Partial melting within the lower crust – Constraints from bulk rock geochemical data and trace element mineral analyses of granulites and migmatites from Central Finland

This PhD thesis concerns geochemical constraints on recycling and partial melting of Archean continental crust. A natural example of such processes was found in the Iisalmi area of Central Finland. The rocks from this area are Middle to Late Archean in age and experienced metamorphism and partial melting between 2.7-2.63 Ga. The work is based on extensive field work. It is furthermore founded on bulk rock geochemical data as well as in-situ analyses of minerals. All geochemical data were obtained at the Institute of Geosciences, University of Mainz using X-ray fluorescence, solution ICP-MS and laser ablation-ICP-MS for bulk rock geochemical analyses. Mineral analyses were accomplished by electron microprobe and laser ablation ICP-MS. Fluid inclusions were studied by microscope on a heating-freezing-stage at the Geoscience Center, University Göttingen. Part I focuses on the development of a new analytical method for bulk rock trace element determination by laser ablation-ICP-MS using homogeneous glasses fused from rock powder on an Iridium strip heater. This method is applicable for mafic rock samples whose melts have low viscosities and homogenize quickly at temperatures of ~1200°C. Highly viscous melts of felsic samples prevent melting and homogenization at comparable temperatures. Fusion of felsic samples can be enabled by addition of MgO to the rock powder and adjustment of melting temperature and melting duration to the rock composition. Advantages of the fusion method are low detection limits compared to XRF analyses and avoidance of wet-chemical processing and use of strong acids as in solution ICP-MS as well as smaller sample volumes compared to the other methods. Part II of the thesis uses bulk rock geochemical data and results from fluid inclusion studies for discrimination of melting processes observed in different rock types. Fluid inclusion studies demonstrate a major change in fluid composition from CO2-dominated fluids in granulites to aqueous fluids in TTG gneisses and amphibolites. Partial melts were generated in the dry, CO2-rich environment by dehydration melting reactions of amphibole which in addition to tonalitic melts produced the anhydrous mineral assemblages of granulites (grt + cpx + pl ± amph or opx + cpx + pl + amph). Trace element modeling showed that mafic granulites are residues of 10-30 % melt extraction from amphibolitic precursor rocks. The maximum degree of melting in intermediate granulites was ~10 % as inferred from modal abundances of amphibole, clinopyroxene and orthopyroxene. Carbonic inclusions are absent in upper-amphibolite facies migmatites whereas aqueous inclusion with up to 20 wt% NaCl are abundant. This suggests that melting within TTG gneisses and amphibolites took place in the presence of an aqueous fluid phase that enabled melting at the wet solidus at temperatures of 700-750°C. The strong disruption of pre-metamorphic structures in some outcrops suggests that the maximum amount of melt in TTG gneisses was ~25 vol%. The presence of leucosomes in all rock types is taken as the principle evidence for melt formation. However, mineralogical appearance as well as major and trace element composition of many leucosomes imply that leucosomes seldom represent frozen in-situ melts. They are better considered as remnants of the melt channel network, e.g. ways on which melts escaped from the system. Part III of the thesis describes how analyses of minerals from a specific rock type (granulite) can be used to determine partition coefficients between different minerals and between minerals and melt suitable for lower crustal conditions. The trace element analyses by laser ablation-ICP-MS show coherent distribution among the principal mineral phases independent of rock composition. REE contents in amphibole are about 3 times higher than REE contents in clinopyroxene from the same sample. This consistency has to be taken into consideration in models of lower crustal melting where amphibole is replaced by clinopyroxene in the course of melting. A lack of equilibrium is observed between matrix clinopyroxene / amphibole and garnet porphyroblasts which suggests a late stage growth of garnet and slow diffusion and equilibration of the REE during metamorphism. The data provide a first set of distribution coefficients of the transition metals (Sc, V, Cr, Ni) in the lower crust. In addition, analyses of ilmenite and apatite demonstrate the strong influence of accessory phases on trace element distribution. Apatite contains high amounts of REE and Sr while ilmenite incorporates about 20-30 times higher amounts of Nb and Ta than amphibole. Furthermore, trace element mineral analyses provide evidence for magmatic processes such as melt depletion, melt segregation, accumulation and fractionation as well as metasomatism having operated in this high-grade anatectic area.

