Isotopic fractionation of the major elements of molten basalt by chemical and thermal diffusion

Samples produced in piston cylinder experiments were used to document the thermal isotopic fractionation of all the major elements of basalt except for aluminum and the fractionation of iron isotopes by chemical diffusion between a natural basalt and rhyolite. The thermal isotopic fractionations are summarized in terms of a parameter Ω_i defined as the fractionation in per mil per 100 °C per atomic mass units difference between the isotopes. For molten basalt we report Ω_Ca = 1.6, Ω_Fe = 1.1, Ω_Si = 0.6, Ω_O = 1.5. In an earlier paper we reported Ω_Mg = 3.6. These fractionations represent a steady state balance between thermal diffusion and chemical diffusion with the mass dependence of the thermal diffusion coefficient being significantly larger than the mass dependence of the chemical diffusion coefficients for isotopes of the same element. The iron isotopic measurements of the basalt-rhyolite diffusion couple showed significant fractionation that are parameterized in terms of a parameter β_Fe = 0.03 when the ratio of the diffusion coefficients D₅₄ and D₅₆ of ⁵⁴Fe and ⁵⁶Fe is expressed in terms of the atomic mass as D₅₄/D₅₆ = (56/54)^β_Fe. This value of β_Fe is smaller than what we had measured earlier for lithium, magnesium and calcium (i.e., β_Li = 0.215, β_Ca = 0.05, β_Mg = 0.05) but still significant when one takes into account the high precision with which iron isotopic compositions can be measured (i.e., ±0.03‰) and that iron isotope fractionations at magmatic temperatures from other causes are extremely small. In a closing section we discuss technological and geological applications of isotopic fractionations driven by either or both chemical and thermal gradients.     

Magnesium isotope fractionation in silicate melts by chemical and thermal diffusion

Two types of laboratory experiments were used to quantify magnesium isotopic fractionations associated with chemical and thermal (Soret) diffusion in silicate liquids. Chemical diffusion couples juxtaposing a molten natural basalt (SUNY MORB) and a molten natural rhyolite (Lake County Obsidian) were run in a piston cylinder apparatus and used to determine the isotopic fractionation of magnesium as it diffused from molten basalt to molten rhyolite. The thermal diffusion experiments were also run in a piston cylinder apparatus but with a sample made entirely of molten SUNY MORB displaced from the hotspot of the assembly furnace so that the sample would have a temperature difference of about 100-200 °C from one end to the other. The chemical diffusion experiments showed fractionations of ²⁶Mg/²⁴Mg by as much as 7‰, which resulted in an estimate for the mass dependence of the self-diffusion coefficients of the magnesium isotopes corresponding to D_26Mg/D_24Mg=(24/26)^β with β = 0.05. The thermal diffusion experiments showed that a temperature difference of about 100 °C resulted in the MgO, CaO, and FeO components of the basalt becoming slightly enriched by about 1 wt% in the colder end while SiO₂ was enriched by several wt% in the hotter end. The temperature gradient also fractionated the magnesium isotopes. A temperature difference of about 150 °C produced an 8‰ enrichment of ²⁶Mg/²⁴Mg at the colder end relative to the hotter end. The magnesium isotopic fractionation as a function of temperature in molten basalt corresponds to 3.6 × 10⁻²‰/°C/amu.     

Liquid composition-dependence of calcium isotope fractionation during diffusion in molten silicates

Liquid phase diffusion experiments were carried out to determine whether diffusive isotopic fractionation of a major chemical element (Ca) varies with chemical composition in high-temperature molten silicates. The objective was to determine how differences in silicate liquid structure, such as the ratio of bridging to non-bridging oxygen atoms, as well as bulk transport properties such as viscosity, relate to isotope discrimination during diffusion. This information, in turn, may relate to the lifetimes and sizes of multi-atom structures in the liquid. Diffusion couples consisting of juxtaposed natural mafic and felsic liquids were held at T = 1450 °C and P = 1.0 GPa for durations of 12-24 h in a standard piston-cylinder assembly. Experiments were done using different mafic endmember compositions (two tholeiitic basalts and a ugandite) and a single rhyolite composition. Major-element diffusion profiles and Ca isotope profiles were measured on the recovered quenched glasses. The starting materials were isotopically indistinguishable, but ⁴⁴Ca/⁴⁰Ca variations of ca. 5‰ arose due to a mass dependence of the Ca diffusion coefficients. Results indicate that the mass dependence of Ca diffusion coefficients varies with the magnitude and direction of aluminum gradients and the viscosity of the liquid. Some Ca fractionations result mainly from Al gradients.A simplified multicomponent diffusion model was used to model the experimental results. The model allows for diffusion of Ca in response to gradients in the concentrations of both CaO as well as Al₂O₃, and the model results are consistent with the inferred existence of at least two distinct species of Ca. The magnitude of isotopic discrimination during diffusion also appears to be stronger on the rhyolite versus the basalt/ugandite side of diffusion couples. The results can largely be accounted for by an adaptation of the model of Dingwell (1990), whereby in high silica liquids, Ca diffuses largely by site hopping through a quasi-stationary aluminosilicate matrix, producing strong isotopic effects because the Ca diffusion is not strongly correlated with the movement of the framework atoms. In low-silica liquids, Ca diffusion is correlated with the movement of the other components and there is less mass discrimination. Combining our Ca results with Ca, Mg, and Li data from previous studies, we show that this model can explain most of the cation- and composition-dependence of diffusive isotopic fractionations observed thus far. A key parameter controlling isotopic discrimination is the ratio of the elemental (Ca, Mg, Li) diffusivity to the Eyring (or Si) diffusivity. However, all experiments done so far also exhibit isotopic features that are not yet fully explained; some of these may relate to small temperature gradients in the capsules, or to more complex coupling effects that are not captured in simplified diffusion models.     

