Distribution of neodymium isotopes and concentrations during M77/3 and M77/4

The radiogenic isotope composition of the Rare Earth Element (REE) neodymium (Nd) is a powerful water mass proxy for present and past ocean circulation. The processes controlling the Nd budget of the global ocean are not quantitatively understood and in particular source and sink mechanisms are still under debate. In this study we present the first full water column data set of dissolved Nd isotope compositions and Nd concentrations for the Eastern Equatorial Pacific (EEP), where one of the globally largest Oxygen Minimum Zones (OMZ) is located. This region is of particular interest for understanding the biogeochemical cycling of REEs because anoxic conditions may lead to release of REEs from the shelf, whereas high particle densities and fluxes potentially remove the REEs from the water column. Data were obtained between 11400N and 161S along a nearshore and an offshore transect. Near surface zonal current bands, such as the Equatorial Undercurrent (EUC) and the Subsurface Countercurrent (SSCC), which are supplying oxygen-rich water to the OMZ are characterized by radiogenic Nd isotope signatures (eNd=-2). Surface waters in the northernmost part of the study area are even more radiogenic (eNd = +3), most likely due to release of Nd from volcanogenic material. Deep and bottom waters at the southernmost offshore station (141S) are clearly controlled by advection of water masses with less radiogenic signatures (eNd=- 7) originating from the Southern Ocean. Towards the equator, however, the deep waters show a clear trend towards more radiogenic values of up to eNd=-2. The northernmost station located in the Panama basin shows highly radiogenic Nd isotope signatures in the entire water column, which indicates that particle scavenging, downward transport and release processes play an important role. This is supported by relatively low Nd concentrations in deep waters (3000-6000 m) in the EEP (20 pmol/kg) compared to locations in the Northern and Central Pacific (40-60 pmol/kg), which suggests enhanced removal of Nd in the EEP.

(Tables 1-3) Water chemistry of cloud forest streams at baseflow conditions, Rio San Francisco, Ecuador

We investigated controls on the water chemistry of a South Ecuadorian cloud forest catchment which is partly pristine, and partly converted to extensive pasture. From April 2007 to May 2008 water samples were taken weekly to biweekly at nine different subcatchments, and were screened for differences in electric conductivity, pH, anion, as well as element composition. A principal component analysis was conducted to reduce dimensionality of the data set and define major factors explaining variation in the data. Three main factors were isolated by a subset of 10 elements (Ca2+, Ce, Gd, K+, Mg2+, Na+, Nd, Rb, Sr, Y), explaining around 90% of the data variation. Land-use was the major factor controlling and changing water chemistry of the subcatchments. A second factor was associated with the concentration of rare earth elements in water, presumably highlighting other anthropogenic influences such as gravel excavation or road construction. Around 12% of the variation was explained by the third component, which was defined by the occurrence of Rb and K and represents the influence of vegetation dynamics on element accumulation and wash-out. Comparison of base- and fast flow concentrations led to the assumption that a significant portion of soil water from around 30 cm depth contributes to storm flow, as revealed by increased rare earth element concentrations in fast flow samples. Our findings demonstrate the utility of multi-tracer principal component analysis to study tropical headwater streams, and emphasize the need for effective land management in cloud forest catchments.

