The geochemistry of the volatile trace elements As, Cd, Ga, In and Sn in the Earth’s mantle: New evidence from in situ analyses of mantle xenoliths

The abundances of 30 trace elements, including the volatile chalcophile/siderophile elements As, Cd, Ga, In and Sn were determined by laser ablation ICP-MS in minerals of 19 anhydrous and 5 hydrous spinel peridotite xenoliths from three continents. The majority of samples were fertile lherzolites with more than 5% clinopyroxene; several samples have major element compositions close to estimates of the primitive mantle. All samples have been previously analysed for bulk-rock major, minor and lithophile trace elements. They cover a wide range of equilibration temperatures from about 850 to 1250 °C and a pressure range from 0.8 to 3.0 GPa. A comparison of results from bulk-rock analyses with concentrations obtained from combining silicate and oxide mineral data with modal mineralogy, gave excellent agreement, with the exception of As. Arsenic is the only element analysed that has high concentrations in sulphides. For all other elements sulphides can be neglected as host phases in these mantle rocks. The major host phase for Cd, In and Sn is clinopyroxene and if present, amphibole. Cadmium and In appear to behave moderately incompatibly during mantle melting similar to Yb.The data yield new and more reliable mantle abundances for Cd (35 ± 7 ppb), In (18 ± 3 ppb) and Sn (91 ± 28 ppb). The In value is similar to the Mg and CI-normalized Zn abundance of the mantle, although In is cosmochemically more volatile than Zn. The high In content suggests a high content of volatile elements in general in proto-Earth material. The lower relative abundances of volatile chalcophile elements such as Cd, S, Se and Te might be explained by sulphide segregation during core formation. The very low relative abundances of volatile and highly incompatible lithophile elements such as Br, Cl and I, and also C, N and rare gases, imply loss during Earth accretion, arguably by collisional erosion from differentiated planetesimals and protoplanets.     

Petrology and geochemistry of peridotites and associated vein rocks of Zabargad Island,Red Sea,Egypt

Summary Zabargad (St. John's) Island in the Red Sea contains three ultramafic bodies, one of which bas produced the famous gem olivine (peridot). The ultramafic rock types consist of two major groups—the peridotites and the vein rocks within them. The peridotites are divided into three groups: primitive, depleted and metasomatized. The primitive peridotites are the most abundant and are represented by mainly pristine spinellherzolites which have chemical compositions representative of the subcontinental upper mantle. The depleted peridotites are mainly harzburgites and nome dunites and both are similar to worldwide occurrences. The most depleted peridotites also appear to have the greatest metasomatic additions of incompatible elements, as has been noted at other localities. Metasomatic additions were clearly accompanied by tectonic shearing. Metasomatism included infiltration of incompatible elements and the formation of porphyroblasts of clinopyroxene, amphibole, Al-spinel and plagioclase; il took place under a variety of p-T conditions and with fluids of differing compositions.The vein rocks are mainly monomineralic and comprise olivinites, orthopyroxenites, clinopyroxenites, websterites, hornblendites and plagioclasites. These rocks are believed to have formed from fluids similar to that which metasomatized the host rock, rather than by some kind of igneous process. The fluids were derived from peridotite reservoirs (fertile and depleted) and apparently were in equilibrium with these reservoirs. Highly abundant fluid inclusions document the hypersaline and CO₂-dominated character of these fluids. Monomineralic vein rocks are closely associated with metasomatic and tectonic processes, and there is a complete transition between metasomatic impregnation and formation of vein rocks. These processes may have also been active in other peridotite bodies of the world, as was earlier recognized and documented in the Seiad Ultramafic Complex, California. Metasomatism is evident along clinopyroxenite and hornblendite veins, whereas orthopyroxenites, olivinites and plagioclasites do not show any interaction with the wall rocks. Olivinites are probably the latest (lowest p-T) vein rock type, and the latest olivine which formed within their open cavities became the gem peridot.Zabargad ultramafic rocks preserve relic phases indicating an initial depth of origin greater than 85 km. Clinopyroxenites preserve the memories of the highest p-T conditions and they may be the first vein rock type formed in the peridotites. The p-T path of uplift coincides with the oceanic geotherm at great depth but deviates systematically from it with falling pressure in a series of tectonic stages accompanied by metasomatism and recrystallization. The p-T and petrologic history indicates rapid uplift, a feature which is supported by extensive contact metamorphism of the associated metasediments.