Non-traditional fractionation of non-traditional isotopes: Evaporation,chemical diffusion and Soret diffusion

Recent developments documenting high temperature isotope fractionations of a variety of elements (Li, Mg, Si, Ca, Fe, Ni) by a variety of processes (evaporation, chemical diffusion and thermal diffusion) are reviewed along with some recent applications of these fractionations to Earth and meteoritic problems.     

An experimental investigation of high-temperature interactions between seawater and rhyolite,andesite, basalt and peridotite

Natural seawater was allowed to react with rhyolite, andesite, basalt, and peridotite at 200°–500° C, and 1,000 bars at water/rock mass ratios of 5 and 50 in order to investigate the effects of rock type, water/rock ratio, and temperature on solution chemistry and alteration mineralogy. The results indicate that interactions of seawater with various igneous rocks are similar in the production of a hydrous Mg-silicate and anhydrite as major alteration products. Fluids involved in the interactions lose Mg to alteration phases while leaching Fe, Mn, and Si from the rocks. The pH of the solutions is primarily controlled by Mg-OH-silicate formation and therefore varies with Mg and Si concentration of the system. Other reactions which involve Mg (such as Mg-Ca exchange) or which produce free H⁺, cause major differences in fluid chemistry between different seawater/ rock systems. High water/rock ratio systems (50/1) are generally more acidic and more efficient in leaching than low ratio systems (5/1), due to relatively more seawater Mg available for Mgsilicate production. The experiments show that large-scale seawater/rock interaction could exert considerable control on the chemistry of seawater, as well as producing large bodies of altered rock with associated ore-deposits.Active plate margins of convergence or divergence are suitable environments for hydrothermal systems due to the concurrence of igneous activity, tectonism, and a nearby water reservoir (seawater or connate water). The experimental data indicate that seawater interactions with igneous host rocks could generate many of the features of ore-deposits such as the Kuroko deposits of Japan, the Raul Mine of Peru, the Bleida deposit of Morocco, and deposits associated with ophiolites. Serpentinization of peridotite and alteration of igneous complexes associated with plate margins can also be explained by seawater interaction with the cooling rock. Geothermal energy production could benefit from experimental investigations of hot water/rock systems by development of chemical, temperature, and pressure control systems to maximize the lifetime of hydrothermal flow.     

Oxygen diffusion in basalt and andesite melts: experimental results and discussion of chemical versus tracer diffusion

Chemical diffusion coefficients for oxygen in melts of Columbia River basalt (Ice Harbor Dam flow) and Mt. Hood andesite have been determined at 1 atm. The diffusion model is that of sorption or desorption of oxygen into a sphere of uniform initial concentration from a constant and semi-infinite atmosphere. The experimental design utilizes a thermogravimetric balance to monitor the rate of weight change arising from the response of the sample redox state to an imposed fO₂. Oxygen diffusion coefficients are approximately an order-ofmagnitude greater for basaltic melt than for andesitic melt. At 1260° C, the oxygen diffusion coefficients are: D=1.65×10^–6cm²/s and D=1.43×10^–7cm²/s for the basalt and andesite melts, respectively. The high oxygen diffusivity in basaltic melt correlates with a high ratio of nonbridging oxygen/tetrahedrally coordinated cations, low melt viscosity, and high contents of network-modifying cations. The dependence of the oxygen diffusion coefficient on temperature is: D=36.4exp(–51,600±3200/RT)cm²/s for the basalt and D=52.5exp(–60,060±4900/RT)cm²/s for the andesite (R in cal/deg-mol; T in Kelvin). Diffusion coefficients are independent of the direction of oxygen diffusion (equilibrium can be approached from extremely oxidizing or reducing conditions) and thus, melt redox state. Characteristic diffusion distances for oxygen at 1260° C vary from 10^-2 to 10² m over the time interval of 1 to 10⁶ years. A compensation diagram shows two distinct trends for oxygen chemical diffusion and oxygen tracer diffusion. These different linear relationships are interpreted as supporting distinct oxygen transport mechanisms. Because oxygen chemical diffusivities are generally greater than tracer diffusivities and their Arrhenius activation energies are less, transport mechanisms involving either molecular oxygen or vacancy diffusion are favored.     

