Petrogenetic evolution of Uralian-Alaskan-type mafic-ultramafic complexes in the southern and middle Urals, Russia

The PhD thesis at hand consists of three parts and describes the petrogenetic evolution of Uralian-Alaskan-type mafic ultramafic complexes in the Ural Mountains, Russia. Uralian-Alaskan-type mafic-ultramafic complexes are recognized as a distinct class of intrusions. Characteristic petrologic features are the concentric zonation of a central dunite body grading outward into wehrlite, clinopyroxenite and gabbro, the absence of orthopyroxene and frequently occurring platinum group element (PGE) mineralization. In addition, the presence of ferric iron-rich spinel discriminates Uralian-Alaskan-type complexes from most other mafic ultramafic rock assemblages. The studied Uralian-Alaskan-type complexes (Nizhnii Tagil, Kytlym and Svetley Bor) belong to the southern part of a 900 km long, N–S-trending chain of similar intrusions between the Main Uralian Fault to the west and the Serov-Mauk Fault to the east. The first chapter of this thesis studies the evolution of the ultramafic rocks tracing the compositional variations of rock forming and accessory minerals. The comparison of the chemical composition of olivine, clinopyroxene and chromian spinel from the Urals with data from other localities indicates that they are unique intrusions having a characteristic spinel and clinopyroxene chemistry. Laser ablation-ICPMS (LA-ICPMS ) analyses of trace element concentrations in clinopyroxene are used to calculate the composition of their parental melt which is characterized by enriched LREE (0.5-5.2 prim. mantle) and other highly incompatible elements (U, Th, Ba, Rb) relative to the HREE (0.25-2.0 prim. mantle). A subduction-related geotectonic setting is indicated by a positive anomaly for Sr and negative anomalies for Ti, Zr and Hf. The mineral compositions monitor the evolution of the parental magmas and decipher differences between the studied complexes. In addition, the observed variation in LREE/HREE (for example La/Lu = 2-24) can be best explained with the model of an episodically replenished and erupted open magma chamber system with the extensive fractionation of olivine, spinel and clinopyroxene. The data also show that ankaramites in a subduction-related geotectonic setting could represent parental magmas of Uralian-Alaskan-type complexes. The second chapter of the thesis discusses the chemical variation of major and trace elements in rock-forming minerals of the mafic rocks. Electron microprobe and LA-ICPMS analyses are used to quantitatively describe the petrogenetic relationship between the different gabbroic lithologies and their genetic link to the ultramafic rocks. The composition of clinopyroxene identifies the presence of melts with different trace element abundances on the scale of a thin section and suggests the presence of open system crustal magma chambers. Even on a regional scale the large variation of trace element concentrations and ratios in clinopyroxene (e.g. La/Lu = 3-55) is best explained by the interaction of at least two fundamentally different magma types at various stages of fractionation. This requires the existence of a complex magma chamber system fed with multiple pulses of magmas from at least two different coeval sources in a subduction-related environment. One source produces silica saturated Island arc tholeiitic melts. The second source produces silica undersaturated, ultra-calcic, alkaline melts. Taken these data collectively, the mixing of the two different parental magmas is the dominant petrogenetic process explaining the observed chemical variations. The results further imply that this is an intrinsic feature of Uralian-Alaskan-type complexes and probably of many similar mafic-ultramafic complexes world-wide. In the third chapter of this thesis the major element composition of homogeneous and exsolved spinel is used as a petrogenetic indicator. Homogeneous chromian spinel in dunites and wehrlites monitors the fractionation during the early stages of the magma chamber and the onset of clinopyroxene fractionation as well as the reaction of spinel with interstitial liquid. Exsolved spinel is present in mafic and ultramafic rocks from all three studied complexes. Its composition lies along a solvus curve which defines an equilibrium temperature of 600°C, given that spinel coexists with olivine. This temperature is considered to be close to the temperature of the host rocks into which the studied Uralian-Alaskan-type complexes intruded. The similarity of the exsolution temperatures in the different complexes over a distance of several hundred kilometres implies a regional tectonic event that terminated the exsolution process. This event is potentially associated with the final exhumation of the Uralian-Alaskan-type complexes along the Main Uralian Fault and the Serov-Mauk Fault in the Uralian fold belt.