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Petrologie und Geochemie der Peridotite und der mit diesen vergesellschafteten Ganggesteine der Insel Zabargad, Rotes Meer, Ägypten

Zusammenfassung Auf der Insel Zabargad (St.John's Island) im Roten Meer befinden sich drei Peridotit-Körper von denen einer seit Jahrtausenden den berühmten Peridot (Edelolivin) geliefert hat. Die ultramafischen Gesteine von Zabargad gliedern sich in zwei Hauptgruppen: die Peridotite und die mit diesen vergesellschafteten Ganggesteine. Die Peridotite können in drei Gruppen gegliedert werden: die primitiven, die verarmten und die metasomatisch veränderten Peridotite. Am meisten verbreitet auf Zabargad sind die primitiven Peridotite. Diese sind meist Spinell-Lherzolithe mit einer chemischen Zusammensetzung, welche dem subkontinentalen Oberen Erdmantel entspricht. Die verarmten Peridotite werden hauptsächlich von Harzburgiten und einigen wenigen Duniten repräsentiert. Beide sind jenen aus anderen Vorkommen der Welt sehr ähnlich. Die am stärksten verarmten Peridotite scheinen auch die stärksten metasomatischen Veränderungen erfahren zu haben—ein Trend, der auch schon an anderen ultramafischen Komplexen erkannt wurde. Metasomatische Anreicherungen inkompatibler Spurenelemente sind häufig direkt mit tektonischer Verformung und Kataklase gekoppelt. Die Metasomatose ist als Infiltration inkompatibler Elemente erkennbar und führte auch zur Bildung von Porphyroblasten von Klinopyroxen, Amphibol, Al-Spinell und Plagioklas. Diese Bildungen fanden unter verschiedenen p-T-Bedingungen statt und erfolgten durch Fluide mit unterschiedlichen Zusammensetzungen.Die (meist ultramafischen) Ganggesteine sind häufig monomineralisch und umfassen Olivinite, Orthopyroxenite, Klinopyroxenite, Websterite, Hornblendite und Plagioklasite. Wir glauben, daß diese Gesteine von Fluiden gebildet wurden, welche ähnlich jenen waren, die die Metasomatosen der Peridotite verursachten. Diese Genese wird von uns der magmatischen vorgezogen. Die Fluide stammten aus peridotitischen Reservoiren (fertilen und verarmten) und waren mit diesen offenbar im Gleichgewicht. Die Ganggesteine sind sehr reich an fluid inclusions, welche allerdings keine Flüssigkeit enthalten, sondern nur Festkörper (Salze) und CO₂ (± N₂), also einen trockenen, hypersalinen Charakter haben. Auch die monomineralischen Ganggesteine sind eng mit tektonischen Prozessen verknüpft und somit auch mit metasomatischen Prozessen. Es existieren vollkommene Übergänge von metasomatischen Imprägnationen bis zu echten Ganggesteinen. Solche Prozesse waren offensichtlich auch weltweit in anderen ultramafschen Komplexen aktiv und wurden schon im Seiad Ultramafc Complex in Kalifornien erkannt und beschrieben. Metasomatismus begleitet überlicherweise die Klinopyroxenit- und Hornblendit-Gänge. Orthopyroxenite, Olivinite und auch Plagioklasite zeigen jedoch keine Wechselwirkung mit den Wirtgesteinen. Olivinite sind wahrscheinlich die zuletzt gebildeten Ganggesteine. Der zuletzt sich bildende Olivin wurde der schönste und zum gesuchten Peridot.Alle ultramafschen Gesteine von Zabargad enthalten Minerale aus verschiedenen Bildungsepochen. Einige Relikte erinnern an eine Herkunft aus einer Tiefe von mehr als 85 km. Klinopyroxenite konservierten die höchsten p-T-Bedingungen. Sie waren daher wahrscheinlich die ersten (noch erhaltenen) Ganggesteine, welche sich im peridotitischen Erdmantel unterhalb des heutigen Roten Meeres bildeten. Der p-T-Pfad der Zabargad Ultramafitite deckt sich in großer Tiefe mit der ozeanischen Geotherme. Mit abnehmender Tiefe entfernt sich dieser Pfad allerdings zunehmend von der Geotherme und läßt eine Reihe von tektonischen Aktivitäten verbunden mit Metasomatose und Rekristallisation erkennen. Die p-T-Geschichte der Zabargad Ultramaftite deuten auf einen raschen Aufstieg aus dem Erdmantel hin. Diese Daten werden durch die weitverbreitete und intensive Kontaktmetamorphose der mit den Peridotiten assoziierten Metasedimenten unterstützt.