Hawaiian basalt and Icelandic rhyolite: Indicators of differentiation and partial melting

In spite of the voluminous basaltic volcanism on the island of Hawaii, rhyolite is not produced. Iceland, on the other hand, exhibits common rhyolitic volcanism amounting to some 10–12% of its surface rocks. This contrast is investigated using the fundamental igneous processes exhibited by sheet-like Hawaiian lava lakes and Shonkin Sag laccolith in Montana. Highly differentiated, residual melts normally reside within inwardly advancing solidification fronts and are generally inaccessible to eruptive processes. Only when a large initial phenocryst population is present, from which a thick basal cumulate can rapidly form, is it possible to supply highly differentiated melt into the active (i.e., eruptable) portion of the magma chamber. Although there is protracted control of differentiation at Hawaii by settling of olivine, further differentiation occurs within the solidification fronts. Only by repeated transport and holding is it possible to differentiate beyond the critical composition of the leading edge of the solidification front ( 7% MgO and 51.5% SiO₂). Crystal size distributions (CSDs) for Hawaii and Shonkin Sag are used to demonstrate the inferred physical and chemical processes of solidification, including the kinetics of crystallization.A ubiquitous feature of these basaltic bodies is the formation of coarse veins and segregations of refined melt and granophyres within the upper solidification front. It is this fundamental bimodal feature which is the key to understanding Icelandic silicic volcanism.Rhyolites in Iceland occur mainly as a bimodal population with basalts associated with central volcanoes. Rhyolites, granophyres, and felsites are common, with the intrusions often being layered. Ash flows and true granite-like intrusions are rare. The voluminous silicic lavas at Torfajokull central volcano contain disequilibrium phenocryst assemblages. This, and the disagreement in oxygen isotopic values between rhyolites and basalts, reflects extensive partial melting of the heterogeneous basaltic crust of Iceland to produce these rhyolites. Relatively small, chemically distinct, and spatially intimate silicic bodies are formed by concentrating granophyric segregations from earlier cycles of solidification. This process is also reflected in the layered granophyric instrusion of Slaufrudalur in eastern Iceland. Slaufrudalur is an unvented subterranean caldera, equivalent in igneous processes and style to the subaerial Torfajokull caldera.Hawaii is dominated by fractional crystallization due to crystal settling and does not produce rhyolite. Iceland's tectonics allow continual and extensive reprocessing of thin, hot basaltic crust which produces rhyolite by concentrating original silicic segregations and veins and by partially melting intermediate extrusives, which have subsided deep into the crust.

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Zusammenfassung Auf Hawaii treten, trotz intensiven Basalt-Vulkanismusses, keine Rhyolithe auf. Auf Island dagegen ist Rhyolith, mit 10–12% des anstehenden Gesteins, verbreitet. Dieser Kontrast wurde anhand grundlegender magmatischer Prozesse untersucht, wie sie in flachen Lava-Seen Hawaiis und im Shonkin Sag Laccolith Montanas auftreten. Hochdifferenzierte Restschmelzen verbleiben innerhalb langsam nach innen vorrückender Erstarrungsfronten und sind meist unerreichbar für eruptive Prozesse. Nur wenn anfänglich bereits große Mengen von Einsprenglingen vorhanden sind, die rasch am Boden der Magmenkammer akkumulieren, kann eine hochdifferenzierte Schmelze in den aktiven (d.h. eruptiven) Teil der Magmenkammer gelangen. Obwohl auf Hawaii die Differentiation durch die Kristallisation von Olivin anhaltend kontrolliert wird, findet an der Erstarrungsfront weitere Differentiation statt. Nur durch wiederholten Transport und zeitweiliges Verharren ist es möglich, über die kritische Zusammensetzung der vordersten Erstarrungsfront hinaus zu differenzieren (ca. 7% MgO und 51,5% SiO₂). An Kristallgrö-ßenverteilungen (CDS) von Hawaii und Shonkin Sag können die angenommenen physikalischen und chemischen Prozesse der Kristallisation und die Kristallisationskinetik gezeigt werden. Ein weit verbreitetes Merkmal dieser Basaltkörper ist die Bildung grobkristalliner Gänge und Absonderung von stark differenzierten Schmelzen und Granophyren innerhalb der oberen Erstarrungsfront. Diese ausgeprägt bimodale Charakteristik ist der Schlüssel zum Verständnis des sauren isländischen Vulkanismus.Isländische Rhyolithe treten meist in bimodaler Verbreitung mit Basalten in Zusammenhang mit zentralen Vulkanen auf. Rhyolithe, Granophyre und Feisite sind häufig, in oft geschichteten Intrusionen. Ignimbrite und echte Granitintrusionen sind selten. Die großen Mengen SiO₂-reicher Laven am Torfajokull-Zentralvulkan enthalten Ein-sprenglinge, die sich nicht im Gleichgewicht mit der Matrix befinden. Dies, und die unterschiedlichen delta-¹⁸O-Werte von Rhyolithen und Basalten, zeigen, daß ausgeprägtes teilweises Aufschmelzen der heterogenen Basaltkruste von Island zur Produktion dieser Rhyolithe führte. Relativ kleine, nahe benachbarte saure Körper, die aber deutliche Unterschiede in ihrem Chemismus aufweisen, werden gebildet durch die Konzentration granophyrischer Teilschmelzen aus früheren Kristallisationszyklen. Dieser Vorgang wird auch widergespiegelt in der »layered intrusions« von Slaufrudalur in Ostisland. Slaufrudalur ist eine geschlossene unterirdische Kaldera, deren magmatische Prozesse und Baustil der subaerischen Torfajokull-Kaldera entsprechen.Die Prozesse in Hawaii sind dominiert von gravitativer Kristallisationsdifferentiation und es werden keine Rhyolithe produziert. Die isländische Tektonik führt zu kontinuierlicher starker Wiederaufarbeitung von dünner, heißer basaltischer Kruste. Dabei wird, durch die Konzentration ursprünglicher saurer Teilschmelzen und Gänge und durch die teilweise Aufschmelzung intermediärer Intrusiva, die tief in die Kruste abgesunken sind, Rhyolith produziert.