The influence of heat treatment on the phase relations in mineral growth systems

ABSTRACT Corundum is one of the most famous gems materials. Different heat treatment methods for enhancement purposes are commonly applied and accepted in the gem market. With this reason, the identification of the natural, unheated corundum is intensively investigated. In this study, aluminium hydroxide minerals and zircon are focused to observe the crystallization and phase change of these minerals during heat treatment procedures. Aluminium hydroxide minerals can be transformed to alumina with the corundum structure by heating. The reaction history of aluminium hydroxide minerals containing corundum was investigated comparing it with diaspore, boehmite, gibbsite and bayerite by TG and DTA methods. These hydroxide minerals were entirely transformed to corundum after heating at 600°C. Zircon inclusions in corundums from Ilakaka, Madagascar, were investigated for the influence of different heat-treatment temperatures on the recovery of their crystalline structure and on possible reactions within and with the host crystals. The host corundum was heated at 500, 800, 1000, 1200, 1400, 1600 and 1800°C. The crystallinity, the trapped pressure, and the decomposition of the zircon inclusions within the host corundum have been investigated by Raman spectroscopy. Radiation-damaged zircon inclusions may be used as an indicator for unheated Ilakaka corundum crystals. They are fully recrystallized after heating at 1000°C influencing the lowering of the 3 Raman band shift, the decreasing of FWHM of the 3 Raman band and the decreasing of the trapped pressure between the inclusion and the host corundum. Under microscopic observation, surface alterations of the inclusions can be firstly seen from transparent into frosted-like appearance at 1400°C. Then, between 1600°C and 1800 °C, the inclusion becomes partly or even completely molten. The decomposition of the zircon inclusion to m-ZrO2 and SiO2-glass phases begins at the rim of the inclusion after heating from 1200°C to 1600°C which can be detected by the surface change, the increase of the 3 Raman band position and the trapped pressure. At 1800°C, the zircon inclusions entirely melt transforming to solid phases during cooling like m-ZrO2 and SiO2-glass accompanied by an increase of pressure between the transformed inclusion and its host.

Effetto dell'addizione di fibre corte di carbonio su microstruttura e proprietà di materiali a base di ZrB2