Forward modelling of petrological crust-forming processes on the early Earth

Tonalite-trondhjemite-granodiorite (TTG) gneisses form up to two-thirds of the preserved Archean continental crust and there is considerable debate regarding the primary magmatic processes of the generation of these rocks. The popular theories indicate that these rocks were formed by partial melting of basaltic oceanic crust which was previously metamorphosed to garnet-amphibolite and/or eclogite facies conditions either at the base of thick oceanic crust or by subduction processes.rnThis study investigates a new aspect regarding the source rock for Archean continental crust which is inferred to have had a bulk compostion richer in magnesium (picrite) than present-day basaltic oceanic crust. This difference is supposed to originate from a higher geothermal gradient in the early Archean which may have induced higher degrees of partial melting in the mantle, which resulted in a thicker and more magnesian oceanic crust. rnThe methods used to investigate the role of a more MgO-rich source rock in the formation of TTG-like melts in the context of this new approach are mineral equilibria calculations with the software THERMOCALC and high-pressure experiments conducted from 10–20 kbar and 900–1100 °C, both combined in a forward modelling approach. Initially, P–T pseudosections for natural rock compositions with increasing MgO contents were calculated in the system NCFMASHTO (Na2O–CaO–FeO–MgO–Al2O3–SiO2–H2O–TiO2) to ascertain the metamorphic products from rocks with increasing MgO contents from a MORB up to a komatiite. A small number of previous experiments on komatiites showed the development of pyroxenite instead of eclogite and garnet-amphibolite during metamorphism and established that melts of these pyroxenites are of basaltic composition, thus again building oceanic crust instead of continental crust.rnThe P–T pseudosections calculated represent a continuous development of their metamorphic products from amphibolites and eclogites towards pyroxenites. On the basis of these calculations and the changes within the range of compositions, three picritic Models of Archean Oceanic Crust (MAOC) were established with different MgO contents (11, 13 and 15 wt%) ranging between basalt and komatiite. The thermodynamic modelling for MAOC 11, 13 and 15 at supersolidus conditions is imprecise since no appropriate melt model for metabasic rocks is currently available and the melt model for metapelitic rocks resulted in unsatisfactory calculations. The partially molten region is therfore covered by high-pressure experiments. The results of the experiments show a transition from predominantly tonalitic melts in MAOC 11 to basaltic melts in MAOC 15 and a solidus moving towards higher temperatures with increasing magnesium in the bulk composition. Tonalitic melts were generated in MAOC 11 and 13 at pressures up to 12.5 kbar in the presence of garnet, clinopyroxene, plagioclase plus/minus quartz (plus/minus orthopyroxene in the presence of quartz and at lower pressures) in the absence of amphibole but it could not be explicitly indicated whether the tonalitic melts coexisting with an eclogitic residue and rutile at 20 kbar do belong to the Archean TTG suite. Basaltic melts were generated predominantly in the presence of granulite facies residues such as amphibole plus/minus garnet, plagioclase, orthopyroxene that lack quartz in all MAOC compositions at pressures up to 15 kbar. rnThe tonalitic melts generated in MAOC 11 and 13 indicate that thicker oceanic crust with more magnesium than that of a modern basalt is also a viable source for the generation of TTG-like melts and therefore continental crust in the Archean. The experimental results are related to different geologic settings as a function of pressure. The favoured setting for the generation of early TTG-like melts at 15 kbar is the base of an oceanic crust thicker than existing today or by melting of slabs in shallow subduction zones, both without interaction of tonalic melts with the mantle. Tonalitic melts at 20 kbar may have been generated below the plagioclase stability by slab melting in deeper subduction zones that have developed with time during the progressive cooling of the Earth, but it is unlikely that those melts reached lower pressure levels without further mantle interaction.rn