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Résumé En dépit du volcanisme basaltique volumineux des îles Hawaï, il n'y existe pas de rhyolite. En Islande, par contre, le volcanisme rhyolitique est commun et représente 10 à 12% des roches de la surface. Ce contraste est examiné sur la base des processus ignés fondamentaux présentés par les lacs de lave d'Hawaï et le laccolite de Shonkin Sag au Montana. Normalement, les liquides résiduels hautement différenciés résident à l'intérieur des fronts de solidification qui progressent vers l'arrière et sont généralement à l'abri des processus éruptifs. Ce n'est que dans le cas d'une population initiale abondante de phénocristaux, qui se rassemblent dans un cumulat basai épais, que des liquides hautement différenciés peuvent être fournis à la portion active (c'est-à-dire »éruptible«) de la chambre magmatique. A Hawaï, bien que la différenciation soit continuellement régie par la cristallisation d'olivine, la poursuite du processus a lieu à l'intérieur des fronts de solidification. Ce n'est que par la répétition d'actions de transport et de stagnation qu'il est possible de différencier audelà de la composition critique du front de solidification (±7% MgO et 51,5% SiO₂). A partir de la distribution de la taille des cristaux à Hawaï et à Shonkin Sag, on peut déduire les processus physique et chimique de la solidification, y compris la cinétique de la cristallisation.Une particularité courante de ces corps basaltiques est la formation de veines grenues et de ségrégations de liquides très différenciés et de granophyres à l'intérieur du front supérieur de solidification. Cette manifestation bimodale est la clé qui permet de comprendre le volcanisme siliceux islandais.En Islande, les rhyolites constituent d'ordinaire une population bimodale avec les basaltes centraux. Les rhyolites, les granophyres et les felsites sont fréquents, et souvent sous forme d'intrusions litées. Les coulées ardentes et les vraies intrusions de type granitique sont rares. Les volumineuses laves siliceuses du volcan central de Torfajokull contiennent des assemblages de phénocristaux en déséquilibre. Ce fait, ainsi que la non concordance des isotopes de l'oxygène entre rhyolites et basaltes, traduisent, à l'origine de ces rhyolites, une fusion partielle extensive de la croûte basaltique hétérogène d'Islande. Des corps siliceux relativement petits et chimiquement distincts bien que d'emplacements très voisins se sont formés par concentration de fusions partielles granophyriques lors des premiers cycles de solidification. Ce processus s'exprime également dans l'intrusion granophyrique litée de Slaufrudalur, en Islande orientale. Slaufrudalur est une caldeira souterraine fermée, équivalente par son style et son processus igné à la caldeira subaérienne de Torfajokull.A Hawaï, le phénomène dominant est la cristallisation fractionnée gravitative, sans production de rhyolite. La tectonique de l'Islande permet la régénération continue et extensive d'une mince croûte basaltique chaude. Les rhyolites y sont engendrées par la concentration des veines et ségrégations siliceuses originelles et par la fusion partielle de masses extrusives intermédiaires descendues profondément dans la croûte.

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, . , 10–12% . , Shonkin Sag Laccolith Montanas. . , , . , . . ( 7% MgO 51,5% SiO₂). (CDS) Shonkin Sag , , . . . . , , . . , Torfajokull , ., ¹⁸O , . , , , , « » («layered intrusions») Slaufrudalur, . , , Torfajokull. . . , , , .