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Dedicated to Prof. Josef Zemann on the occasion of his 70th birthday

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With 12 Figures     

Model parameter optimization for site-dependent simulation of ground motion by simulated annealing: Re-evaluation of the Ashigara Valley prediction experiment

More than 40 groups from 10 different countries participated in a weak- and strong-motion prediction experiment at Ashigara Valley which required the blind prediction of time series, spectra and spectral ratios for selected and instrumented sedimentary sites with well-known geotechnical properties. The wide scatter of the results of this experiment have raised a number of questions as to how to model high-frequency ground motion in the presence of available geotechnical and geophysical data. Using a simulated annealing waveform inversion method, we have tried to optimize and automate the model construction for ID site-dependent ground-motion simulation. We found a whole set of successfull models which provide good waveform fit (r > 0.8) for the observed displacement records at site KS2 but also yield sufficiently accurate response spectra and peak value predictions for both surface and downhole site. This shows that ID models are fully adequate to model the site conditions at least for the weak motion data. The resulting successful layer models consistently show a slower, less dense, and slightly thicker low velocity coverage with stronger damping than the official geotechnical model. Furthermore, their statistical properties directly measure the sensitivity of the individual parameters for the simulations. The critical re-evaluation of our own prediction which was based on stochastic simulation shows that although this approach has its greatest merits in situations where little information is available, it can also be successfully applied to model individual records if sufficient care is taken to determine the source parameters. Simulated annealing waveform inversion has shown to be a powerful tool to optimize that process.     

Characterization of dissolved organic matter in anoxic rock extracts and in situ pore water of the Opalinus Clay

Dissolved organic matter (DOM) from the Opalinus Clay, a potential host rock for the disposal of radioactive waste, was isolated under strictly anoxic conditions from ground rock material and compared with DOM of in situ pore water samples. For the extractions, deionized water, synthetic pore water (SPW, water containing all major ions at pore water concentrations but no organic matter) and 0.1 M NaOH were used. The influence of the solid-to-liquid ratio, extraction time, acid-pretreatment and O₂ exposure of the rock material on the isolated DOM were investigated. Liquid chromatography coupled with a total organic C detector (LC-OCD) and reverse-phase ion chromatography were used to characterize the DOM size distributions and to determine the low molecular weight organic acid (LMWOA) contents in the pore water samples and the rock extracts.The results revealed that only a small portion of the total organic C of the rock material (<0.38%) was extractable, even after removal of carbonates by acid-pretreatment. The concentrations of dissolved organic C (DOC) were found to range from 3.9 ± 0.4 to 8.0 ± 0.8 mg/L in the anoxic extracts. The pore waters exhibited similar DOC concentrations ranging from 1.2 to 15.8 ± 0.5 mg/L. The analysis by LC-OCD showed that the DOM extracted under anoxic conditions and the pore water DOM mainly consisted of hydrophilic compounds of less than 500 Da. The DOM extracted with SPW was most similar in size to the pore water DOM. Grinding the rock under oxic conditions increased the DOC yields and shifted the size distribution toward higher molecular weight compounds compared to the strictly anoxic treatment. Acetate, lactate and formate were identified in all extracts and in the pore water. In total, LMWOA accounted for 36% of the total DOC in both pore water and SPW extracts. The results imply that controlled anoxic conditions and the use of SPW as an extractant are required to isolate DOM from Opalinus Clay rocks which most resembles the in situ pore water DOM with respect to its size distribution and the LMWOA contents.     