Petrogenesis of rift-related tephrites, phonolites and trachytes (Central European Volcanic Province, Rhon, FRG): Constraints from Sr, Nd, Pb and O isotopes

The volcanic rocks of the Rhön area (Central European Volcanic Province, Germany) belong to a moderately alkali basaltic suite that is associated with minor tephriphonolites, phonotephrites, tephrites, phonolites and trachytes. Based on isotope sytematics (87Sr/86Sr: 0.7033–0.7042; 143Nd/144Nd: 0.51279–0.51287; 206Pb/204Pb: 19.1–19.5), the inferred parental magmas formed by variable degrees of partial melting of a common asthenospheric mantle source (EAR: European Asthenospheric Reservoir of Cebriá and Wilson, 1995). Tephrites, tephriphonolites, phonotephrites, phonolites and trachytes show depletions and enrichments in some trace elements (Sr, Ba, Nb, Zr, Y) indicating that they were generated by broadly similar differentiation processes that were dominated by fractionation of olivine, clinopyroxene, amphibole, apatite and titaniferous magnetite ± plagioclase ± alkalifeldspar. The fractionated samples seem to have evolved by two distinct processes. One is characterized by pure fractional crystallization indicated by increasing Nb (and other incompatible trace element) concentrations at virtually constant 143Nd/144Nd ~ 0.51280 and 87Sr/86Sr ~ 0.7035. The other process involved an assimilation–fractional crystallization (AFC) process where moderate assimilation to crystallization rates produced evolved magmas characterized by higher Nb concentrations at slightly lower 143Nd/144Nd down to 0.51275. Literature data for some of the evolved rocks show more variable 87Sr/86Sr ranging from 0.7037 to 0.7089 at constant 143Nd/144Nd ~ 0.51280. These features may result from assimilation of upper crustal rocks by highly differentiated low-Sr (< 100 ppm Sr) lavas. However, based on the displacement of the differentiated rocks from this study towards lower 143Nd/144Nd ratios and modeled AFC processes in 143Nd/144Nd vs. 87Sr/86Sr and 207Pb/204Pb vs. 143Nd/144Nd space assimilation of lower crustal rocks seems more likely. The view that assimilation of lower crustal rocks played a role is confirmed by high-precision double-spike Pb isotope data that reveal higher 207Pb/204Pb ratios (15.62–15.63) in the differentiated rocks than in the primitive basanites (15.58–15.61). This is compatible with incorporation of radiogenic Pb from lower crustal xenoliths (207Pb/204Pb: 15.63–15.69) into the melt. However, 206Pb/204Pb ratios are similar for the differentiated rocks (19.13–19.35) and the primitive basanites (19.12–19.55) implying that assimilation involved an ancient crustal end member with a higher U/Pb ratio than the mantle source of the basanites. In addition, alteration-corrected δ18O values of the differentiated rocks range from c. 5 to 7‰ which is the same range as observed in the primitive alkaline rocks. This study confirms previous interpretations that highlighted the role of AFC processes in the evolution of alkaline volcanic rocks in the Rhön area of the Central European Volcanic Province.

Boron-Bearing Kornerupine from Fiskenaesset, West Greenland: A Reexamination of Specimens from the Type Locality