     

Iron isotope fractionation during leaching of granite and basalt by hydrochloric and oxalic acids

Transport of iron (Fe) within hydrothermal and soil environments involves the transferral into aqueous solutions by leaching of complex, polyminerallic rocks. Understanding the isotope fractionation mechanisms during this process is key for any application of the Fe-isotope system to biogeochemical studies. Here, we reacted biotite granite and tholeiite-basalt with 0.5 M hydrochloric acid and 5 mM oxalic acid solutions at ambient temperature. Solution aliquots were recovered over a seven-day period and analysed for major and trace element concentrations and Fe isotopic compositions. In all experiments, Fe initially released into solution was isotopically lighter, with Δ⁵⁶Fe_{solution-rock} as low as −1.80‰ in the granite-hydrochloric acid system. The oxalic acid experiments showed similar patterns but smaller fractionation. In all experiments, the Δ⁵⁶Fe_{solution-rock} reduced over time, which would be in line with the formation of a leached layer as proposed before [Brantley S. L., Liermann L. J., Guynn R. L., Anbar A., Icopini G. A., and Barling J. (2004) Fe isotopic fractionation during mineral dissolution with and without bacteria. Geochim. Cosmochim. Acta68(15), 3189-3204]. Granite and basalts reacting with hydrochloric acid reached apparent steady-state values of −0.60 ± 0.15‰ and −0.40 ± 0.20‰, respectively, whilst experimental values with oxalic acid were −1.0 ± 0.15‰ and −0.50 ± 0.15‰. During the granite experiments, alteration of biotite to chlorite, followed by dissolution of chlorite, were likely the dominant processes, whilst in the basalt experiments, dissolution of pigeonite was likely the principal source of Fe. Variations in pH during the hydrochloric acid experiments were minimal, remaining below 0.5 at all times. In oxalic acid solutions, the pH increased to over 4, leading likely to precipitation of secondary minerals and adsorption/co-precipitation of Fe onto mineral surfaces. These processes could contribute to the greater fractionation observed in the final stages of the oxalic acid experiments. Our results highlight the importance of mineralogy and fluid composition on the Fe-isotope systematics during weathering. The fractionation processes identified for granites and basalts are in line with those inferred from field observations in soils, sediments, groundwater and hydrothermal deposits and from laboratory studies of single-mineral leaching.     

Water diffusion in basalt and andesite melts under high pressures

Water diffusion is one of the most important characteristics of many processes dealt with in magmatic geochemistry, petrology, and volcanology. We have experimentally examined water diffusion in Fe-free andesite and basalt melts (stoichiometric mixtures of the minerals albite + diopside + wollastonite) at 3 and 100 MPa, 1300×C, up to approximately 4 wt % water in the melts, and a total (lithostatic) pressure of 100 MPa on a high gas pressure apparatus equipped with a unique internal device. The experiments were conducted simultaneously with the use of two different methods: diffusion hydration and couples. Water solubility in the melts and water concentrations along the diffusion profiles (C _{H 2 O}) were determined by quantitative IR microspectroscopy, using the Beer-Lambert law. A structural chemical model is proposed for calculating and predicting the concentration dependence of the molar absorption coefficient of the hydroxyl group and water molecules in andesite and basalt glasses. The diffusion coefficients of water (D _{H 2 O}) are derived by the mathematical analysis of concentration profiles and the analytical solution of the second Fick diffusion law. Preliminary results indicated D _{H 2 O} is roughly one order of magnitude higher in basaltic melts than in andesitic ones (at the same temperatures and P _{H 2 O}) and significantly (exponentially) increases with increasing water concentrations in andesitic and basaltic melts. The newly obtained experimental data are proved to be fully consistent with the results obtained on the D _{H 2 O} dependence on C _{H 2 O} in melts of acid rocks (rhyolite and obsidian). The derived quantitative dependence between D _{H 2 O} and melt viscosity is used to develope principles of a new method for predicting and calculating the temperature, concentration, and pressure dependences of D _{H 2 O} in magmatic melts of the of acid-basic series (up to 3 wt % C _{H 2 O}) at crustal T, P parameters.     

Chemical modification of enclave magma by post-emplacement crystal fractionation,diffusion and metasomatism

Hornblende-bearing microgranitoid enclaves from the Swifts Creek Pluton (SCP), SE-Australia display mineralogical and textural variations from their margins to their centers. Margins are fine grained and display quench textures and are enriched in amphibole, biotite and in some cases magnetite relative to their coarser grained centers. Enclaves of this type and their adjacent granitoid host rocks have been sectioned into 0.3 to 1 cm thick slabs in order to determine the chemical variations associated with these mineralogical changes. The fine grained margins are variably enriched in Ti, Al, Mg, Fe, Mg, K, Rb, Ba, Nb, Y, Sc, V, Ni and the REE up to a factor of three relative to the enclave centers. This enrichment is compensated by a depletion of Si and Zr. Elements like Ca, Na and Sr show less coherent variation from margin to center. Host rocks in immediate contact with these enclaves are depleted in Mg, Na, K, Rb and Ba relative to host rocks that are not exposed to enclaves. No one single process can account for all the variations. Instead, we propose that the chemical variations are related to a combination of in situ crystal fractionation of isolated magma globules, mass transfer by diffusion and metasomatic exchange.     