Geochemistry of Atlantis Massif crust

The Atlantis Massif (Mid-Atlantic Ridge, 30°N) is an oceanic core complex marked by distinct variations in crustal architecture, deformation and metamorphism over distances of at least 5 km. We report Sr and Nd isotope data and Rare Earth Element (REE) concentrations of gabbroic and ultramafic rocks drilled at the central dome (IODP Hole 1309D) and recovered by submersible from the southern ridge of the massif that underlie the peridotite-hosted Lost City Hydrothermal Field. Systematic variations between the two areas document variations in seawater penetration and degree of fluid-rock interaction during uplift and emplacement of the massif and hydrothermal activity associated with the formation of Lost City. Homogeneous Sr and Nd isotope compositions of the gabbroic rocks from the two areas (87Sr/86Sr: 0.70261-0.70429 and epsilon-Nd: +9.1 to +12.1) indicate an origin from a depleted mantle. At the central dome, serpentinized peridotites are rare and show elevated seawater-like Sr isotope compositions related to serpentinization at shallow crustal levels, whereas unaltered mantle isotopic compositions preserved in the gabbroic rocks attest to limited seawater interaction at depth. This portion of the massif remained relatively unaffected by Lost City hydrothermal activity. In contrast, pervasive alteration and seawater-like Sr and Nd isotope compositions of serpentinites at the southern wall (87Sr/86Sr: 0.70885-0.70918; epsilon-Nd: -4.7 to +11.3) indicate very high fluid-rock ratios (~20 and up to 10**6) and enhanced fluid fluxes during hydrothermal circulation. Our studies show that Nd isotopes are most sensitive to high fluid fluxes and are thus an important geochemical tracer for quantification of water-rock ratios in hydrothermal systems. Our results suggest that high fluxes and long-lived serpentinization processes may be critical to the formation of Lost City-type systems and that normal faulting and mass wasting in the south facilitate seawater penetration necessary to sustain hydrothermal activity.

An alkalic volcanic suite of the Labrador Trough, Labrador

The Nimish Subgroup igneous suite is a linear belt of volcanic and plutonic rocks in the Dyke Lake area of the southern Labrador Trough. The volcanics are interbedded with the sediments of the Wishart and Sokoman Formations of the Aphebian aged, Knob Lake Group. The sokoman Formation forms a time stratigraphic horizon that separates the lower Petitsikapau Lake Formation from the upper Astray Lake formation of the Nimish Subgroup. The occurrence of these volcanics within the Knob Lake Group is unique relative to Labrador Trough stratigraphy, as elsewhere the Knob Lake Group is a dominantly sedimentary succession and volcanics are restricted to the younger Doublet Group. Stratigraphic relationships between the Nimish Subgroup and the Sokoman formation indicate contemporaneous volcanic, clastic and chemical sedimentary activity. The internal stratigraphy of the Sokoman Formation exhibits a three-fold subdivision that is broadly correlatable with similar subdivisions in the Schefferville "main ore zone", 30 miles to the northwest. A detailed facies and paleogeographic model relating the volcanic activity to iron formation deposition in the Dyke Lake is presented. The rocks of the Dyke Lake area have been affected by lower greenschist facies metamorphism during the Hudsonian orogenic event, circa 1735 my. Geochemical evidence indicates that the igneous rocks of the Nimish Subgroup have been metasomatized with large degrees of mobility in Na₂O, K₂O, CaO, MgO, SiO₂, FeO and Fe₂O₃ suspected. The "immobile trace elements", Ti, Zr, Nb, Y and Ga imply that the Nimish lavas are a mildly alkaline suite that has an alkali basalt-trachyandesite-comendite differentiation scheme. The rare earth element, REE, geochemistry of the Nimish Subgroup is supportive of the alkaline nature of the volcanics and has been used to model the fractional crystallization petrogenesis involved in the two volcanic cycles. The geological, geochemical and geophysical evidence indicates that the Nimish Subgroup lavas are possibly a rift facies, alkaline suite related to the tensional tectonic regime that preceeded the extrusion of voluminous tholeiitic lavas of the Doublet Group.