In 1884, Lorenzen proposed the formula MgAI2SiO6 for his new mineral kornerupine from Fiskenæsset and did not suspect it to contain boron. Lacroix and de Gramont (1919) reported boron in Fiskenæsset kornerupine, while Herd (1973) found none. New analyses (ion microprobe mass analyser and spectrophotometric) of kornerupine in three specimens from the type locality, including the specimens analysed by Lorenzen and Herd, indicate the presence of boron in all three, in amounts ranging from 0.50 to 1.44 wt.% B203, e.g. (Li0.04 Na0.01 Ca0.01) (Mg3.49 Mn0.01 Fe0.17 Ti0.01 Al5.64)Σ9.30 (Si3.67 Al1.02 B0.31)Σ5 O21 (OH0.99 F0.01) for Lorenzen's specimen. Textures and chemical compositions suggest that kornerupine crystallized in equilibrium in the following assemblages, all with anorthite (An 92-95) and phlogopite (XFe = atomic Fe/(Fe + Mg) = 0.028-0.035): (1) kornerupine (0.045)-gedrite (0.067); (2) kornerupine (0.038-0.050)-sapphirine (0.032-0.035); and (3) kornerupine (0.050)-hornblende. Fluorine contents of kornerupine range from 0.01 to 0.06%, of phlogopite, from 0.09 to 0.10%. In the first assemblage, sapphirine (0.040) and corundum are enclosed in radiating bundles of kornerupine; additionally sapphirine, corundum, and/or gedrite occur with chlorite and pinite (cordierite?) as breakdown products of kornerupine. Kornerupine may have formed by reactions such as: gedrite + sapphirine + corundum + B203 (in solution) + H20 = kornerupine + anorthite + Na-phlogopite under conditions of the granulite facies. Boron for kornerupine formation was most likely remobilized by hydrous fluids from metasedimentary rocks occurring along the upper contact of the Fiskenæsset gabbro-anorthosite complex with amphibolite.

Prismatine: Revalidation for Boron-Rich Compositions in the Kornerupine Group

Kornerupine and prismatine were introduced independently by Lorenzen in 1884 (but published in 1886 and 1893) and by Sauer in 1886, respectively. Ussing (1889) showed that the two minerals were sufficiently close crystallographically and chemically to be regarded as one species. However, recent analyses of boron using the ion microprobe and crystal structure refinement, indicate that the boron content of one tetrahedral site in kornerupine ranges from 0 to 1. Kornerupine and prismatine, from their respective type localities of Fiskenaesset, Greenland and Waldheim, Germany, are distinct minerals, members of an isomorphic series differing in boron content. For this reason, we re-introduce Sauer's name prismatine for kornerupines with B > 0.5 atoms per formula unit (p.f.u.) of 22(O,OH,F), and restrict the name kornerupine sensu stricto to kornerupines with B < 0.5 p.f.u. Kornerupine sensu lato is an appropriate group name for kornerupine of unknown boron content. Kornerupine sensu stricto and prismatine from the type localities differ also in Fe2+/Mg ratio, Si - (Mg + Fe2+ + Mn) content, Al content, F content, colour, density, cell parameters, and paragenesis. Both minerals formed under granulite-facies conditions with sapphirine and phlogopite, but kornerupine sensu stricto is associated with anorthite and homblende or gedrite, whereas prismatine is found with oligoclase (An9-13), sillimanite, garnet, and/or tourmaline. Occurrences at other localities suggest that increasing boron content extends the stability range of prismatine relative to that of kornerupine sensu stricto.

XMapTools: a MATLAB©-based program for electron microprobe X-ray image processing and geothermobarometry

XMapTools is a MATLAB©-based graphical user interface program for electron microprobe X-ray image processing, which can be used to estimate the pressure–temperature conditions of crystallization of minerals in metamorphic rocks. This program (available online at http://www.xmaptools.com) provides a method to standardize raw electron microprobe data and includes functions to calculate the oxide weight percent compositions for various minerals. A set of external functions is provided to calculate structural formulae from the standardized analyses as well as to estimate pressure–temperature conditions of crystallization, using empirical and semi-empirical thermobarometers from the literature. Two graphical user interface modules, Chem2D and Triplot3D, are used to plot mineral compositions into binary and ternary diagrams. As an example, the software is used to study a high-pressure Himalayan eclogite sample from the Stak massif in Pakistan. The high-pressure paragenesis consisting of omphacite and garnet has been retrogressed to a symplectitic assemblage of amphibole, plagioclase and clinopyroxene. Mineral compositions corresponding to ~165,000 analyses yield estimates for the eclogitic pressure–temperature retrograde path from 25 kbar to 9 kbar. Corresponding pressure–temperature maps were plotted and used to interpret the link between the equilibrium conditions of crystallization and the symplectitic microstructures. This example illustrates the usefulness of XMapTools for studying variations of the chemical composition of minerals and for retrieving information on metamorphic conditions on a microscale, towards computation of continuous pressure–temperature-and relative time path in zoned metamorphic minerals not affected by post-crystallization diffusion.