顽火辉石中Li同位素扩散与分馏

顽火辉石作为斜方辉石晶系的重要Mg端元矿物,是地球上地幔主要组成矿物之一。Li同位素作为重要的地幔地球化学示踪剂,在主要地幔矿物中(如橄榄石,辉石等)的扩散分馏相关性质的研究显得尤为重要。我们通过经典力学的方法,计算模拟了原子尺度下Li同位素在顽火辉石晶格以2种不同的迁移机制(填隙机制和取代空位机制)迁移的活化能和其在不同晶格位上不同温度条件下的分馏作用程度。计算结果表明,Li同位素易以填隙位机制在顽火辉石中迁移。重同位素~7Li会更多的进入晶格填隙位中,而6Li相对更多进入Mg位。温度是影响这种分馏作用的1个关键因素,相应的结果可用来解释地幔Li同位素组成特征及冷却条件下的同位素分馏等科学问题。     

利用地球化学方法判别大陆玄武岩和岛弧玄武岩

大陆地壳或岩石圈的混染作用可以给出似消减带信号,并导致将受到混染的大陆玄武岩误判为岛弧玄武岩。没有受到混染的软流圈(或地幔柱)源大陆玄武质岩石通常是以(Th/Nb)N<1、Nb/La≥1、低87Sr/86Sr(t)比值、高εNd(t)值及La/Nb和La/Ba比值与洋岛玄武岩相似并以具有缺乏Nb、Ta、Ti负异常的“隆起”状多元素地幔标准化分配型式为特征。当在所研究的火山岩系中发现有未受到混染的软流圈(或地幔柱)源玄武质岩石存在,基本上就可以排除它们有属于岛弧或活动大陆边缘火山岩系的可能。对于那些具有消减带信号的基性熔岩,可以根据Zr含量和Zr/Y比值,或利用Zr/Y-Zr图解,判断它们是否真正是岛弧或活动大陆边缘玄武岩。     

Sea floor basalt alteration: Some chemical and Sr isotopic effects

Major element, Sr isotope and trace element data for 16 elements are reported for various weathered zones in three submarine basalt pillows. During the initial stages of alteration, it appears that SiO₂, Al₂O₃, CaO, S, and Ga are lost from the basalt, whereas Fe₂O₃, total Fe, MnO, K₂O, H₂O, Cl, B, Rb, and Cs increase. Sr⁸⁷/Sr⁸⁶ ratios also increase during weathering. MgO, Na₂O, P₂O₅, Ba, Ni and Cu show significant (10–50%) but less consistent changes. TiO₂, Zr, Sr and V show only minor changes (<7%). Zn, Cr, Co, Y and Nb show no changes outside experimental error.     

Calculated diffusion coefficients and the growth rate of olivine in a basalt magma

Concentration gradients in glass adjacent to skeletal olivines in a DSDP basalt have been examined by electron probe. The glass is depleted in Mg, Fe, and Cr and enriched in Si, Al, Na, and Ca relative to that far from olivine. Ionic diffusion coefficients for the glass compositions are calculated from temperature, ionic radius and melt viscosity, using the Stokes-Einstein relation. At 1170°C, the diffusion coefficient of Mg²⁺ ions in the basalt is 4·5.10^?9 cm²/s. Comparison with measured diffusion coefficients in a mugearite suggests this value may be 16 times too small. The concentration gradient data and the diffusion coefficients are used to calculate instantaneous olivine growth rates of 2–6.10^?7 cm/s. This is too slow for olivine to have grown in situ during quenching. Growth necessarily preceded emplacement such that the composition of the crystals plus the enclosing glass need not be that of a melt. The computed olivine growth rates are compatible with the rate of crystallization deduced for the Skaegaard intrusion.     

Trace element and isotopic evidence for REE migration and fractionation in salts next to a basalt dyke

Neodymium and Sr isotopic compositions and the rare earth elements (REE) distribution patterns have been determined in salts adjacent to a basaltic dyke along 2 parallel horizontal profiles. The salts, originally consisting of carnallite (KMgCl₃ · 6H₂O), have been transformed during basalt intrusion mainly into halite (NaCl) and sylvite (KCl) by fluids saturated in NaCl. The Sr isotope data suggests that much more fluid penetrated the upper than the lower horizon. The Nd isotope data shows that in the upper horizon, where fluid flow was stronger, Nd is essentially derived from the basalt. In contrast, in the lower horizon a strong salt Nd component is present.The REE data document in both horizons is a strong depletion of Ce, Pr, Nd, Sm and Eu with increasing distance from the basalt. This depletion of the light rare earths (LREE) is stronger in the upper horizon where fluid flow was stronger. The authors suggest that this REE fractionation is more likely due to precipitation of LREE-enriched accessory minerals such as apatite, than to differential REE solubility caused by selective REE complexation. This finding is of interest for REE behaviour in brines in general, and for the behaviour of radioactive REE and actinides in a salt repository for high-level nuclear waste in particular.     