Upper-Pleistocene terrace deposits in Mediterranean climate: geomorphological and source-rock control on mineral and geochemical signatures (Betic Cordillera, SE Spain)

Mineral and chemical composition of alluvial Upper-Pleistocene deposits from the Alto Guadalquivir Basin (SE Spain) were studied as a tool to identify sedimentary and geomorphological processes controlling its formation. Sediments located upstream, in the north-eastern sector of the basin, are rich in dolomite, illite, MgO and KB2BO. Downstream, sediments at the sequence base are enriched in calcite, smectite and CaO, whereas the upper sediments have similar features to those from upstream. Elevated rare-earth elements (REE) values can be related to low carbonate content in the sediments and the increase of silicate material produced and concentrated during soil formation processes in the neighbouring source areas. Two mineralogical and geochemical signatures related to different sediment source areas were identified. Basal levels were deposited during a predominantly erosive initial stage, and are mainly composed of calcite and smectite materials enriched in REE coming from Neogene marls and limestones. Then the deposition of the upper levels of the alluvial sequences, made of dolomite and illitic materials depleted in REE coming from the surrounding Sierra de Cazorla area took place during a less erosive later stage of the fluvial system. Such modification was responsible of the change in the mineralogical and geochemical composition of the alluvial sediments.

Evolution of neodymium isotopic signature of seawater during the Late Cretaceous: Implications for intermediate and deep circulation

Neodymium isotopic compositions (εNd) have been largely used for the last fifty years as a tracer of past ocean circulation, and more intensively during the last decade to investigate ocean circulation during the Cretaceous period. Despite a growing set of data, circulation patterns still remain unclear during this period. In particular, the identification of the deep-water masses and their spatial extension within the different oceanic basins are poorly constrained. In this study we present new deep-water εNd data inferred from the Nd isotope composition of fish remains and Fe-Mn oxyhydroxide coatings on foraminifera tests, along with new εNd data of residual (partly detrital) fraction recovered from DSDP sites 152 (Nicaraguan Rise), 258 (Naturaliste Plateau), 323 (Bellinghausen Abyssal Plain), and ODP sites 690 (Maud Rise) and 700 (East Georgia Basin, South Atlantic). The presence of abundant authigenic minerals in the sediments at sites 152 and 690 detected by XRD analyses may explain both middle rare earth element enrichments in the spectra of the residual fraction and the evolution of residual fraction εNd that mirror that of the bottom waters at the two sites. The results point towards a close correspondence between the bottom water εNd values of sites 258 and 700 from the late Turonian to the Santonian. Since the deep-water Nd isotope values at these two sites are also similar to those at other proto-Indian sites, we propose the existence of a common intermediate to deep-water water mass as early as the mid-Cretaceous. The water mass would have extended from the central part of the South Atlantic to the eastern part of proto-Indian ocean sites, beyond the Kerguelen Plateau. Furthermore, data from south and north of the Rio Grande Rise-Walvis Ridge complex (sites 700 and 530) are indistinguishable from the Turonian to Campanian, suggesting a common water mass since the Turonian at least. This view is supported by a reconstruction of the Rio Grande Rise-Walvis Ridge complex during the Turonian, highlighting the likely existence of a deep breach between the Rio Grande Rise and the proto-Walvis Ridge at that time. Thus deep-water circulation may have been possible between the different austral basins as early as the Turonian, despite the presence of potential oceanic barriers. Comparison of new seawater and residue εNd data on Nicaraguan Rise suggest a westward circulation of intermediate waters through the Caribbean Seaway during the Maastrichtian and Paleocene from the North Atlantic to the Pacific. This westward circulation reduced the Pacific water influence in the Atlantic, and was likely responsible for more uniform, less radiogenic εNd values in the North Atlantic after 80 Ma. Additionally, our data document an increasing trend observed in several oceanic basins during the Maastrichtian and the Paleocene, which is more pronounced in the North Pacific. Although the origin of this increase still remains unclear, it might be explained by an increase in the contribution of radiogenic material to upper ocean waters in the northern Pacific. By sinking to depth, these waters may have redistributed to some extent more radiogenic signatures to other ocean basins through deep-water exchanges.