Valle d’Aosta section of the Sesia Zone: multi-stage HP metamorphism and assembly of a rifted continental margin

The spectrum characteristic of the EMC ranges from eclogites (containing omphacite and/or jadeite, garnet, phengite, glaucophane, zoisite, chloritoid, rutile) to phengite schists, calcschists, and marbles, as well as a variety of orthogneisses. Despite the intense polyphase deformation and HP-metamorphic recrystallization, it is possible in some locations to recognize pre-Alpine characteristics in some of the protoliths. For instance, two types of felsic orthogneiss can be distinguished in the Aosta Valley, one derived from Permian granitoids (with local preservation of intrusive contacts, magmatic inclusions, leucocratic veins and other magmatic structures; Stop 3), the other derived from pre-Variscan leuco-monzogranite, such as the building stone mined at the “Argentera” quarry near Settimo Vittone / Montestrutto (Stop 2; so-called “Verde Argento” contains jadeite, phengite, K-feldspar, quartz). Polycyclic and more rarely monocyclic metasediments contain evidence of a complex Alpine PTDt-evolution, locally including relics of their prograde history from blueschist, one or more stages at eclogite facies. Recent petrochronological studies have dated this HP-evolution of the Sesia Zone in some detail. In the area visited, clear evidence of HP-cycling has been identified in one km-size tectonic slice (Stop 1), but not in adjacent parts of the EMC, indicating “yo-yo tectonics”. Partial retrogression and attendant ductile to brittle deformation of the HP-rocks is evident in one of the outcrops (Stop 4). Apart from the four localities in the Sesia Zone, a final outcrop introduces HP-rocks of the adjacent Piemonte oceanic unit, specifically calc-schists and ophiolite members of the “Zermatt-Saas” zone. The hilltop outcrop (Stop 5) displays foliated antigorite schist with peridotite relics (clinopyroxene, spinel) containing lenses derived from doleritic dykes. These fine-grained metarodingites and the folded veins containing Mg-chlorite and titanoclinohumite within serpentinite once again indicate equilibration under low-temperature eclogite facies conditions. However, these units reached that HP stage more than 20 Ma after the youngest eclogite facies imprint recognized in the Sesia Zone. Despite nearly half a century of intense study in the Sesia Zone, the complex assembly of its HP-terranes and their relation to more external parts of the Western Alps remains incompletely understood. This field guide merely introduces a few of the classic outcrops and discusses some of the critical evidence they contain, but it could not incorporate details on each stage of the evolution recognized so far.

The behaviour of incompatible elements during hydrous melting of metasomatized peridotite at 4–6 GPa and 1000 °C–1200 °C

Trace element behavior during hydrous melting of a metasomatized garnet–peridotite was examined at pressures of 4–6 GPa and temperatures of 1000 °C–1200 °C, conditions appropriate for fluid penetrating the mantle wedge atop the subducting slab. Experiments were performed in a rocking multi-anvil apparatus using a diamond-trap setup. The compositions of the fluid and melt phases were measured using the cryogenic LA-ICP-MS technique. The water-saturated solidus of the K-lherzolite composition is located between 900 °C and 1000 °C at 4 GPa and between 1000 °C and 1100 °C at 5 and 6 GPa. The partition coefficients between fluid or melt and clinopyroxene reveal an asymmetric MREE trough with a minimum at Dy. The clinopyroxene in equilibrium with aqueous fluids is characterized by DUfluid–cpx > DThfluid–cpx while DUmelt–cpx tends to be similar to DThmelt–cpx. The partition coefficients between fluid or melt and garnet reveal very strong light to heavy REE fractionation, DLa/DLu from 95 (hydrous melt) to 1600 (aqueous fluid). The LILE are highly incompatible with partition coefficients > 50. The behavior of HFSE are decoupled, with DZr,Hf close to 1 while DNb,Ta > 10. Garnet is characterized by DUmelt/fluid–garnet < DThmelt/fluid–garnet. A comparison of our experimental partitioning results for trivalent cations as well as the results from the literature and the calculations carried out using the lattice strain model adapted to the presence of water in the bulk system indicates that H2O in the fluid or melt phase has a prominent effect on trace element partitioning. Garnet in mantle rocks in equilibrium with an aqueous fluid is characterized by significantly higher Do(3 +) for REE in the X site of the garnet compared with the partitioning values of the optimal cation in garnet in equilibrium with hydrous melts. Our data show for the first time that the change in the nature of the mobile phase (fluid vs. melt) does affect the affinities of trace elements into the garnet crystal at conditions below the second critical endpoint of the system. The same also applies for clinopyroxene, although this is less clear. Consequently, our new data allow for refinements in predictive modeling of element transfer from the slab to the mantle wedge and of possible compositions of metasomatized mantle that sources OIB magmatism.

