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.     

Mafic Late Miocene–Quaternary volcanic rocks in the Kamchatka back arc region: implications for subduction geometry and slab history at the Pacific–Aleutian junction

New ⁴⁰Ar/³⁹Ar and published ¹⁴C ages constrain voluminous mafic volcanism of the Kamchatka back-arc to Miocene (3–6 Ma) and Late Pleistocene to Holocene (<1 Ma) times. Trace elements and isotopic compositions show that older rocks derived from a depleted mantle through subduction fluid-flux melting (>20%). Younger rocks form in a back arc by lower melting degrees involving enriched mantle components. The arc front and Central Kamchatka Depression are also underlain by plateau lavas and shield volcanoes of Late Pleistocene age. The focus of these voluminous eruptions thus migrated in time and may be the result of a high fluid flux in a setting where the Emperor seamount subducts and the slab steepens during rollback during terrain accretions. The northern termination of Holocene volcanism locates the edge of the subducting Pacific plate below Kamchatka, a “slab-edge-effect” is not observed in the back arc region.     

The rhombohedral framework of the Scandinavian Caledonides and their foreland

The Baltic Shield of northern Europe is transsected by approximately N-S and NW-SE striking Proterozoic fault and fracture zones that were remobilized during the Late Precambrian opening of the Iapetus ocean and the SE-directed thrusting of the Caledonian nappes in Mid-Paleozoic time. Remobilizations of these older structures account for a distinct subsidence history and sedimentological evolution over each fault-bounded basement segment during opening of the Iapetus and for a distinct metamorphic and structural development found within each block during overthrusting of the Caledonian nappes and the exhumation of the orogen. The two fault sets define basement blocks with rhombus-like plan sections which had individual subsidence histories during Iapetus rifting as is expressed by their Late Precambrian (Riphean and Vendian) to Silurian sedimentary cover of contrasting thickness and facies. This contrasting subsidence history of the various basement blocks may have contributed to differences in thrusting level, thrust excision (nappe size), and tectonic style. Correlative Caledonian nappes from adjacent faultbounded basement blocks were thrust diachronously resulting in transport transverse to the general thrusting direction. Thrusting oblique to the NW-SE fault zones and orogen parallel extension resulted in lateral-ramp folds in the cover and reactivation along the NW-SE faults imbricated the overlying nappes. The extent of basement imbrication and duplex formation is variable in the different segments. Within single segments, the basement imbrication and duplex-formation defined basement highs that roughly align in two parallel zones within the orogen. The site of the basement duplexes is probably controlled by older N-S fracture zones while the pinch- and-swell structure parallel to the orogen is caused by the individual deformation and thrusting behavior of the basement and cover sequences that are bound by the NW-SE fault zones. Thus the Caledonian orogen appears to have inherited the Precambrian structural grain of the underlying, Baltic Shield.