Effects of synthetic conditions on the structural, stability and ion conducting properties of Li0.30(La0.50Ln0.50)0.567TiO3 (Ln= La, Pr, Nd) solid electrolytes for rechargeable lithium batteries

The structure, thermal stability, morphology and ion conductivity of titanium perovskites with the general formula Li3xLn2/3−xTiO3 (Ln = rare earth element; 3x= 0.30) are studied in the context of their possible use as solid electrolyte materials for lithium ion batteries. Materials are prepared by a glycine-nitrate method using different sintering treatments, with a cation-disorder-induced structural transition from tetragonal to cubic symmetry, detected as quenching temperature increases. SEM images show that the average grain size increases with increasing sintering temperature and time. Slightly higher bulk conductivity values have been observed for quenched samples sintered at high temperature. Bulk conductivity decreases with the lanthanide ion size. A slight conductivity enhancement, always limited by grain boundaries, is observed for longer sintering times. TDX measurements of the electrolyte/cathode mixtures also show a good stability of the electrolytes in the temperature range of 30-1100ºC.

Síntese e caracterização de catalisadores de LaNiO3 não suportados e suportados em Al2O3 e ZrO2 para a reforma a vapor do metano

Ionic oxides with ABO3 structure, where A represents a rare earth element or an alkaline metal and B is a transition metal from group VIII of the periodic table are potential catalysts for oxidation and good candidates for steam reforming reaction. Different methods have been considered for the synthesis of the oxide materials with perovskite structure to produce a high homogeneous material with low amount of impurities and low calcination temperatures. In the current work, oxides with the LaNiO3 formula had been synthesized using the method of the polymeric precursors. The thermal treatment of the materials took place at 300 ºC for 2h. The material supported in alumina and/or zirconia was calcined at 800 ºC temperature for 4h. The samples had been characterized by the following techniques: thermogravimetry; infrared spectroscopy; X-ray diffraction; specific surface area; distribution of particle size; scanning electron microscopy and thermo-programmed reduction. The steam reforming reaction was carried out in a pilot plant using reducing atmosphere in the reactor with a mixture of 10% H2-Argon, a mass about 5g of catalyst, flowing at 50 mL.min-1. The temperature range used was 50 - 1000 oC with a heating rate of 10 oC.min-1. A thermal conductivity detector was used to analyze the gas after the water trapping, in order to permit to quantify the consumption of hydrogen for the lanthanum nickelates (LaNiO3). The results showed that lanthanum nickelate were more efficient when supported in alumina than when supported in zirconia. It was observed that the methane conversion was approximately 100% and the selectivity to hydrogen was about 70%. In all cases were verified low selectivity to CO and CO2

Life Cycle of Deccan Trap Magma Chambers: A Crystal Scale Elemental and Strontium Isotopic Investigation

The Deccan Trap basalts are the remnants of a massive series of lava flows that erupted at the K/T boundary and covered 1-2 million km2 of west-central India. This eruptive event is of global interest because of its possible link to the major mass extinction event, and there is much debate about the duration of this massive volcanic event. In contrast to isotopic or paleomagnetic dating methods, I explore an alternative approach to determine the lifecycle of the magma chambers that supplied the lavas, and extend the concept to obtain a tighter constraint on Deccan’s duration. My method relies on extracting time information from elemental and isotopic diffusion across zone boundary in an individual crystal. I determined elemental and Sr-isotopic variations across abnormally large (2-5 cm) plagioclase crystals from the Thalghat and Kashele “Giant Plagioclase Basalts” from the lowermost Jawhar and Igatpuri Formations respectively in the thickest Western Ghats section near Mumbai. I also obtained bulk rock major, trace and rare earth element chemistry of each lava flow from the two formations. Thalghat flows contain only 12% zoned crystals, with 87Sr/86Sr ratios of 0.7096 in the core and 0.7106 in the rim, separated by a sharp boundary. In contrast, all Kashele crystals have a wider range of 87Sr/86Sr values, with multiple zones. Geochemical modeling of the data suggests that the two types of crystals grew in distinct magmatic environments. Modeling intracrystalline diffusive equilibration between the core and rim of Thalghat crystals led me to obtain a crystal growth rate of 2.03x10-10 cm/s and a residence time of 780 years for the crystals in the magma chamber(s). Employing some assumptions based on field and geochronologic evidence, I extrapolated this residence time to the entire Western Ghats and obtained an estimate of 25,000 – 35,000 years for the duration of Western Ghats volcanism. This gave an eruptive rate of 30 – 40 km3/yr, which is much higher than any presently erupting volcano. This result will remain speculative until a similarly detailed analytical-modeling study is performed for the rest of the Western Ghats formations.