Il lavoro di tesi, svolto presso l’Istituto di Scienza e Tecnologia dei Materiali Ceramici (ISTEC-CNR, Faenza, RA), ha affrontato la produzione e la caratterizzazione di ceramici a base di boruro di zirconio (ZrB2) con lo scopo di valutare l’efficacia delle fibre corte di carbonio come potenziale rinforzo. Il boruro di zirconio appartiene a una famiglia di materiali noti come UHTC (Ultra-High Temperature Ceramics) caratterizzati da elevato punto di fusione e in grado di mantenere la resistenza meccanica e operare con limitata ossidazione a temperature superiori ai 2000°C. Il principale ostacolo nella produzione dei materiali a base di ZrB2 è il processo di sintesi, infatti, a causa della loro elevata temperatura di fusione, per ottenere un materiale completamente denso è necessario utilizzare processi a temperatura e pressione elevati (T > 2000°C e P > 30 MPa), condizioni che vanno ad influenzare la microstruttura della matrice e delle fibre e di conseguenza le proprietà meccaniche del materiale. L’aggiunta di additivi di sinterizzazione idonei permette di ottenere materiali perfettamente densi anche a temperature e pressioni inferiori. Tuttavia lo ZrB2 non viene ampiamente utilizzato per applicazioni strutturali a causa della sua fragilità, per far fronte alla sua bassa tenacità il materiale viene spesso rinforzato con una fase allungata (whiskers o fibre). È già oggetto di studi l’utilizzo di fibre corte e whiskers di SiC per tenacizzare lo ZrB2, tuttavia la forte interfaccia che viene a crearsi tra fibra e matrice, che non permette il pull-out delle fibre, ci porta a credere che una fibra che non tenda a reagire con la matrice, presentando un’interfaccia più debole, possa portare ad una tenacizzazione più efficace. Per questo scopo sono stati realizzati mediante pressatura a caldo due materiali rinforzati con fibre corte di carbonio: ZrB2 + 5% vol MoSi2 + 8% vol fibre di carbonio e [ZrB2 + 2 % peso C] + 8% vol fibre di carbonio, indicati rispettivamente con Z5M_Cf e Z2C_Cf. Sono stati analizzati e discussi diversi aspetti del materiale rinforzato tra cui: il comportamento di densificazione durante la pressatura a caldo, l’evoluzione della microstruttura della matrice, la distribuzione e la morfologia delle fibre, l’influenza del rinforzo sulle proprietà meccaniche di durezza e tenacità e sulla resistenza all’ossidazione. L’elaborato è strutturato come segue: inizialmente sono state introdotte le caratteristiche generali dei ceramici avanzati tra cui le proprietà, la produzione e le applicazioni; successivamente è stata approfondita la descrizione dei materiali a base di boruro di zirconio, in particolare i processi produttivi e l’influenza degli additivi di sinterizzazione sulla densificazione e sulle proprietà; ci si è poi concentrati sull’effetto di una seconda fase allungata per il rinforzo del composito. Per quanto riguarda la parte sperimentale vengono descritte le principali fasi della preparazione e caratterizzazione dei materiali: le materie prime, disperse in un solvente, sono state miscelate mediante ball-milling, successivamente è stato evaporato il solvente e la polvere ottenuta è stata formata mediante pressatura uniassiale. I campioni, dopo essere stati sinterizzati mediante pressatura uniassiale a caldo, sono stati tagliati e lucidati a specchio per poter osservare la microstruttura. Quest’ultima è stata analizzata al SEM per studiare l’effetto dell’additivo di sinterizzazione (MoSi2 e carbonio) e l’interfaccia tra matrice e fase rinforzante. Per approfondire l’effetto del rinforzo sulle proprietà meccaniche sono state misurate la durezza e la tenacità del composito; infine è stata valutata la resistenza all’ossidazione mediante prove in aria a 1200°C e 1500°C. L’addizione di MoSi2 ha favorito la densificazione a 1800°C mediante formazione di una fase liquida transiente, tuttavia il materiale è caratterizzato da una porosità residua di ~ 7% vol. L’addizione del carbonio ha favorito la densificazione completa a 1900°C grazie alla reazione dall’additivo con gli ossidi superficiali dello ZrB2. La microstruttura delle matrici è piuttosto fine, con una dimensione media dei grani di ~ 2 μm per entrambi i materiali. Nel caso del materiale con Z5M_Cf sono presenti nella matrice particelle di SiC e fasi MoB derivanti dalla reazione dell’additivo con le fibre e con la matrice; invece nel materiale Z2C_Cf sono presenti grani di carbonio allungati tra i bordi grano, residui delle reazioni di densificazione. In entrambi i materiali le fibre sono distribuite omogeneamente e la loro interfaccia con la matrice è fortemente reattiva. Nel caso del materiale Z5M_Cf si è formata una struttura core-shell con lo strato più esterno formato da SiC, formato dalla reazione tra il siliciuro e la fibra di C. Nel caso del materiale Z2C_Cf non si forma una vera e propria interfaccia, ma la fibra risulta fortemente consumata per via dell’alta temperatura di sinterizzazione. I valori di durezza Vickers dei materiali Z5M_Cf e Z2C_Cf sono rispettivamente 11 GPa e 14 GPa, valori inferiori rispetto al valore di riferimento di 23 GPa dello ZrB2, ma giustificati dalla presenza di una fase meno dura: le fibre di carbonio e, nel caso di Z5M_Cf, anche della porosità residua. I valori di tenacità dei materiali Z5M_Cf e Z2C_Cf, misurati con il metodo dell’indentazione, sono rispettivamente 3.06 MPa·m0.5 e 3.19 MPa·m0.5. L’osservazione, per entrambi i materiali, del fenomeno di pull-out della fibra, sulla superficie di frattura, e della deviazione del percorso della cricca, all’interno della fibra di carbonio, lasciano supporre che siano attivi questi meccanismi tenacizzanti a contributo positivo, unitamente al contributo negativo legato allo stress residuo. La resistenza all’ossidazione dei due materiali è confrontabile a 1200°C, mentre dopo esposizione a 1500°C il materiale Z5M_Cf risulta più resistente rispetto al materiale Z2C_Cf grazie alla formazione di uno strato di SiO2 protettivo, che inibisce la diffusione dell’ossigeno all’interno della matrice. Successivamente, sono stati considerati metodi per migliorare la densità finale del materiale e abbassare ulteriormente la temperatura di sinterizzazione in modo da minimizzare la degenerazione della fibra. Da ricerca bibliografica è stato identificato il siliciuro di tantalio (TaSi2) come potenziale candidato. Pertanto è stato prodotto un terzo materiale a base di ZrB2 + Cf contenente una maggiore quantità di siliciuro (10% vol TaSi2) che ha portato ad una densità relativa del 96% a 1750°C. Questo studio ha permesso di approcciare per la prima volta le problematiche legate all’introduzione delle fibre di carbonio nella matrice di ZrB2. Investigazioni future saranno mirate alla termodinamica delle reazioni che hanno luogo in sinterizzazione per poter analizzare in maniera più sistematica la reattività delle fibre nei confronti della matrice e degli additivi. Inoltre riuscendo ad ottenere un materiale completamente denso e con fibre di carbonio poco reagite si potrà valutare la reale efficacia delle fibre di carbonio come possibili fasi tenacizzanti.