Oxygen and iron isotope constraints on near-surface fractionation effects and the composition of lunar mare basalt source regions

Oxygen and iron isotope analyses of low-Ti and high-Ti mare basalts are presented to constrain their petrogenesis and to assess stable isotope variations within lunar mantle sources. An internally-consistent dataset of oxygen isotope compositions of mare basalts encompasses five types of low-Ti basalts from the Apollo 12 and 15 missions and eight types of high-Ti basalts from the Apollo 11 and 17 missions. High-precision whole-rock δ¹⁸O values (referenced to VSMOW) of low-Ti and high-Ti basalts correlate with major-element compositions (Mg#, TiO₂, Al₂O₃). The observed oxygen isotope variations within low-Ti and high-Ti basalts are consistent with crystal fractionation and match the results of mass-balance models assuming equilibrium crystallization. Whole-rock δ⁵⁶Fe values (referenced to IRMM-014) of high-Ti and low-Ti basalts range from 0.134‰ to 0.217‰ and 0.038‰ to 0.104‰, respectively. Iron isotope compositions of both low-Ti and high-Ti basalts do not correlate with indices of crystal fractionation, possibly owing to small mineral-melt iron fractionation factors anticipated under lunar reducing conditions.The δ¹⁸O and δ⁵⁶Fe values of low-Ti and the least differentiated high-Ti mare basalts are negatively correlated, which reflects their different mantle source characteristics (e.g., the presence or absence of ilmenite). The average δ⁵⁶Fe values of low-Ti basalts (0.073 ± 0.018‰, n = 8) and high-Ti basalts (0.191 ± 0.020‰, n = 7) may directly record that of their parent mantle sources. Oxygen isotope compositions of mantle sources of low-Ti and high-Ti basalts are calculated using existing models of lunar magma ocean crystallization and mixing, the estimated equilibrium mantle olivine δ¹⁸O value, and equilibrium oxygen-fractionation between olivine and other mineral phases. The differences between the calculated whole-rock δ¹⁸O values for source regions, 5.57‰ for low-Ti and 5.30‰ for high-Ti mare basalt mantle source regions, are solely a function of the assumed source mineralogy. The oxygen and iron isotope compositions of lunar upper mantle can be approximated using these mantle source values. The δ¹⁸O and δ⁵⁶Fe values of the lunar upper mantle are estimated to be 5.5 ± 0.2‰ (2σ) and 0.085 ± 0.040‰ (2σ), respectively. The oxygen isotope composition of lunar upper mantle is identical to the current estimate of Earth’s upper mantle (5.5 ± 0.2‰), and the iron isotope composition of the lunar upper mantle overlaps within uncertainty of estimates for the terrestrial upper mantle (0.044 ± 0.030‰).     

Isotopic fractionation of noble gases by diffusion in liquid water: Molecular dynamics simulations and hydrologic applications

Despite their great importance in low-temperature geochemistry, diffusion coefficients of noble gas isotopes in liquid water (D) have been measured only for the major isotopes of helium, neon, krypton and xenon. Data on the diffusion coefficients of minor noble gas isotopes are essentially non-existent and so typically have been estimated by a kinetic-theory model in which D varies as the inverse square root of the isotopic mass (m): D ∝ m^−0.5. To examine the validity of the kinetic-theory model, we performed molecular dynamics (MD) simulations of the diffusion of noble gases in ambient liquid water. Our simulation results agree with available experimental data on the solvation structure and diffusion coefficients of the major noble gas isotopes and reveal for the first time that the isotopic mass-dependence of all noble gas self-diffusion coefficients has the power-law form D ∝ m^−β with 0 < β < 0.2. Thus our results call into serious question the widespread assumption that the ‘square-root’ model can be applied to estimate the kinetic fractionation of noble gas isotopes caused by diffusion in ambient liquid water. To illustrate the importance of this finding, we used the diffusion coefficients determined in our MD simulations to reconsider the geochemical modeling of ²⁰Ne/²²Ne and ³⁶Ar/⁴⁰Ar isotopic ratios in three representative hydrologic studies. Our new modeling results indicate that kinetic isotopic fractionation by diffusion may play a significant role in noble gas transport processes in groundwater.     

Mixing of rhyolite,trachyte and basalt magma erupted from a vertically and laterally zoned reservoir,composite flow P1, Gran Canaria

