance are proportional to the square root of experimental duration, consistent with diffusive dissolution. D_MgO and C₀ are obtained from the experimental results. D_MgO displays Arrhenian dependence on temperature, but the pressure dependence is small and not resolved. C₀ increases with increasing temperature and decreases with increasing pressure. Comparison with literature data shows that D_MgO depends strongly on the initial melt composition, while C₀ does not. δ is estimated from fluid dynamics. D_MgO/δ, which characterizes the kinetic and dynamic aspects of convective crystal dissolution, is parameterized as a function of temperature, pressure, and olivine composition. Convective olivine dissolution rate in basaltic melt can be conveniently calculated from the model results. Application to convective crystal growth and xenolith digestion is discussed.     

Halogen diffusion in a basaltic melt

The diffusion of the halogens fluorine, chlorine and bromine was measured in a hawaiitic melt from Mt. Etna at 500 MPa and 1.0 GPa, 1250 to 1450 °C at anhydrous conditions; the diffusion of F and Cl in the melt was also studied with about 3 wt% of dissolved water. Experiments were performed using the diffusion-couple technique in a piston cylinder. Most experiments were performed with only one halogen diffusing between the halogen-enriched and halogen-poor halves of the diffusion couple, but a few experiments with a mixture of halogens (F, Cl and Br) were also performed in order to investigate the possibility of interactions between the halogens during diffusion. Fluorine and chlorine diffusivity show a very similar behavior, slightly diverging at low temperature. Bromine diffusion is a factor of about 2-5 lower than the other halogens in this study. Diffusion coefficients for fluorine range between 2.3 × 10⁻¹¹ and 1.4 × 10⁻¹⁰ m² s⁻¹, for chlorine between 1.1 × 10⁻¹¹ and 1.3 × 10⁻¹⁰ and for bromine between 9.4 × 10⁻¹² and 6.8 × 10⁻¹¹ m² s⁻¹. No pressure effect was detected at the conditions investigated. In experiments involving mixed halogens, the diffusivities appear to decrease slightly (by a factor of ∼3), and are more uniform among the three elements. However, activation energies for diffusion do not appear to differ between experiments with individual halogens or when they are all mixed together. The effect of water increases the diffusion coefficients of F and Cl by no more than a factor of 3 compared to the anhydrous melt (D_F = 4.0 × 10⁻¹¹ to 1.6 × 10⁻¹⁰ m² s⁻¹; D_Cl = 3.0 × 10⁻¹¹ to 1.9 × 10⁻¹⁰ m² s⁻¹). Comparing our results to the diffusion coefficients of other volatiles in nominally dry basaltic melts, halogen diffusivities are about one order of magnitude lower than H₂O, similar to CO₂, and a factor of ∼5 higher than S. The contrasting volatile diffusivities may affect the variable extent of volatile degassing upon melt depressurization and vesiculation, and can help our understanding of the compositions of rapidly grown magmatic bubbles.     

In situ determination of long-term basaltic glass dissolution in the unsaturated zone

Maximum in situ weathering rates of basaltic glass measured at the El Malpais National Monument in New Mexico are on the order of 2–5×10⁻¹⁹ mol/cm² s. Rates were calculated from backscattered electron (BSE) imaging of weathered porosity and are equivalent to 1.7–5% of the surface per 1000 years. Weathering is independent of glass composition but appears to increase with flow elevation at El Malpais. Measured rates represent weathering over 3000 years and are substantially lower than glass dissolution rates measured in the laboratory over much shorter time spans. Basaltic glass is a close chemical analogue to glass hosts proposed for encapsulation of high-level nuclear wastes. Radionuclide release rates predicted from the basis of in situ field rates are substantially less than those predicted from short-term laboratory experiments.     

Plagioclase nucleation and growth kinetics in a hydrous basaltic melt by decompression experiments