Caratterizzazione sperimentale dell'ossido di stronzio per l'assorbimento del diossido di carbonio da correnti gassose ad alta temperatura e considerazioni sulla sua applicazione industriale in processi CCS

Del granulato di ossido di stronzio (anche nella formula carbonato) è stato testato come nuovo possibile materiale di utilizzo per la cattura ad alta temperatura di diossido di carbonio da effluenti gassosi di scarto. Sono stati condotti diversi esperimenti con strumentazioni già preposte, quali test termogravimetrici, microscopia elettronica (SEM) e Xray (XRD). Mentre per la sperimentazione in quantità più rilevanti di materiale è stato costruito un impianto a letto fisso ex novo. Le prove TG hanno evidenziato una capacità media di sorbente parti a circa il 5% in massa di ossido, a temperature tra i 1100°C e i 1200°C, in situazione di regime (dopo numerosi cicli di carb/calc), con una buona conservazione nel tempo delle proprietà adsorbitive, mentre per le prove a letto fisso, si è registrato un calo di valori variabile tra il 3 e il 4%, con un netto miglioramento nel caso di calcinazione in vapore surriscaldato fino al 5%. Il trattamento in vapore ha sortito l’importante effetto di calcinazione del diossido di carbonio dal sorbente, quindi facilmente separabile dal flusso in uscita, misurato tramite cattura in una soluzione di idrossido di bario. Importanti fenomeni di sintering e densificazione hanno portato ad occludere completamente la camera di reazione sviluppando notevoli sovrappressioni interne. Tali fenomeni sono stati approfonditi tramite analisi SEM e XRD. Si è constatato un aumento notevole della grandezza dei granuli in caso di trattamento in vapore con la formazione di legami stabili e con conservazione della porosità. Nel caso di trattamento senza vapore surriscaldato i granuli hanno sinterizzato tramite formazione di legami, ma sempre con conservazione della macroporosità. Il lavoro di tesi è stato inquadrato nel contesto tecnologico al riguardo le tecniche CCS esistenti ed in progetto, con un attento studio bibliografico riguardo lo stato dell’arte, impianti esistenti, costi, metodi di cattura usati, metodologie di trasporto dei gas, metodologie di stoccaggio esistenti e in progetto. Si sono considerati alcuni aspetti economici per sviluppare un modello previsionale di spesa per una possibile applicazione di cattura per un impianto di produzione energetica. Con la progettazione e dimensionamento di un sistema integrato di adsorbimento tramite l’accoppiamento di 2 reattori dedicati ai cicli di carbonatazione e calcinazione del materiale sorbente. Infine si sono considerati gli aspetti salienti dello stoccaggio del diossido di carbonio in reservoir tramite le tecniche di EOR e EGR (Enhanced Oil/Gas Recovery) utilizzando la stessa CO2 come fluido spiazzante degli idrocarburi in posto. Concludendo il lavoro di tesi e di sperimentazione ha contribuito in modo tangibile allo scopo prefissato, andando a caratterizzare un nuovo materiale per la cattura di diossido di carbonio da effluenti gassosi ad alta temperatura, ed andando a verificare un’importante fenomeno rigenerativo non previsto delle capacità sorbitive dei materiali sottoposti a test.

Composition of minerals from peridotides at the Mid-Atlantic Ridge, 13°N

Peridotites (diopside-bearing harzburgites) found at 13°N of the Mid-Atlantic Ridge fall into two compositional groups. Peridotites P1 are plagioclase-free rocks with minerals of uniform composition and Ca-pyroxene strongly depleted in highly incompatible elements. Peridotites P2 bear evidence of interaction with basic melt: mafic veinlets; wide variations in mineral composition; enrichment of minerals in highly incompatible elements (Na, Zr, and LREE); enrichment of minerals in moderately incompatible elements (Ti, Y, and HREE) from P1 level to abundances 4-10 times higher toward the contacts with mafic aggregates; and exotic mineral assemblages Cr-spinel + rutile and Cr-spinel + ilmenite in peridotite and pentlandite + rutile in mafic veinlets. Anomalous incompatible-element enrichment of minerals from peridotites P2 occurred at the spinel-plagioclase facies boundary, which corresponds to pressure of about 0.8-0.9 GPa. Temperature and oxygen fugacity were estimated from spinel-orthopyroxene-olivine equilibria. Peridotites P1 with uniform mineral composition record temperature of the last complete recrystallization at 940-1050°C and FMQ buffer oxygen fugacity within the calculation error. In peridotites P2, local assemblages have different compositions of coexisting minerals, which reflects repeated partial recrystallization during heating to magmatic temperatures (above 1200°C) and subsequent reequilibration at temperatures decreasing to 910°C and oxygen fugacity significantly higher than FMQ buffer (delta log fO2 = 1.3-1.9). Mafic veins are considered to be a crystallization product from basic melt enriched in Mg and Ni via interaction with peridotite. The geochemical type of melt reconstructed by the equilibrium with Ca-pyroxene is defined as T-MORB: (La/Sm)_N~1.6 and (Ce/Yb) )_N~2.3 that is well consistent with compositional variations of modern basaltic lavas in this segment of the Mid-Atlantic Ridge, including new data on quenched basaltic glasses.