The 14.1 Ma composite welded ignimbrite P1 (45 km³ DRE) on Gran Canaria is compositionally zoned from a felsic lower part to a basaltic top. It is composed of four component magmas mixed in vertically varying proportions: (1) Na-rhyolite (10 km³) zoned from crystal-poor to highly phyric; (2) a continuously zoned, evolved trachyte to sodic trachyandesite magma group (6 km³); (3) a minor fraction of Na-poor trachyandesite (<1 km³); and (4) nearly aphyric basalt (26 km³) zoned from 4.3 to 5.2 wt% MgO. We distinguish three sites and phases of mixing: (a) Mutual mineral inclusions show that mixing between trachytic and rhyolitic magmas occurred during early stages of their intratelluric crystallization, providing evidence for long-term residence in a common reservoir prior to eruption. This first phase of mixing was retarded by increasing viscosity of the rhyolite magma upon massive anorthoclase precipitation and accumulation. (b) All component magmas probably erupted through a ring-fissure from a common upper-crustal reservoir into which the basalt intruded during eruption. The second phase of mixing occurred during simultaneous withdrawal of magmas from the chamber and ascent through the conduit. The overall withdrawal and mixing pattern evolved in response to pre-eruptive chamber zonation and density and viscosity relationships among the magmas. Minor sectorial variations around the caldera reflect both varying configurations at the conduit entrance and unsteady discharge. (c) During each eruptive pulse, fragmentation and particulate transport in the vent and as pyroclastic flows caused additional mixing by reducing the length scale of heterogeneities. Based on considerations of magma density changes during crystallization, magma temperature constraints, and the pattern of withdrawal during eruption, we propose that eruption tapped the P1 magma chamber during a transient state of concentric zonation, which had resulted from destruction of a formerly layered zonation in order to maintain gravitational equilibrium. Our model of magma chamber zonation at the time of eruption envisages a basal high-density Na-poor trachyandesite layer that was overlain by a central mass of highly phyric rhyolite magma mantled by a sheath of vertically zoned trachyte-trachyandesite magma along the chamber walls. A conventional model of vertically stacked horizontal layers cannot account for the deduced density relationships nor for the withdrawal pattern.     

Enrichment of basalt and mixing of dacite in the rootzone of a large rhyolite chamber: inclusions and pumices from the Rattlesnake Tuff, Oregon

 A variety of cognate basalt to basaltic andesite inclusions and dacite pumices occur in the 7-Ma Rattlesnake Tuff of eastern Oregon. The tuff represents ∼280 km³ of high-silica rhyolite magma zoned from highly differentiated rhyolite near the roof to less evolved rhyolite at deeper levels. The mafic inclusions provide a window into the processes acting beneath a large silicic chamber. Quenched basaltic andesite inclusions are substantially enriched in incompatible trace elements compared to regional primitive high-alumina olivine tholeiite (HAOT) lavas, but continuous chemical and mineralogical trends indicate a genetic relationship between them. Basaltic andesite evolved from primitive basalt mainly through protracted crystal fractionation and multiple cycles (≥10) of mafic recharge, which enriched incompatible elements while maintaining a mafic bulk composition. The crystal fractionation history is partially preserved in the mineralogy of crystal-rich inclusions (olivine, plagioclase ± clinopyroxene) and the recharge history is supported by the presence of mafic inclusions containing olivines of Fo₈₀. Small amounts of assimilation (∼2%) of high-silica rhyolite magma improves the calculated fit between observed and modeled enrichments in basaltic andesite and reduces the number of fractionation and recharge cycles needed. The composition of dacite pumices is consistent with mixing of equal proportions of basaltic andesite and least-evolved, high-silica rhyolite. In support of the mixing model, most dacite pumices have a bimodal mineral assemblage with crystals of rhyolitic and basaltic parentage. Equilibrium dacite phenocrysts are rare. Dacites are mainly the product of mingling of basaltic andesite and rhyolite before or during eruption and to a lesser extent of equilibration between the two. The Rattlesnake magma column illustrates the feedback between mafic and silicic magmas that drives differentiation in both. Low-density rhyolite traps basalts and induces extensive fractionation and recharge that causes incompatible element enrichment relative to the primitive input. The basaltic root zone, in turn, thermally maintains the rhyolitic magma chamber and promotes compositional zonation. Received: 1 June 1998 / Accepted: 5 February 1999     

Oxygen isotope fractionation between zoisite and water

Oxygen isotope fractionations between zoisite and water have been studied at 400–700°C, PH₂O = 13.4 kbar, using the three-isotope method described by Matsuhisaet al. (1978) and Matthewset al. (1983a). The zoisite-waier exchange reaction takes place extremely slowly and consequently direct-exchange calibration of equilibrium ${}^{18}\text{O}{}^{16}\text{O}$ fractionation factors was possible only at 600 and 700°C. Fractionation factors at 400–600°C were determined from samples hydrothermally crystallized from a glass of the anhydrous zoisite composition. At 600°C, both exchange procedures gave identical fractionations within experimental error. Scanning electron microscope studies showed that the zoisite-water exchange reaction occurs largely by solution-precipitation mass-transfer mechanisms. The slow kinetics of zoisite-water exchange may be typical of hydrous silicates, since additional experiments on tremolite-water and chlorite-water exchange also showed very low rates. When the zoisite-water fractionation factors determined in this study are combined with the quartz and albite-water data of Matsuhisaet al. (1979) and the calcite-water data of O'Nellet al. (1969), mineral-pair fractionations are obtained for which the coefficients “A” in the equation 1000 In α = A × 10⁶T^?2 are:

     

	Ab	Cc	Zo
Q	0.50	0.50	1.56
Ab		0.00	1.06
Cc			1.06