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Zusammenfassung Der Baltische Schild Nordeuropas ist von im Proterozoikum angelegten Verwerfungen und Scherzonen mit nördlichem sowie und nordwestlichem Streichen durchzogen, welche während der spätpräkambrischen Öffnung des Iapetus-Ozeanes und der anschließenden, südöstlich gerichteten Überschiebung der kaledonischen Decken im ausgehenden Alt-Paläozoikum reaktiviert worden sind. Die Wiederbelebung dieses ererbten, durch steilstehende Störungen gekennzeichneten, rhombenförmigen Strukturmusters führte zu unterschiedlichen Absenkungsraten der Störungsbegrenzten Grundgebirgsblöcke und steuerte somit die Ablagerungsbedingungen in entstehenden Sedimentationströgen während der Öffnungsphase des Iapetus-Ozeans. Durch diesen Prozeß lassen sich latterale Unterschiede in Mächtigkeit und Fazies der jungpräkambrischen bis altpaläozoischen Deckensedimente entlang dem Nordwestrande des damaligen Kontinentes Baltica, sowie Differenzen in der metamorphen und strukturellen Entwicklung der durch Störungen begrenzten Blöcke während der Überschiebung der kaledonischen Decken und der Hebung des Gebirges erklären. Vertikale Blockverschiebungen und Kippungen von Blöcken relativ zueinander können beobachtete Unterschiede in den Abscherungs- und Überschiebungsniveaus, sowie unterschiedliche tektonische Baustile auf und vor (vor allem) zwischen Blöcken erklären helfen. Untereinander korrelierbare kaledonische Deckensegmente haben, in Bezug auf Transportrichtung und Strecke, voneinander unterschiedliche Wege oberhalb ihrer Untergrundsegmente zurückgelegt. Während dieser Überschiebung auf ein sich simultan veränderndes Relief ist es dabei zu Teilbewegungen schräg zur Hauptüberschiebungsrichtung gekommen, was seinerseits zu seitlichen Verzahnungen benachbarter Deckensegmente geführt hat. Die NWSE streichenden Blockgrenzen haben während lokaler Überschiebungen leicht schräg zu dieser Hauptrichtung als Widerlager und Rampen (lateral ramps) für die darübergleitenden Decken gewirkt, welche sich ihrerseits bei diesem Prozeß in orogentransversale Falten gelegt haben. Je nach ihrer Lage und Neigung sind die verschiedenen Segmente während der Kollisionsphase des kaledonischen Orogens in unterschiedlichem Grade von internen Störungen betroffen worden. Die durch intensive Internscherung hervorgerufenen Krustenverdickungen zeigen eine perlschnurartige Anordnung in zwei orogenparallele zonen, deren Anlage sich auf unterliegende und mitverfrachtete N-S Störungszonen zurückführen lassen kann. Das Anschwellen und Ausdünnen (pinch- and-swell) von tektonischen Einheiten entlang der Längsrichtung des Orogens läßt sich durch unterschiedliche Deformationsverhalten innerhalb der durch NW-SE Störungen begrenzten Segmente erklären. Die Kaledoniden Skandinaviens haben offensichtlich das strukturelle Gepräge ihrer präkaledonischen Unterlage ererbt.

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Résumé Le bouclier baltique est traversé par des fractures protérozoïques orientées approximativement N-S et NW-SE. Ces failles furent réactivées d'abord au Précambrien tardif lors de l'extension correspondant à l'ouverture de l'Océan lapétus, ensuite au Protérozoïque moyen lors du charríage des nappes calédoniennes vers le SE. La réactivation de ces vieilles structures explique qu'on observe pour chaque bloc du socle faillé une subsidence et une sédimentation différente pendant la phase d'extension (ouverture du lapétus), ainsi qu'une évolution métamorphique et structurale distincte pendant le charriage des nappes calédoniennes et l'exhumation de l'orogène. Les deux groupes de failles définissent dans le socle des blocs à sections rhombiques qui présentaíent chacun une subsidence particulière pendant l'ouverture du lapétus, comme l'indiquent les variations d'épaisseur et de facies de leur couverture sédimentaire tardi-précambrienne (vendienne) à silurienne. Cette subsidence variable selon les blocs pourrait avoir contribué à induire des différences dans les niveaux de décollement et de charriage des nappes, ainsi que dans le style tectonique. Les unités tectonostratigraphiques des blocs adjacents furent charriées de façon diachronique avec comme résultat un transport transverse par rapport à la direction dominante du charriage. Ce déplacement oblique vers les zones de failles NW-SE et l'extension parallèle de l'orogène ont produit des plis transversaux dans la couverture; la réactivation des failles NW-SE s'est traduite par l'imbrication des nappes surincombantes. L'importance de cette imbrication et de la formation de duplex est variable selon les différents segments du socle. Pour chaque segment particulier, l'imbrication du socle et la formation de duplex ont engendré des culminations de socle alignés selon deux zones parallèles dans l'orogène. La position des duplex est probablement régie par de vieilles failles N-S alors que la structure en «pinch- and-swell» le long de l'orogène est causée par le caractère individuel de la déformation et du charriage du socle et de sa couverture, propre à chaque bloc limité par des failles NW-SE. L'orogenèse calédonienne a été ainsi fortement afffectée par les structures précambriennes du bouclier baltique sous-jacent.

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, lapetus - . , , , , , lapetus. - - , , . , , , . , , . , . NW-SE (»side-wall ramps«) , . . , , , ; , , , - . (pinck- and-swell) , , NW-S . , - .