Isothermal single-step decompression experiments (at temperature of 1075 °C and pressure between 5 and 50 MPa) were used to study the crystallization kinetics of plagioclase in hydrous high-K basaltic melts as a function of pressure, effective undercooling (ΔT _eff) and time. Single-step decompression causes water exsolution and a consequent increase in the plagioclase liquidus, thus imposing an effective undercooling (?T _eff), accompanied by increased melt viscosity. Here, we show that the decompression process acts directly on viscosity and thermodynamic energy barriers (such as interfacial-free energy), controlling the nucleation process and favoring the formation of homogeneous nuclei also at high pressure (low effective undercoolings). In fact, this study shows that similar crystal number densities (N _a) can be obtained both at low and high pressure (between 5 and 50 MPa), whereas crystal growth processes are favored at low pressures (5–10 MPa). The main evidence of this study is that the crystallization of plagioclase in decompressed high-K basalts is more rapid than that in rhyolitic melts on similar timescales. The onset of the crystallization process during experiments was characterized by an initial nucleation event within the first hour of the experiment, which produced the largest amount of plagioclase. This nucleation event, at short experimental duration, can produce a dramatic change in crystal number density (N _a) and crystal fraction (?), triggering a significant textural evolution in only 1 h. In natural systems, this may affect the magma rheology and eruptive dynamics on very short time scales.     

Nitrogen solubility in basaltic melt. Part I. Effect of oxygen fugacity

The role of the oxygen fugacity on the incorporation of nitrogen in basaltic magmas has been investigated using one atmosphere high temperature equilibration of tholeiitic-like compositions under controlled nitrogen and oxygen partial pressures in the [C-N-O] system. Nitrogen was extracted with a CO₂ laser under high vacuum and analyzed by static mass spectrometry. Over a redox range of 18 oxygen fugacity log units, this study shows that the incorporation of nitrogen in silicate melts follows two different behaviors. For log fO₂ values between −0.7 and −10.7 (the latter corresponding to IW − 1.3), nitrogen dissolves as a N₂ molecule into cavities of the silicate network (physical solubility). Nitrogen presents a constant solubility (Henry’s) coefficient of 2.21 ± 0.53 × 10⁻⁹ mol g⁻¹ atm⁻¹ at 1425°C, identical within uncertainties to the solubility of argon. Further decrease in the oxygen fugacity (log fO₂ between −10.7 and −18 corresponding to the range from IW − 1.3 to IW − 8.3) results in a drastic increase of the solubility of nitrogen by up to 5 orders of magnitude as nitrogen becomes chemically bounded with atoms of the silicate melt network (chemical solubility). The present results strongly suggest that under reducing conditions nitrogen dissolves in silicate melts as N³⁻ species rather than as CN⁻ cyanide radicals. The nitrogen content of a tholeiitic magma equilibrated with N₂ is computed from thermochemical processing of our data set as

     

Experimental determination of F and Cl partitioning between lherzolite and basaltic melt

We experimentally determined F and Cl partition coefficients together with that of 19 trace elements (including REE, U-Th, HFSE and LILE) between basaltic melt and lherzolite minerals: olivine, orthopyroxene, clinopyroxene, plagioclase and garnet. Under conditions from 8 to 25 kbars and from 1,265 to 1,430°C, compatibilities of F and Cl are globally ordered as D ^Cpx/melt > D ^Opx/melt > D ^Grt/melt > D ^Ol/melt > D ^Plag/melt, and D _F ^mineral/melt is larger than D _Cl^mineral/melt. Four other major results were brought to light. (1) Chlorine partition coefficients positively correlate with the jadeite component in orthopyroxene, and increase of the CaTs component promotes Cl incorporation in clinopyroxene. (2) Variations of fluorine partition coefficients correlate strongly with melt viscosity. (3) F and Cl partition coefficients correlate with the Young’s modulus (E ₀) of pyroxene octahedral sites (M sites) and with Raman vibrational modes of pyroxenes. This demonstrates a fundamental interaction between the M site of pyroxenes and the incorporation of F and Cl. (4) We also determined the parameters of the lattice-strain model applied to 3+ cation trace elements for the two M sites in orthopyroxene and clinopyroxene: D ₀^M1, D ₀^M2, r ₀^M1, r ₀^M2, E ₀^M1 and E ₀^M2.     

Tracer diffusion of some alkali,alkaline-earth and transition element ions in a basaltic and an andesitic melt,and the implications concerning melt structure

The diffusion properties of Na, Cs, Sr, Ba, Co, Mn, Fe and Sc ions in a basaltic and an andesitic melt have been determined experimentally using the radiotracer residual-activity method, and narrow platinum capillaries, over the temperature range 1,300–1,400° C. Diffusion of all cations follows an Arrhenius relationship; the values of the activation energies range from 24 kcal mol^–1 for Na to 67 kcal mol^–1 for Co in the andesitic melt, and from 39 kcal mol^–1 for Na to 65 kcal mol^–1 for Cs in the basaltic melt. Relative diffusivities in the basaltic melt, but not in the andesitic melt, correlate with assumed ionic radii values. Each cation, except Na⁺, diffuses faster in the basaltic melt than in the andesitic melt over the studied temperature range. Sodium shows similar diffusivity in the two melts.Compensation diagrams incorporating new and some previously-published data indicate that Cs probably diffuses by different mechanisms in different silicate glass and melt systems. Iron has a relatively high activation energy which is consistent with its part occupancy of tetrahedral co-ordination polyhedra.     