Chemistry of basalts of ODP Hole 111-504B

The effect of oxygen fugacity (fO2) on the partition relationship of Mg and Fe between Plagioclase and sillicate liquid was investigated at 1 atm for basaltic samples recovered during ODP Leg 111 from Hole 504B. Samples 111-504B-143R-2 (Piece 8) and 111-504B-169R-1 (Piece 1) have Plagioclase as the liquidus phase. The distribution coefficient of Mg between Plagioclase and melt is constant at about 0.04 against the variation of fO2, whereas that of Fe (total Fe) varies from 0.3 at f(O2) = 0.2 atm to 0.03 at f(o2) = 10**-11.5 at 1200°C. The distribution coefficient of Mg is slightly higher than that calculated from the phenocryst and bulk-rock compositions, suggesting a kinetic disequilibrium effect on the distribution of Mg in Plagioclase. Because Mg, Fe, and Fe3+ have similar diffusion coefficients in silicate melt, the disequilibrium effect is greatly reduced for the exchange reaction of Mg and total Fe between Plagioclase and liquid. The exchange partition coefficient is highly dependent on fo2, with log fo2 ranging from -0.7 to - 11.5 at approximately 1200°C. Using this relationship, the f(O2) of crystallization of the magmas is estimated to be near the one defined by the fayalite-quartz-magnetite assemblage.

Petrology of high-MgO bronzite andesite resembling boninite at DSDP Hole 60-458

A high-MgO andesite which is texturally similar to boninite and a variolitic basalt collected from Site 458, about 100 km west of the Mariana Trench, have been studied through microprobe analyses and melting experiments at high water pressures. The boninite-type andesite is very similar in composition and texture to a boninite from Bonin Islands, except that the former is more calcic than the latter. The variolitic basalt contains magnesian pigeonite (Ca12Mg74Fe14) in cores of augite microphenocrysts. This pigeonite crystallized at temperatures above 1200°C. In the melting experiments of the boninite-type rock, clinopyroxene crystallizes as a liquidus phase at pressures at least above 8 kbar. No olivine crystallizes near the liquidus temperatures, indicating that the magma of this rock cannot be in equilibrium with the upper mantle periodotite (lherzolite) at depths at least greater than 25 km. The boninite-type rock is probably a product of fractional crystallization of a more primitive magma (e.g., olivine-bearing boninite magma) by separation of olivine and orthopyroxene. The magma of the variolitic basalt also cannot be in equilibrium with the upper mantle peridotite, and may be a product of fractional crystallization of a more primitive basaltic magma.

Geochemistry of basaltic rocks from ODP Site 129-801

Middle Jurassic basaltic lavas obtained from Site 801 in the western Pacific Pigafetta Basin represent ocean crust from the oldest segment of the present-day Pacific Ocean. A composite 131 m section shows the basement to be composed of an upper alkalic basalt sequence (about 157 Ma) with ocean island basalt chemical features and a lower tholeiitic basalt sequence (about 167 Ma) with typical normal-type mid-ocean ridge basalt features. The basalt sequences are separated by a quartz-cemented, yellow goethite hydrothermal deposit. Most basalts are altered to some degree and exhibit variable, low-grade smectite-celadonite-pyrite-carbonate-zeolite assemblages developed under a mainly hydrated anoxic environment. Oxidation is very minor, later in development than the hydration assemblages, and largely associated with the hydrothermal deposit. The tholeiitic normal-type mid-ocean ridge basalt has characteristically depleted incompatible element patterns and all compositions are encompassed by recent mid-ocean ridge basalt from the East Pacific Rise. Chemically, the normal-type mid-ocean ridge basalt is divided into a primitive plagioclase-olivine +/- spinel phyric group (Mg* = 72-60) and an evolved (largely) aphyric group of olivine tholeiites (Mg* = 62-40). Both groups form a single comagmatic suite related via open-system fractionation of initial olivine-spinel followed by olivine-plagioclase-clinopyroxene. The alkalic ocean island basalt are largely aphyric and display enriched incompatible element abundances within both relatively primitive olivine-rich basalts and evolved olivine-poor hawaiites related via mafic fractionation. In gross terms, the basement lithostratigraphy is a typical mid-ocean ridge basalt crust, generated at a spreading center, overlain by an off-axis seamount with ocean island basalt chemical characters.