     

岩石样品中低含量铂族元素和锇同位素比值的高精度测量方法

铂族元素（Os,Ir,Pt,Ru,Rh,Pd)具有强亲铁性和强亲铜性,为一组地球化学性质相近的相容元素,铂族元素包含两个同位素衰变体系（^190Pt-^186Os和^187Re-^187Os)。近年来,铂族元素和Re-Os同位素在研究各类不同地持作用过程中,尤其是在地幔岩石的研究中,作用独特,效果显著。由于地幔岩石的铂族元素含量较低,因此高精度,高灵敏度的分析测试方法的研究就显得十分重要。以往的分析方法（如常规的ICP－MS和中子活化分析方法）,对含10^-9-10^012级低含量铂族元素的产品分析精度一般较差（＞15％－100％）。所采用的分析流程通常也无法同时获得样品的铂族元素含量和Os同位素比值。本文采用新的熔样方法（HAP－S高温高压釜酸溶法）,新的化学流程（溶剂萃取和阴离子交换树脂柱）和新的分析仪器（多接收等离子体质谱MC－ICPMS和负离子热电离质谱N－TIMS）。用同位素稀释法对低含量地幔橄榄岩样品同时测定的铂族元素含量和Os同位素比值,获得了高精度的分析结果。对所分析的地橄榄样品中的铂族元素分配曲线和Os同位素组成的地质意义进行了初步探讨。     

Effects of seed particle size and composition on heterogeneous nucleation of n-nonane

Heterogeneous nucleation of supersaturated n-nonane vapour on seed particles of different size and composition has been investigated using a fast expansion chamber. Monodisperse seed particle sizes were ranging from about 4 nm up to about 24 nm in diameter. By using different types of particle generators WO_x, Ag and (NH₄)₂SO₄ particles were generated. For direct comparison between different particle compositions overlapping sizes have been generated for WO_x and Ag at about 7 nm particle diameter as well as for Ag and (NH₄)₂SO₄ at about 15 nm. Nucleation temperature was kept constant at about 278 K. Experimental data were compared to Kelvin equation and Fletcher theory including the effect of line tension. It was found that heterogeneous nucleation of n-nonane seems to be independent of seed particle composition and starts well below the Kelvin curve. Good agreement was achieved with Fletcher theory including the effect of line tension.     

Response of the Asian summer Monsoons to a high-latitude thermal forcing: mechanisms and nonlinearities

This study investigates mechanisms and nonlinearities in the response of the Asian Summer Monsoons (ASM) to high-latitude thermal forcings of different amplitudes. Using a suite of runs carried out with an intermediate-complexity atmospheric general circulation model, we find that the imposed forcings produce a strong precipitation response over the eastern ASM but a rather weak response over the southern ASM. The forcing also causes a precipitation dipole with wet conditions over the eastern Tibetan Plateau (TP) and dry conditions over the Bay of Bengal (BoB) and southeast Asia. A moderate increase of precipitation along the southern margin of the TP is also produced. Simulations designed to isolate the causal mechanisms show that thermodynamic interactions involving the tropical surface oceans are far less important than the water-vapour feedback for the transmission of information from the high-latitudes to the ASM. Additionally, we assess the nonlinearity of the ASM precipitation response to the forcing amplitude using a novel application of the empirical orthogonal function method. The response can be decomposed in two overlapping patterns. The first pattern represents a precipitation dipole with wet conditions over the eastern TP and dry conditions over BoB, which linearly increases with forcing amplitude becoming quasi-stationary for large forcing amplitudes (i.e. amplitudes leading to Arctic temperature anomalies larger than 10 °C). The second pattern is associated with increased precipitation over the southeastern TP and is nonlinearly dependent on forcing, being most important for intermediate forcing amplitudes (i.e. amplitudes leading to Arctic temperature anomalies between 5 and 10 °C).     