Hf-W isotope systematics of chondrites, eucrites, and martian meteorites: Chronology of core formation and early mantle differentiation in Vesta and Mars

The timescale of accretion and differentiation of asteroids and the terrestrial planets can be constrained using the extinct ¹⁸²Hf-¹⁸²W isotope system. We present new Hf-W data for seven carbonaceous chondrites, five eucrites, and three shergottites. The W isotope data for the carbonaceous chondrites agree with the previously revised ¹⁸²W/¹⁸⁴W of chondrites, and the combined chondrite data yield an improved ?_W value for chondrites of −1.9 ± 0.1 relative to the terrestrial standard. New Hf-W data for the eucrites, in combination with published results, indicate that mantle differentiation in the eucrite parent body (Vesta) occurred at 4563.2 ± 1.4 Ma and suggest that core formation took place 0.9 ± 0.3 Myr before mantle differentiation. Core formation in asteroids within the first ∼5 Myr of the solar system is consistent with the timescales deduced from W isotope data of iron meteorites. New W isotope data for the three basaltic shergottites EETA 79001, DaG 476, and SAU 051, in combination with published ¹⁸²W and ¹⁴²Nd data for Martian meteorites reveal the preservation of three early formed mantle reservoirs in Mars. One reservoir (Shergottite group), represented by Zagami, ALH77005, Shergotty, EETA 79001, and possibly SAU 051, is characterized by chondritic ¹⁴²Nd abundances and elevated ?_W values of ∼0.4. The ¹⁸²W excess of this mantle reservoir results from core formation. Another mantle reservoir (NC group) is sampled by Nakhla, Lafayette, and Chassigny and shows coupled ¹⁴²Nd-¹⁸²W excesses of 0.5-1 and 2-3 ? units, respectively. Formation of this mantle reservoir occurred 10-20 Myr after CAI condensation. Since the end of core formation is constrained to 7-15 Myr, a time difference between early silicate mantle differentiation and core formation is not resolvable for Mars. A third early formed mantle reservoir (DaG group) is represented by DaG 476 (and possibly SAU 051) and shows elevated ¹⁴²Nd/¹⁴⁴Nd ratios of 0.5-0.7 ? units and ?_W values that are indistinguishable from the Shergottite group. The time of separation of this third reservoir can be constrained to 50-150 Myr after the start of the solar system. Preservation of these early formed mantle reservoirs indicates limited convective mixing in the Martian mantle as early as ∼15 Myr after CAI condensation and suggests that since this time no giant impact occurred on Mars that could have led to mantle homogenization. Given that core formation in planetesimals was completed within the first ∼5 Myr of the solar system, it is most likely that Mars and Earth accreted from pre-differentiated planetesimals. The metal cores of Mars and Earth, however, cannot have formed by simply combining cores from these pre-differentiated planetesimals. The ¹⁸²W/¹⁸⁴W ratios of the Martian and terrestrial mantles require late effective removal of radiogenic ¹⁸²W, strongly suggesting the existence of magma oceans on both planets. Large impacts were probably the main heat source that generated magma oceans and led to the formation metallic cores in the terrestrial planets. In contrast, decay of short-lived ²⁶Al and ⁶⁰Fe were important heat sources for melting and core formation in asteroids.     

Experimental petrochemistry of some highly siderophile elements at high temperatures, and some implications for core formation and the mantle''s early history

The highly siderophile elements (HSE's: Ru, Rh, Pd, Re, Os, Ir, Pt and Au) and those elements with distribution coefficients between Fe-rich metal and silicate phases which exceed 10⁴. The large magnitude of these distribution coefficients makes them exceedingly difficult to measure experimentally. We describe a new experimental campaign aimed at obtaining reliable values of D_M^{mets/sil melt} for selected HSE's indirectly, by measuring the solubilities of the pure metals (or simple HSE alloys) in haplobasaltic melts as a function of oxygen fugacity.

Preliminary results for Pd, Au, Ir and Re indicate that the HSE's may dissolve in silicate melts in unusually low valence states, e.g., 2+ for Ir and 1+ for the others. These unusual valence states may be important in understanding the geochemical properties of the HSE's. Inferred values of D_M^{met/sil melt} from the solubility data at 1400°C and IW −1 are 10⁷ for Pd and Au, and 10⁹−10¹² for Ir. Metal/silicate partition coefficients are thus confirmed to be very large, and are also different for the different HSE's.