Major elements oxides and mineralogy of primary minerals in ODP Hole 195-1201D basalts

The basement cored at Site 1201 (west Philippine Basin) during Ocean Drilling Program Leg 195 consists of a 91-m-thick sequence of basalts, mostly pillow lavas and perhaps one sheet lava flow, with a few intercalations of hyaloclastite and interpillow sedimentary material. Hydrothermal alteration pervasively affected the basalt sequence, giving rise to a variety of secondary minerals such as K-Fe-Mg-clay minerals, oxyhydroxides and clay minerals mixtures, natrolite group zeolites, analcite, alkali feldspar, and carbonate. The primary minerals of pillow and sheet basalts that survived the intense hydrothermal alteration were investigated by electron microprobe with the aim of characterizing their chemical composition and variability. The primary minerals are mostly plagioclase, ranging in composition from bytownite through labradorite to andesine, chromian-magnesian-diopside, and spinels, both Ti magnetite (partially maghemitized) and chromian spinel. Overall, the chemical features of the primary minerals of Site 1201 basalts correspond to the primitive character of the bulk rocks, suggesting that the parent magma of these basalts was a mafic tholeiitic magma that most likely only suffered limited fractional crystallization and crystallized at high temperatures (slightly below 1200°C) and under increasing fO2 conditions. The major element composition of clinopyroxene suggests a backarc affinity of the mantle source of Site 1201 basement.

Composition of matrix glasses and melt inclusions of fallout tephra from ODP Hole 125-782A

We studied the systematics of Cl, F and H2O in Izu arc front volcanic rocks using basaltic through rhyolitic glass shards and melt inclusions (Izu glasses) from Oligocene to Quaternary distal fallout tephra. These glasses are low-K basalts to rhyolites that are equivalent to the Quaternary lavas of the Izu arc front (Izu VF). Most of the Izu glasses have Cl ~400-4000 ppm and F ~70-400 ppm (normal-group glasses). Rare andesitic melt inclusions (halogen-rich andesites; HRA) have very high abundances of Cl (~6600-8600 ppm) and F (~780-910 ppm), but their contents of incompatible large ion lithophile elements (LILE) are similar to the normal-group glasses. The preeruptive H2O of basalt to andesite melt inclusions in plagioclase is estimated to range from ~2 to ~10 wt% H2O. The Izu magmas should be undersaturated in H2O and the halogens at their preferred levels of crystallization in the middle to lower crust (~3 to ~11 kbar, ~820° to ~1200°C). A substantial portion of the original H2O is lost due to degassing during the final ascent to surface. By contrast, halogen loss is minor, except for loss of Cl from siliceous dacitic and rhyolitic compositions. The behavior of Cl, F and H2O in undegassed melts resembles the fluid mobile LILE (e.g.; K, Rb, Cs, Ba, U, Pb, Li). Most of the Cl (>99%), H2O (>95%) and F (>53%) in the Izu VF melts appear to originate from the subducting slab. At arc front depths, the slab fluid contains Cl = 0.94+/-0.25 wt%, F = 990+/-270 ppm and H2O = 25+/-7 wt%. If the subducting sediment and the altered basaltic crust were the only slab sources, then the subducted Cl appears to be almost entirely recycled at the Izu arc (~77-129%). Conversely, H2O (~13-22% recycled at arc) and F (~4-6% recycled) must be either lost during shallow subduction or retained in the slab to greater depths. If a seawater-impregnated serpentinite layer below the basaltic crust were an additional source of Cl and H2O, the calculated percentage of Cl and H2O recycled at arc would be lower. Extrapolating the Izu data to the total length of global arcs (~37000 km), the global arc outflux of fluid-recycled Cl and H2O at subduction zones amounts to Cl ~2.9-3.8 mln ton/yr and H2O ~70-100 mln ton/yr, respectively - comparable to previous estimates. Further, we obtain a first estimate of global arc outflux of fluid-recycled F of ~0.3-0.4 mln ton/yr. Despite the inherent uncertainties, our results support models suggesting that the slab becomes strongly depleted in Cl and H2O in subduction zones. In contrast, much of the subducted F appears to be returned to the deep mantle, implying efficient fractionation of Cl and H2O from F during the subduction process. However, if slab devolatilization produces slab fluids with high Cl/F (~9.5), slab melting will still produce components with low Cl/F ratios (~0.9), similar to those characteristic of the upper continental crust (Cl/F ~0.3-0.9).