Zur Tektonik am Nordostrand der Münchberger Gneismasse bei Hof

Zusammenfassung In der Umgebung von Hof wird unterschieden eine ältere Pressungstektonik in der sudetischen Phase der variskischen Orogenese und eine jüngere Zerrungstektonik. Die Pressungstektonik ist dem NW-Rahmen der Münchberger Gneismasse ähnlich, jedoch von geringerer Intensität. In einer 1. Phase kommt es zu einer Schicht- und Schieferungsfaltung, in einer unmittelbar anschließenden 2. Phase besonders an den Grenzen größerer Schichtkomplexe zu Überschiebungen mit NW- bis N-Vergenz. Die Überschiebungen reißen öfter an NW streichenden Blattverschiebungen auseinander, wodurch das Gefüge im Uhrzeigersinn verdreht wird. Durch die jüngere Zerrungstektonik wurden viele dieser Blattverschiebungen in SW fallende Abschiebungen umgewandelt. Der Wartturmberg wird als autochthone Aufpressung aus der Tiefe gedeutet.     

Kankan diamonds (Guinea) I: from the lithosphere down to the transition zone

Peridotitic inclusions in alluvial diamonds from the Kankan region of Guinea in West Africa are mainly of lherzolitic paragenesis. Nevertheless, extreme Cr₂O₃ contents (max. 17 wt%) in some of the exclusively lherzolitic garnets document that the diamond source experienced a previous stage of melt extraction in the spinel stability field. This initial depletion was followed by at least two metasomatic stages: (1) enrichment of LREE and Sr and (2) introduction mainly of MREE–HREE and other HFSE (Ti, Y, Zr, Hf). The Ti- and HFSE-poor character of stage (1) points towards a CHO-rich fluid or carbonatitic melt, the high HFSE in stage (2) favour silicate melts as enriching agent. Eclogitic inclusions are derived from a large depth interval ranging from the lithosphere through the asthenosphere into the transition zone. The occurrence of negative Eu anomalies in garnet and clinopyroxene from both lithosphere and transition zone suggests a possible relationship to subducted oceanic crust. Lithospheric eclogitic inclusions are derived from heterogeneous sources, that may broadly be divided into a low-Ca group with LREE depleted trace element patterns and a high-Ca group representing a source with negative LREE–HREE slope that is moderately enriched in incompatible elements relative to primitive mantle. High-Ca inclusions of majoritic paragenesis are significantly more enriched in incompatible elements, such as in Sr and LREE. Calculated whole rock compositions require metasomatic enrichment even if a derivation from MORB is assumed. Received: 26 January 2000 / Accepted: 18 May 2000     

Der petrogenetische Werdegang der Klinopyroxene in den tertiären Vulkaniten der Hocheifel

The course of crystallization of basalt forming clinopyroxenes in the olivine-basalt-hawaiite-mugearite-trachyte-and basanitoid (= basanite)-series from the Hocheifel area (Western Germany) has been presented by the author in two earlier papers (Hucken-holz, 1965 a, 1965 b). The present paper deals with the evolution of clinopyroxenes from the ankaramites in the same area. The ankaramites are richer in olivines and clinopyroxenes than the normal olivine basalts and may be a product of accumulation of olivines and clinopyroxenes in an olivine basalt magma. The first clinopyroxene formed in the ankaramites is a greenish chromian salite Ca_47.1 Mg_40.9 Fe_12.0 which is preserved in the cores of the phenocrysts. Strongly zoned brown titansalite Ca₄₅ Mg₄₂Fe₁₃ surrounds the chromian salite (HF 5) or appears in independent microphenocrysts (HF53). The groundmass clinopyroxene is titansalite Ca₄₅Mg₃₇Fe₁₈ with a small optic axial angle. Phenocrysts of nickel-rich olivine Fe_12–14 and chrome spinell were formed together with chromium clinopyroxene. The same minerals together with orthopyroxenes have been observed in the olivine basalts, hawaiites and basanitoids (= basanites). This paragenesis indicates high pressure and high temperature in the alkali basalts of the Hocheifel during an initial stage of magmatic evolution. With the decrease of pressure, mineral reaction occurred with the alkali basalt melt. The high pressure clinopyroxenes of the ankaramites and basanitoids (= basanites) were changed to a larger extent than the clinopyroxenes of the olivine basalts and hawaiites or were completely destroyed (HF 53) because they are in contact with the hot magma for a longer period of time. This favours the reaction between the solids and the melt, and the high pressure garnet and/or enstatite components in the clinopyroxenes are substituted by Ca-Tschermak’s and titanaugite molecules.