A review of the abundance of the HSE's in the Earth's upper mantle shows that they are all present at 0.8% of chondritic, i.e. they have the same relative abundance, and the ratios of their concentrations are chondritic (e.g., Re/Os). Both the low degree of depletion (compared to the high values of D_M^{met/sil melt}) and the chondritic relative abundances support the idea that the mantle's HSE's were added in a “late veneer” after the cessation of core formation. Sulfur is even more depleted in the mantle relative to CI chondrites than the HSE's: this implies a late veneer which was depleted in volatile elements, and which was added to a mantle stripped of S. Since considerable S dissolves in silicate melt, this further implies that core formation in the Earth either occurred under P−T conditions below the solicate solidus, or, if the process occurred over a range of temperatures in a cooling Earth, then the process continued down to conditions below the silicate solidus.

The chondritic relative abundances of the HSE's in the upper mantle argue for a chemically unstratified primitive mantle, unless the late veneer was mixed only into the upper mantle.     

The AD 1717 rock avalanche deposits in the upper Ferret Valley (Italy): a dating approach with cosmogenic 10Be

On 12 September AD 1717, a rock volume larger than 10 million m³ collapsed onto the Triolet Glacier, mobilized a mass composed of ice and sediment and travelled more than 7 km downvalley in the upper Ferret Valley, Mont Blanc Massif (Italy). This rock avalanche destroyed two small settlements, causing seven casualties and loss of livestock. No detailed maps were made at the time. Later investigators attributed accumulations of granitic boulders and irregular ridges on the upper valley floor to either glacial deposition, or the AD 1717 rock avalanche, or a complex mixture of glacial deposition, earlier rock avalanche and AD 1717 rock avalanche origin. In this study, we present cosmogenic ¹⁰Be exposure ages from nine boulders in the extensive chaotic boulder deposit with irregular ridges, two from Holocene glacier‐free areas, and one from a Little Ice Age moraine. Exposure ages between 330 ± 23 and 483 ± 123 a from eight of nine boulders from the chaotic deposit indicate that at least seven were deposited by the AD 1717 rock avalanche. The other three boulders yielded ¹⁰Be exposure ages of 10 900 ± 400, 9700 ± 400 and 244 ± 97 a, respectively. Our results are in good agreement with the existing chronology from dendrochronology and lichenometry, and radiocarbon analysis of wood samples, but not with older ¹⁴C ages from a peat bog in the upper part of the valley. Based on the new age control, the rock avalanche deposits cover the whole bottom of the upper Ferret valley. Copyright © 2012 John Wiley & Sons, Ltd.     

Sulfur and selenium in chondritic meteorites

Abstract— We report here new analyses of S and Se in carbonaceous chondrites (2 CIs, 11 CMs, 6 CO3s, 7 CV3s, 2 C4s, 4 CRs, and 1 CH), 2 rumurutiites, ordinary chondrites (2 Hs, 2 Ls, and 1 LL), 3 anomalous chondrites, 3 acapulcoites, 3 lodranites, and in silicate inclusions of the Landes IAB iron meteorite. To avoid problems from inhomogeneous distribution of sulfides, the same samples that had been analysed for Se by INAA were analysed for S using a Leybold Heraeus Carbon and Sulfur Analyser (CSA 2002). With the measured CI contents of 5.41% S and 21.4 ppm Se a CI S/Se ratio of 2540 is obtained. A nearly identical S/Se ratio of 2560 ± 150 is found for carbonaceous chondrites (average of falls). The average ratio of all meteorite falls analysed in this study was 2500 ± 270. These data suggest that the new S content of Orgueil with 5.41% provides a reliable estimate for the average Solar System. The new solar system abundance of S of 4.62 × 10⁵ (atoms/10⁶ Si) is in good agreement with the solar photospheric abundance of 7.21 (log (a(H)) = E12) (Anders and Grevesse, 1989). Among the 50 analysed meteorites, 24 were finds from hot (Australia, Africa) and cold (Antarctica) deserts. Weathering effects in the carbonaceous chondrites and in one lodranite from the hot deserts resulted in losses of S, Se, Na and occasionally Ni. Sulfur is apparently more affected by weathering than Se. No losses were observed in ordinary chondrite finds and in meteorites collected in the Antarctica, except for the obvious loss of Na in the CM-chondrite Y 74662. The low S-content of 0.096% in Gibson, a lodranite, is probably not representative of this group of meteorites. Gibson is a find from the Australian desert and has lost S and also Se by weathering. Two other lodranites, finds from Antarctica, have about 2% S.