Crystal morphologies and pyroxene compositions in boninites and tholeiitic basalts at DSDP Holes 60-458 and 60-459B

Not all boninites are glassy lavas. Those of Hole 458 in the Mariana fore-arc region are submarine pillow lavas and more massive flows in which glass occurs only in quenched margins. Pillow and flow interiors have abundant Plagioclase spherulites, microlites, or even larger crystals but can be recognized as boninites by (1) occurrence of bronzite, (2) presence of augite-bronzite microphenocryst intergrowths, and (3) reversal of the usual basaltic groundmass crystallization sequence of plagioclase-augite to augite-plagioclase. The latter is accentuated by sharply contrasting augite and Plagioclase crystal morphologies near pillow margins, a consequence of rapid cooling rates. This crystallization sequence appears to be a consequence of boninites having higher SiO2 and Mg/Mg + Fe than basalts but lower CaO/Al2O3. Microprobe data are used to illustrate the effects of rapid cooling on the compositions of pyroxene and microphenocrysts in a glassy boninite sample and to estimate temperatures of crystallization of coexisting bronzite and augite. A range from 1320°C to 1200°C is calculated with an average of 1250°C. This is higher by 120°-230° than the known range for western Pacific arc tholeiites and by over 300° than for calc-alkalic andesites. Boninites of Hole 458 lack olivine and clinoenstatite but are otherwise chemically and petrographically similar to boninites that have these minerals. In order to distinguish the two types, the Hole 458 lavas are here termed boninites and the others are termed olivine boninites. Arc tholeiite pillow lavas from Holes 458 and 459B are briefly described and their textures compared to fractionated, moderately iron-enriched, abyssal tholeiites. Massive tholeiite flows contain striking quartz-alkali feldspar micrographic intergrowths with coarsely spherulitic textures resulting from in situ magmatic differentiation. Such intergrowths are rare in massive abyssal tholeiites cored by DSDP and probably occur here because arc tholeiites have higher normative quartz at comparable degrees of iron enrichment - a result of higher oxygen fugacities and earlier separation of titanomagnetite - than abyssal tholeiites.

Chemistry of peridotites from ODP 109-670A

During Leg 109 of the Ocean Drilling Program, about 100 m of serpentinized peridotites were drilled on the western wall of the M.A.R. axial rift valley, 45 km south of the Kane Fracture Zone. The present study reports petrological and mineralogical data obtained from 29 small pieces of these ultramafic rocks, including about 60% serpentinized harzburgites, 26% serpentinized lherzolites, 14% serpentinized dunites, and one sample of olivine websterite. Modal analyses show that all these rocks are plagioclase-free four-phase peridotites equilibrated in the spinel lherzolite facies. The estimated average modal composition of the sample set is about 80% olivine, 14% opx, 5% cpx, and 1% spinel, that is, a cpx-poor lherzolite. The well developed porphyroclastic structures and mineralogical characteristics of these rocks indicate their affinity with the group of residual mantle tectonites, among the abyssal peridotites. Features typical of magmatic cumulates are lacking. The high contents in Al2O3 of the cpx (average 5.4%) and of the opx (average 4.3%) porphyroclasts, the low Cr# of the spinels (average 22.9%), and the rather high content in modal cpx (about 5%), indicate a moderate percentage of melting, of the order of 10%-15%. Site 670 peridotites plot close to the least depleted mantle rocks collected in the oceans in most diagrams used to define the average trend of the ocean-floor peridotites. Microprobe traverses across the cores of the exsolved opx and cpx porphyroclasts permitted the recalculation of the magmatic compositions of these pyroxenes: the 'primitive' opx were equilibrated at about 1300°C, probably at the end of the main melting episodes, whereas the 'primitive' cpx show lower equilibration temperatures, at about 1200°C, reflecting a more complex thermal history. The subsolidus evolution is well recorded, from 1200°C to about 950CC, by the exsolved pyroxenes and the olivine and spinel phases. Unusually high blocking temperatures, close to 1000°C, indicate that the peridotite body was cooled very rapidly between 1000°C and the beginning of serpentinization. Oxygen fugacities, calculated for 10 kb and at the blocking temperatures indicated by the olivine/spinel geothermometer, are close to the usual fugacities calculated in oceanic peridotites and basalts (of the order of 10**-10 to 10**-11, on the QFM buffer). Site 670 peridotites have compositions close to those of the peridotites collected in the Kane Fracture Zone area, and obviously belong to the moderately depleted mantle peridotites which characterize abyssal peridotites collected away from mantle plumes and oceanic islands. In particular, they differ from the highly residual harzburgites collected along the M.A.R. over the Azores bulge.