单斜辉石中石英出溶体的显微结构和成因机制

矿物出溶结构保存有早期母体矿物的物理化学条件信息,对其开展研究不仅有助于了解寄主岩石的来源深度,而且有助于研究减压折返的动力学演化过程.在世界许多高压-超高压带的榴辉岩和石榴辉石岩中,人们普遍发现单斜辉石中有定向排列的针状或棒状SiO₂析出物,其矿物相主要为α石英,有时会伴生钙质角闪石等含水矿物.这些定向针状或棒状体通常平行于单斜辉石c[001]轴方向延伸,石英长轴可以为其c[0001]轴或a[1120]轴.电子背散射衍射(EBSD)测试结果表明,多数石英(96%)析出物与寄主单斜辉石具有结晶学取向关系:(1) 50%的石英c轴平行,并且[0001]_Qz//[001]_Cpx;(2)35%的石英至少有一个a轴平行,并且[1120]_Qz//[001]_Cpx;(3)11%的石英至少有一个s{1121}面平行,并且(1121)_Qz//(100)_Cpx.钙质角闪石析出物与寄主单斜辉石也具有密切结晶学取向关系:(100)_Amp//(100)_Cpx、[010]_Amp//[010]_Cpx、[001]_Amp//[001]_Cpx、[100]_Amp∧[100]_Cpx≈32°.上述定量显微构造证据表明,单斜辉石中定向石英析出物是由出溶作用所形成,并且多数石英出溶体形成于α石英稳定域.已有高温高压实验研究数据表明,单斜辉石中空位的形成和钙埃斯科拉组分(CaEs)的含量均受化学组成、压力、温度等多种因素综合影响:单斜辉石中CaEs含量对化学组成非常敏感,并受到共生矿物体系中自由SiO₂相和蓝晶石的共同缓冲;相同化学组成和等压条件下,CaEs含量总体上随温度升高缓慢降低;相同化学组成和等温条件下,CaEs含量在＜6 GPa区间随压力升高而增加,在＞6 GPa区间随压力升高而降低.单斜辉石定向SiO₂析出物的形成可能涉及多种因素,高压只是其中必要条件之一.榴辉岩质单斜辉石中“石英±角闪石”析出物很可能形成于开放体系,与熔流体活动密切相关,涉及多阶段物质扩散、晶体成核生长、重结晶、退变质反应等复杂作用过程.单斜辉石中定向SiO₂析出物的显微结构特征并非超高压岩石的必要条件,这种特殊显微结构也不能作为证明超高压的充分条件.      

Numerical modeling of major element distribution between chromian spinel and basaltic melt, with application to chromian spinel in MORBs

A set of empirical equations is developed which allows calculation of chromian spinel composition in equilibrium with a basaltic melt under a known set of conditions. These equations are calibrated with published experimental data for the temperature range from 1,093 to 1,490 °C and a pressure of up to 20 kbar. It is demonstrated that the composition of chromian spinel from the experiments, which crystallizes from basaltic, boninitic, and komatiitic melt and varies from high-Al to high-Cr, and high-Fe³⁺ can be successfully reproduced using the suggested model. The composition of chromian spinel has been calculated using the glass composition for a set of primitive basaltic lavas using the suggested set of empirical equations. Good agreement between the calculated composition and composition of rims of chromian spinel included in glass is achieved for compositionally diverse spinel from a Hawaiian sample and 15 MORB samples. The Fe₂O₃ content in the chromian spinels is, however, often variable and higher than the calculated Fe₂O₃ content. Additional calculations using 76 published MORB glass analyses reproduced most of the MORB chromian spinel range, except for the most Cr- and Mg-rich. The crystallization of these Cr-rich chromian spinels likely occurred from a more primitive Al-poor melt than that of the 76 MORB glasses. An example of a more primitive glass can occasionally be found as glass inclusions in these Cr- and Mg-rich chromian spinel microphenocrysts.     