Rare and trace element analyses from DSDP Holes 31-291 and 31-294 from the Philippine Sea

Metal-rich sediments were found in the West Philippine Basin at DSDP sites 291 (located about 500 km SW of the Philippine Ridge or Central Basin Fault) and 294/295 (located about 580 km NE of the Philippine Ridge). In both cases the metalliferous deposits constitute a layer, probably Eocene in age, resting directly above the basaltic basement at the bottom of the sediment column. The chemistry of the major (including Fe and Mn) and trace elements (including trace metals, rare earth elements, U and Th) suggest a strong similarity of these deposits to metalliferous deposits produced by hydrothermal activity at oceanic spreading centers. Well-crystallized hematite is a major component of the metal-rich deposits at site 294/295. We infer that the Philippine Sea deposits were formed at some spreading center by hydrothermal processes of metallogenesis, similar to processes occurring at oceanic spreading centers. A locus for their formation might have been the Philippine Ridge (Central Basin Fault), probably an extinct spreading center. We conclude that metallogenesis of the type occurring at oceanic spreading centers can take place also in marginal basins. This has implications for the origin of metal deposits found in some ophiolite complexes, such as those in Luzon (Philippines), which may represent fragments of former marginal basins rather than of oceanic lithosphere.

Constraints on mantle melting from major and trace element systematics in residual abyssal peridotites