Whole rock and Cr-rich spinel geochemistry of ODP Legs 152 and 163 and DSDP Hole 38-338 samples

Coring during Ocean Drilling Program and Deep Sea Drilling Project Legs 163, 152, 104, 81, and 38 recovered sequences of altered basalt from North Atlantic seaward-dipping reflector sequences (SDRS) erupted during the initial rifting of Greenland from northern Europe and likely associated with excessive mantle temperatures caused by an impacting mantle plume head. Cr-rich spinel is found abundantly as inclusions and groundmass crystals within the olivine-rich lavas of Hole 917A (Leg 152) cored into the Southeast Greenland SDRS, but only rarely as inclusions within plagioclase in the lavas of the Vøring Plateau SDRS, and it is absent from other cored SDRS lavas from the Rockall Plateau and Southeast Greenland. Eruptive melt compositions determined from inferred, thermodynamically-defined, spinel-melt exchange equilibria indicate that the most primitive melts represented by Hole 917A basalts have Mg/(Mg + Fe2+) at least as high as 0.70 and approach near-primary mantle melt compositions. In contrast, Cr-rich spinels from Hole 338 (Leg 38) lavas on the Vøring Plateau SDRS give evidence for melt with Mg/(Mg + Fe2+) only as high as 0.64. This study underlines that primitive melts similar to those from Hole 917A comprise only a small fraction of the eruptive North Atlantic SDRS melts, and that most SDRS basalts were, in fact, too evolved to have precipitated Cr-rich spinel, with true melt Mg/(Mg + Fe2+) likely below 0.60. The evolved nature of the SDRS basalts implies large amounts of fractionation at the base of the crust or deep within it, consistent with seismic results that indicate an abnormally thick Layer 3 underlying the SDRS.

Isostatic pressing of UO₂ in high temperature metals /

The hot isostatic pressing process has been applied at temperatures up to 1500°C for the fabrication of high temperature fuel rods composed of UO₂ clad in columbium and UO₂ in iron-aluminum type alloy. The fused UO₂ powder apparently becomes quite plastic at temperatures above 1200°C and can be isostatically compacted at 1500°C to 98% of its theoretical density. Columbian tubes particularly lend themselves to the fabrication of fuel rods by simultaneously compacting and cladding UO₂ powders in the tubes, but the cast iron-aluminum type alloy that was used was unsatisfactory because of its brittleness.

Phase equilibria in the Fe-Zn-O system at conditions relevant to zinc sintering and smelting

Zincite and spinel phases are present in the complex slag systems encountered in zinc/lead sintering and zinc smelting processes. These phases form extensive solid solutions and are stable over a wide range of compositions, temperatures and oxygen partial pressures. Accurate information on the stability of these phases is required in order to develop thermodynamic models of these slag systems. Phase equilibria in the Fe–Zn–O system have been experimentally studied for a range of conditions, between 900°C and 1580°C and oxygen partial pressures (pO2) between air and metallic iron saturation, using equilibration and quenching techniques. The compositions of the phases were measured using Electron probe X-ray microanalysis (EPMA). The ferrous and ferric bulk iron concentrations were determined using a specially developed wet-chemical analysis procedure based on the use of ammonium metavanadate. XRD was used to confirm phase identification. A procedure was developed to overcome the problems associated with evaporation of zinc at low pO2 values and to ensure the achievement of equilibria. An isothermal section of the system FeO–Fe2O3–ZnO at high ZnO concentrations at 1200°C was constructed. The maximum solubilities of iron and zinc in zincite and spinel phases in equilibrium were determined at pO2 = 1 × 10-6 atm at 1200°C and 1300°C. The morphology of the zincite crystals sharply changes in air between 1200–1300°C from rounded to plate-like. This is shown to be associated with significant increase in total iron concentration, the additional iron being principally in the form of ferric iron. Calculations performed by FactSage with a thermodynamically optimised database have been compared with the experimental results.