Dating prograde fluid pulses during subduction by in situ U–Pb and oxygen isotope analysis

Keywords High-pressure fluids · Whiteschists · U–Pb dating · Oxygen isotopes · Ion microprobe · Metasomatism Introduction The subduction of crustal material to mantle depths and its chemical modification during burial and exhumation contribute to element recycling in the mantle and the formation of new crust through arc magmatism. Crustal rocks that Abstract The Dora-Maira whiteschists derive from metasomatically altered granites that experienced ultrahighpressure metamorphism at ~750 °C and 40 kbar during the Alpine orogeny. In order to investigate the P–T–time– fluid evolution of the whiteschists, we obtained U–Pb ages from zircon and monazite and combined those with trace element composition and oxygen isotopes of the accessory minerals and coexisting garnet. Zircon cores are the only remnants of the granitic protolith and still preserve a Permian age, magmatic trace element compositions and δ18O of ~10 ‰. Thermodynamic modelling of Si-rich and Si-poor whiteschist compositions shows that there are two main fluid pulses during prograde subduction between 20 and 40 kbar. In Si-poor samples, the breakdown of chlorite to garnet + fluid occurs at ~22 kbar. A first zircon rim directly overgrowing the cores has inclusions of prograde phlogopite and HREE-enriched patterns indicating zircon growth at the onset of garnet formation. A second main fluid pulse is documented close to peak metamorphic conditions in both Si-rich and Si-poor whiteschist when talc + kyanite react to garnet + coesite + fluid. A second metamorphic overgrowth on zircon with HREE depletion was observed in the Si-poor whiteschists, whereas a single metamorphic overgrowth capturing phengite and talc inclusions was observed in the Si-rich whiteschists. Garnet rims, zircon rims and monazite are in chemical and isotopic equilibrium for oxygen, demonstrating that they all formed at peak metamorphism at 35 Ma as constrained by the age of monazite (34.7 ± 0.4 Ma) and zircon rims (35.1 ± 0.8 Ma). The prograde zircon rim in Si-poor whiteschists has an age that is within error indistinguishable from the age of peak metamorphic conditions, consistent with a minimum rate of subduction of 2 cm/year for the Dora-Maira unit. Oxygen isotope values for zircon rims, monazite and garnet are equal within error at 6.4 ± 0.4 ‰, which is in line with closed-system equilibrium fractionation during prograde to peak temperatures. The resulting equilibrium Δ18Ozircon-monazite at 700 ± 20 °C is 0.1 ± 0.7 ‰. The in situ oxygen isotope data argue against an externally derived input of fluids into the whiteschists. Instead, fluidassisted zircon and monazite recrystallisation can be linked to internal dehydration reactions during prograde subduction. We propose that the major metasomatic event affecting the granite protolith was related to hydrothermal seafloor alteration post-dating Jurassic rifting, well before the onset of Alpine subduction.

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.