ZusammenfassungDie Bildung von mittelozeanischen Rückenbasalten (MORB) ist einer der wichtigsten Stoffflüsse der Erde. Jährlich wird entlang der 75.000 km langen mittelozeanischen Rücken mehr als 20 km3 neue magmatische Kruste gebildet, das sind etwa 90 Prozent der globalen Magmenproduktion. Obwohl ozeanische Rücken und MORB zu den am meisten untersuchten geologischen Themenbereichen gehören, existieren weiterhin einige Streit-fragen. Zu den wichtigsten zählt die Rolle von geodynamischen Rahmenbedingungen, wie etwa Divergenzrate oder die Nähe zu Hotspots oder Transformstörungen, sowie der absolute Aufschmelzgrad, oder die Tiefe, in der die Aufschmelzung unter den Rücken beginnt. Diese Dissertation widmet sich diesen Themen auf der Basis von Haupt- und Spurenelementzusammensetzungen in Mineralen ozeanischer Mantelgesteine.Geochemische Charakteristika von MORB deuten darauf hin, dass der ozeanische Mantel im Stabilitätsfeld von Granatperidotit zu schmelzen beginnt. Neuere Experimente zeigen jedoch, dass die schweren Seltenerdelemente (SEE) kompatibel im Klinopyroxen (Cpx) sind. Aufgrund dieser granatähnlichen Eigenschaft von Cpx wird Granat nicht mehr zur Erklärung der MORB Daten benötigt, wodurch sich der Beginn der Aufschmelzung zu geringeren Drucken verschiebt. Aus diesem Grund ist es wichtig zu überprüfen, ob diese Hypothese mit Daten von abyssalen Peridotiten in Einklang zu bringen ist. Diese am Ozeanboden aufgeschlossenen Mantelfragmente stellen die Residuen des Aufschmelz-prozesses dar, und ihr Mineralchemismus enthält Information über die Bildungs-bedingungen der Magmen. Haupt- und Spurenelementzusammensetzungen von Peridotit-proben des Zentralindischen Rückens (CIR) wurden mit Mikrosonde und Ionensonde bestimmt, und mit veröffentlichten Daten verglichen. Cpx der CIR Peridotite weisen niedrige Verhältnisse von mittleren zu schweren SEE und hohe absolute Konzentrationen der schweren SEE auf. Aufschmelzmodelle eines Spinellperidotits unter Anwendung von üblichen, inkompatiblen Verteilungskoeffizienten (Kd's) können die gemessenen Fraktionierungen von mittleren zu schweren SEE nicht reproduzieren. Die Anwendung der neuen Kd's, die kompatibles Verhalten der schweren SEE im Cpx vorhersagen, ergibt zwar bessere Resultate, kann jedoch nicht die am stärksten fraktionierten Proben erklären. Darüber hinaus werden sehr hohe Aufschmelzgrade benötigt, was nicht mit Hauptelementdaten in Einklang zu bringen ist. Niedrige (~3-5%) Aufschmelzgrade im Stabilitätsfeld von Granatperidotit, gefolgt von weiterer Aufschmelzung von Spinellperidotit kann jedoch die Beobachtungen weitgehend erklären. Aus diesem Grund muss Granat weiterhin als wichtige Phase bei der Genese von MORB betrachtet werden (Kapitel 1).Eine weitere Hürde zum quantitativen Verständnis von Aufschmelzprozessen unter mittelozeanischen Rücken ist die fehlende Korrelation zwischen Haupt- und Spuren-elementen in residuellen abyssalen Peridotiten. Das Cr/(Cr+Al) Verhältnis (Cr#) in Spinell wird im Allgemeinen als guter qualitativer Indikator für den Aufschmelzgrad betrachtet. Die Mineralchemie der CIR Peridotite und publizierte Daten von anderen abyssalen Peridotiten zeigen, dass die schweren SEE sehr gut (r2 ~ 0.9) mit Cr# der koexistierenden Spinelle korreliert. Die Auswertung dieser Korrelation ergibt einen quantitativen Aufschmelz-indikator für Residuen, welcher auf dem Spinellchemismus basiert. Damit kann der Schmelzgrad als Funktion von Cr# in Spinell ausgedrückt werden: F = 0.10×ln(Cr#) + 0.24 (Hellebrand et al., Nature, in review; Kapitel 2). Die Anwendung dieses Indikators auf Mantelproben, für die keine Ionensondendaten verfügbar sind, ermöglicht es, geochemische und geophysikalischen Daten zu verbinden. Aus geodynamischer Perspektive ist der Gakkel Rücken im Arktischen Ozean von großer Bedeutung für das Verständnis von Aufschmelzprozessen, da er weltweit die niedrigste Divergenzrate aufweist und große Transformstörungen fehlen. Publizierte Basaltdaten deuten auf einen extrem niedrigen Aufschmelzgrad hin, was mit globalen Korrelationen im Einklang steht. Stark alterierte Mantelperidotite einer Lokalität entlang des kaum beprobten Gakkel Rückens wurden deshalb auf Primärminerale untersucht. Nur in einer Probe sind oxidierte Spinellpseudomorphosen mit Spuren primärer Spinelle erhalten geblieben. Ihre Cr# ist signifikant höher als die einiger Peridotite von schneller divergierenden Rücken und ihr Schmelzgrad ist damit höher als aufgrund der Basaltzusammensetzungen vermutet. Der unter Anwendung des oben erwähnten Indikators ermittelte Schmelzgrad ermöglicht die Berechnung der Krustenmächtigkeit am Gakkel Rücken. Diese ist wesentlich größer als die aus Schweredaten ermittelte Mächtigkeit, oder die aus der globalen Korrelation zwischen Divergenzrate und mittels Seismik erhaltene Krustendicke. Dieses unerwartete Ergebnis kann möglicherweise auf kompositionelle Heterogenitäten bei niedrigen Schmelzgraden, oder auf eine insgesamt größere Verarmung des Mantels unter dem Gakkel Rücken zurückgeführt werden (Hellebrand et al., Chem.Geol., in review; Kapitel 3).Zusätzliche Informationen zur Modellierung und Analytik sind im Anhang A-C aufgeführt