Geobarometry for Mantle Eclogites: Solubility Of Ca-Tschermaks in Clinopyroxene

A garnet-clinopyroxene barometer is proposed for mantle eclogites on the basis of the Ca-Tscher-mack (CaTs) solubility in clinopyroxene coexisting with garnet. This barometer permits estimation of P-T conditions for garnet-clinopyroxene equilibration in the range 650°C ≤ T ≤ 1700°C and 20 ≤ P ≤ 70 kbar, with a total uncertainty of 19%. This model is applicable to pyroxenes that are sodium rich (i.e., have high jadeite contents). Application of this barometer results in high P-T estimates for Monastery and Argyle diamond inclusions. Estimates also are lower for the host Yakutian eclogites than for the diamonds included in them. This suggests differences in re-equilibration between the diamond inclusions and their host xenoliths. The results suggest that eclogite equilibration in the mantle occurs at depths from 60 to 230 km, characterized by two main types of geothermal gradients, lying close to established peridotite geotherms (Boyd, 1973).     

巨晶普通辉石的M1位分裂

巨晶普通辉石的Ｍ１位分裂李一良，支霞臣，李玉芝，李铁，张裕恒（中国科学技术大学，合肥２３００２６）关键词巨晶辉石，Ｍ１位分裂，面积约束法，近邻边效应，Ｔ位铁单斜辉石的穆斯堡尔谱学研究历时已久。但由于其晶体结构和成份的复杂性、化学不均一性及出溶现象等［...     

Natural Clinopyroxene Reference Materials for In Situ Microanalysis

Two clinopyroxene megacrysts, DMP-2 and DMP-3, were collected from Cenozoic alkali basalts in the Hannuoba region of China. They were characterised for major and trace element compositions for in situ microanalysis. EPMA and LA-ICP-MS analyses indicate homogeneity in the element mass fractions in both clinopyroxene samples. Bulk analyses using various techniques (XRF, ICP-OES and solution ICP-MS) also reveal good consistency in their major and trace element data. They, thus, can be used as potential reference materials for elemental in situ microanalysis. Accordingly, element mass fractions are recommended for thirty-two elements.     

Clinopyroxene composition in mafic lavas from different tectonic settings

Many metamorphosed and weathered basalts contain fresh clinopyroxene crystals set in an altered groundmass. Microprobe analysis of these relict grains can be used to identify the magma type of the host lava. Statistical discrimination of clinopyroxenes from known magma types provides a test of the effectiveness of this method, showing that any attempt to classify an unknown clinopyroxene as either an ocean-floor basalt, a volcanic arc basalt, a within plate tholeiite or a within plate alkali basalt magma type should have a 70% chance of success. Identification of within plate alkali basalts is most likely to be successful because their pyroxenes characteristically have high Na and Ti and low Si contents. Within plate tholeiites can usually be distinguished from volcanic arc basalts because their pyroxenes contain more Ti, Fe and Mn. However, neither of these last two magma types can be easily distinguished from ocean floor basalts on the basis of pyroxene analyses. Diagrams of pyroxene composition based on discriminant functions and on Na₂O vs MnO vs TiO₂, SiO₂ vs TiO₂ and SiO₂ vs Al₂O₃ provide the basis for visual discrimination. The discrimination achieved is mainly due to differences in the bulk chemistry of the host magmas and in the partitioning of cations into the pyroxene lattice; differences in temperature and crystallization histroy of the magmas are of lesser, but nevertheless finite, importance. Application of this technique to pyroxenes in metabasalts from Othris, Greece gave results consistent with, but more ambiguous than, results obtained from immobile trace element studies.     

Electron Petrography of Exsolution Textures in an Iron-Rich Clinopyroxene

Ion-thinned samples of an iron-rich augite in an inninmoritepitchstone from Ardnamurchan, Scotland, have been examined bytransmission electron microscopy at 100 and 1000 kV. Eutecticcrystallization of augite and pigeonite occurred and subsequentlysemi-coherent irregularly-shaped regions and coherent (001)lamellae of pigeonite were exsolved in the augite. Nucleationoccurred heterogeneously at grain boundaries and subsequentgrowth of the lamellae proceeded by the migration of ledgesalong the (001) interface. The analytical electron microscope EMMA-4 has been used to analysethe exsolved pigeonite lamellae. Their composition was foundto be similar to that of the co-existing primary pigeonite. It is concluded that the augite cooled through the solvus slowlyenough for heterogeneous nucleation and growth to occur whereaspyroxenes which cool rapidly unmix by the mechanism of spinodaldecomposition.