Noble metal abundances in ODP Leg 115 basalts (Table 1)

A comparison of 50 basalts recovered at Sites 706, 707, 713, and 715 along the Reunion hotspot trace during Ocean Drilling Program Leg 115 in the Indian Ocean shows that seafloor alteration had little effect on noble metal concentrations (Au, Pd, Pt, Rh, Ru, and Ir), determined by inductively coupled plasma-mass spectrometry (ICP-MS), which generally tend to decrease with magma evolution. Their compatible-element behavior may be related to the precipitation of Ir-Os-based alloys, chromite, sulfides, and/or olivine and clinopyroxene in some combination. The simplest explanation indicates silicate control of concentrations during differentiation. Basalts from the different sites show varying degrees of alkalinity. Noble metal abundances tend to increase with decreasing basalt alkalinity (i.e., with increasing percentages of mantle melting), indicating that the metals behave as compatible elements during mantle melting. The retention of low-melting-point Au, Pd, and Rh in mantle sulfides, which mostly dissolve before significant proportions of Ir-Os-based alloys melt, explains increasing Pd/Ir ratios with decreasing alkalinity (increasing melting percentages) in oceanic basalts. High noble metal concentrations in Indian Ocean basalts (weighted averages of Au, Pd, Rh, Pt, Ru, and Ir in Leg 115 basalts are 3.2, 8.1, 0.31, 7.3, 0.22, and 0.11 ppb, respectively), compared with basalts from some other ocean basins, may reflect fundamental primary variations in upper- mantle noble metal abundances

Petrology and geochemistry at DSDP Site 89-462

The 16 samples of Deep Sea Drilling Project (DSDP) Leg 89 basalts that we analyzed for whole rock major and trace elements and for mineralogic compositions are identical to some of the basalts recovered during Leg 61. Leg 89 samples are mostly olivine-plagioclase-clinopyroxene sparsely phyric basalts and exhibit a wide variety of textures. These basalts have lower TiO2 at a given Mg/(Mg+Fe2+)*100 than MORB (midocean ridge basalt). We recognize three major chemical types of basalts in the Nauru Basin. We believe that different degrees of partial melting, modified by fractional crystallization and possibly by magma mixing at shallow depths, can explain the chemical differences among the three groups. This petrogenetic model is consistent with the observed downhole chemical-chronostratigraphic relations of the samples. New 87Sr/86Sr and U3Nd/144Nd analyses of basalt samples from DSDP Site 462 indicate that the Nauru Basin igneous complex is within the Sr-Nd isotopic range of ocean island basalt. Thus the Nauru Basin igneous complex resembles MORB in many aspects of its chemistry, morphology, and secondary alteration patterns (Larson, Schlanger, et al., 1981), but not in its isotopic characteristics. If it were not for the unambiguous evidence that the Nauru Basin complex was erupted off-ridge, the complex could easily be interpreted as normal oceanic layer 2. For this reason, we speculate that the Nauru Basin igneous complex was produced in an oceanic riftlike environment when multiple, fast-propagating rifts were formed during the fast seafloor spreading episode in the Cretaceous.

Clay mineral and heavy metal composition of sea-bed surface sediments and pre-Holocene sediment samples taken during POLARSTERN cruise ANT-XXIII/9

Surface mineralogical compositions and their association to modern processes are well known from the east Atlantic and south-west Indian sectors of the Southern Ocean, but data from the interface of these areas - the Prydz Bay-Kerguelen region - is still missing. The objective of our study was to provide mineralogical data of reference samples from this region and to relate these mineralogical assemblages to hinterland geology, weathering, transport and depositional processes. Clay mineral assemblages were analysed by means of X-ray diffraction technique. Heavy mineral assemblages were determined by counting of gravity-separated grains under a polarizing microscope. Results show that by use of clay mineral assemblages four mineralogical provinces can be subdivided: i) continental shelf, ii) continental slope, iii) deep sea, iv) Kerguelen Plateau. Heavy mineral assemblages in the fine sand fraction are relatively uniform except for samples taken from the East Antarctic shelf. Our findings show that mineralogical studies on sediment cores from the study area have the potential to provide insights into past shifts in ice-supported transport and activity and provenance of different water masses (e.g. Antarctic slope current and deep western boundary current) in the Prydz Bay-Kerguelen region.