Stable-Isotope and Trace Element Time Series from Fedchenko Glacier (Pamirs) Snow/Firn Cores

In summer 2005, two pilot snow/firn cores were obtained at 5365 and 5206 m a.s.l. on Fedchenko glacier, Pamirs, Tajikistan, the world's longest and deepest alpine glacier. The well-defined seasonal layering appearing in stable-isotope and trace element distribution identified the physical links controlling the climate and aerosol concentration signals. Air temperature and humidity/precipitation were the primary determinants of stable-isotope ratios. Most precipitation over the Pamirs originated in the Atlantic. In summer, water vapor was re-evaporated from semi-arid regions in central Eurasia. The semi-arid regions contribute to non-soluble aerosol loading in snow accumulated on Fedchenko glacier. In the Pamir core, concentrations of rare earth elements, major and other elements were less than those in the Tien Shan but greater than those in Antarctica, Greenland, the Alps and the Altai. The content of heavy metals in the Fedchenko cores is 2-14 times lower than in the Altai glaciers. Loess from Afghan-Tajik deposits is the predominant lithogenic material transported to the Pamirs. Trace elements generally showed that aerosol concentration tended to increase on the windward slopes during dust storms but tended to decrease with altitude under clear conditions. The trace element profile documented one of the most severe droughts in the 20th century.

Variations of clinopyroxene/melt element partitioning during assimilation of olivine/peridotite by low-Mg diorite magma

The effects of crystal chemistry and melt composition on the control of clinopyroxene/melt element partitioning (D) during the assimilation of olivine/peridotite by felsic magma have been investigated in Mesozoic high-Mg diorites from North China. The assimilation resulted in significant increase of Mg, Cr and Ni and only slight (< 30%) decrease of incompatible elements of the magma, and the compositional variations have been mirrored by the normally and reversely zoned clinopyroxene microphenocrysts formed at the early stage of the magma evolution. The Mg# [100 × Mg / (Mg + Fe)] values of the reversely zoned clinopyroxenes increase from 65 to 75 in the core to 85–90 in the high-Mg midsection, and reduce back to 73–79 at the rim. Trace element profiles across all these clinopyroxene domains have been measured by LA-ICP-MS. The melt trace element composition has been constrained from bulk rock analyses of the fine-grained low- and high-Mg diorites. Clinopyroxene/melt partition coefficients for rare earth elements (REE) and Y in the high-Mg group zonings (Mg# > 73–79, DDy < 1.2) are positively correlated with tetrahedral IVAl and increase by a factor of 3–4 as tetrahedral IVAl increases from 0.01 to 0.1 per formula unit (pfu). These systematic variations are interpreted to be controlled by the clinopyroxene composition. In contrast, partition coefficients for low-Mg group zonings (Mg# < 75–79, DDy > 1.2) are elevated by up to an order of magnitude (for REE and Y) or more (for Zr and Hf) at similar IVAl, indicating dominant control of melt composition/structure. DZr and DHf show a larger sensitivity to the compositional change of crystal and melt than DREE. DTi values for the low- and high-Mg zonings show a uniform dependence on IVAl. DSr and DLi are insensitive to the compositional change of clinopyroxene and melt, resulting in Sr depletions in the clinopyroxene zonings with elevated REE without crystallization of plagioclase. Our observations show that crystal chemistry and melt composition/structure may alternatively control clinopyroxene/melt partitioning during the assimilation of peridotite by felsic magma, and may be useful for deciphering clinopyroxene compositions and related crust–mantle processes.

The Interplay between Melting, Refertilization and Carbonatite Metasomatism in Off-Cratonic Lithospheric Mantle under Zealandia: an Integrated Major, Trace and Platinum Group Element Study

It is widely accepted that stabilization of the continental crust requires the presence of sub-continental lithospheric mantle. However, the degree of melt depletion required to stabilize the lithosphere and whether widespread refertilization is a significant process remain unresolved. Here, major and trace element, including platinum group elements (PGE), characterization of 40 mantle xenoliths from 13 localities is used to constrain the melt depletion, refertilization and metasomatic history of lithospheric mantle underneath the micro-continent Zealandia. Our previously published Re–Os isotopic data for a subset of these xenoliths indicate Phanerozoic to Paleoproterozoic ages and, reinterpreted with the new major and trace element data presented here, demonstrate that a large volume (>2 million km3) of lithospheric mantle with an age of 1·99 ± 0·21 Ga is present below the much younger crust of Zealandia. A peritectic melting model using moderately incompatible trace elements (e.g. Yb) in bulk-rocks demonstrates that these peridotites experienced a significant range of degrees of partial melting, between 3 and 28%. During subsolidus equilibration clinopyroxene gains significant rare earth elements (REE), which then leads to the underestimation of the degree of partial melting by ≤12% in fertile xenoliths. A new approach taking into account the effects of subsolidus re-equilibration on clinopyroxene composition effectively removes discrepancies in the calculated degree of melting and provides consistent estimates of between 4 and 29%. The estimated amount of melting is independent of the Re–Os model ages of the samples. The PGE patterns record simple melt depletion histories and the retention of primary base metal sulfides in the majority of the xenoliths. A rapid decrease in Pt/IrN observed at c. 1·0 wt % Al2O3 is a direct result of the exhaustion of sulfide in the mantle residue at c. 20–25% partial melting and the inability of Pt to form a stable alloy phase. Major elements preserve evidence for refertilization by a basaltic component that resulted in the formation of secondary clinopyroxene and low-forsterite olivine. The majority of xenoliths show the effects of cryptic metasomatic overprinting, ranging from minor to strong light REE enrichments in bulk-rocks (La/YbN = 0·16–15·9). Metasomatism is heterogeneous, with samples varying from those with weak REE enrichment and notable positive Sr and U–Th anomalies and negative Nb–Ta anomalies in clinopyroxene to those that have extremely high concentrations of REE, Th–U and Nb. Chemical compositions are consistent with a carbonatitic component contributing to the metasomatism of the lithosphere under Zealandia. Notably, the intense metasomatism of the samples did not affect the PGE budget of the peridotites as this was controlled by residual sulfides.

Major and trace element concentrations of sediments from the IODP Exp302 sites

We analyzed a suite of sediment samples recovered in the central Arctic Ocean for major, trace, and rare earth elements in order to assess changes in terrigenous source material throughout the Cenozoic. The terrigenous component consists of two end-members. Input from a shale-like composition dominates bulk sediments, especially those deposited during the Paleocene and since the Miocene, and may represent sediment supply from the eastern Laptev Sea. Therefore, even though the environment and transport mechanisms may have varied from ice free to ice dominated, sequences of the early Paleogene and later Neogene appear to have been influenced by a single major terrigenous source. This suggests similar transport capabilities and trajectories for both ocean and drift currents through significant parts of the Cenozoic. Influence from a more mafic source appears to be more important through the early Eocene to the middle Miocene and most likely represents material from the western Laptev Sea or Kara Sea. Thus, Eocene major changes in surface water productivity appear broadly synchronous with those in terrigenous provenance. A combination of regional sea level variations, local shelf processes, and transport mechanisms are among the more probable causes for the observed source changes. Although the assignment of sources using chemistry presently is constrained by a lack of data from certain regions (e.g., eastern Siberian Sea) our results generally agree with inferences based on mineralogy or radiogenic isotopes and shed further light on long-term reconstructions of the central Arctic Ocean.