Meteoritic material at five large impact craters

Sixteen crater samples were analyzed by radiochemical neutron activation analysis for Ge, Ir, Ni, Os, Pd and Re. Two impact melt rock samples from Clearwater East (22 km) showed strong, uniform enrichments in all elements except Ge, corresponding to 7.4% C1 chondrite material. Interelement ratios suggest that the meteorite was a C1 (or C2) chondrite, not an iron, stony iron, or chondrite of another type. An Ivory Coast tektite (related to the 10 km Bosumtwi crater) was enriched in Ir + Os and Ni to about 0.04 and 1.6% of C1 chondrite levels, but in the absence of data on country rocks, the meteorite cannot yet be characterized.Impact melt rock samples from Clearwater West (32km), Manicouagan (70km), and Mistastin (28 km) showed no detectable meteoritic component. Upper limits, as Cl chondrite equivalent, were Os ≤ 2 × 10^?3% (~0.01 ppb), Ni ≤ 2 × 10^?1% (~20ppm). Possible causes are high impact velocity and/or a chemically inconspicuous meteorite (achondrite, Ir,Os-poor iron or stony iron). However, a more likely reason is that some fraction of the impact melt remains meteorite-free, especially at craters with central peaks.Clearwater East is the first terrestrial impact crater found to be associated with a stony meteorite. Apparently the consistent absence of stony projectiles at small craters (< 1 km diameter) reflects their destruction in the atmosphere, as proposed by Öpik.     

Experimental determination of Ni diffusion coefficients in olivine and their dependence on temperature, composition, oxygen fugacity, and crystallographic orientation

Diffusion couple experiments were carried out with San Carlos olivine (Fo₉₀) and NiFe alloys (Ni₁₀₀, Ni₉₇Fe₃, Ni₉₀Fe₁₀) or other olivine compositions (Fo₁₀₀, Fo₂₅) in order to determine the dependence on temperature, oxygen fugacity, composition and crystallographic orientation of Ni diffusion coefficient (D_Ni) in olivine. Experiments at 1 atmosphere total pressure cover a temperature range of 900-1445°C with run durations from 48 to 2155 h at different oxygen fugacities. In an Arrhenius plot the best fit for all data for Fo₉₀ yields an activation energy (E_D) of 220 ± 14 kJ/mol and an fO₂ dependence of (1/4.25)·Δ log fO₂ = Δ log D_Ni. The relationship between diffusion coefficients along different crystallographic axes at 1200°C is given by D_[001] ≈ 6·D_[100] ≈ 6·D_[010]. D_Ni depends strongly on the major element (i.e. Fe/Mg) composition of olivine and decreases by about 1 order of magnitude as the olivine composition changes from Fo₃₅ to Fo₉₀. Thus, experimental investigations in Fe-free systems cannot be applied to natural samples. For calculation of residence times or cooling rates the present Ni data yield shorter timescales compared to those obtained using diffusion data published until now.In addition to Ni diffusion coefficients, Fe-Mg, Mn and Ca diffusion data were obtained from some of the same diffusion couples (Fo₉₀-Fo₁₀₀). It is found that the activation energies, E_D[Ni] ≅ E_D[Fe-Mg] ≅ E_D[Mn] ≤ E_D[Ca]. All diffusion coefficients are strongly dependent on the major element composition of olivine.     

Soil formation and weathering in a permafrost environment of the Swiss Alps: a multi‐parameter and non‐steady‐state approach

Spatially discontinuous permafrost conditions frequently occur in the European Alps. How soils under such conditions have evolved and how they may react to climate warming is largely unknown. This study focuses on the comparison of nearby soils that are characterised by the presence or absence of permafrost (active‐layer thickness: 2–3 m) in the alpine (tundra) and subalpine (forest) range of the Eastern Swiss Alps using a multi‐method (geochemical and mineralogical) approach. Moreover, a new non‐steady‐state concept was applied to determine rates of chemical weathering, soil erosion, soil formation, soil denudation, and soil production. Long‐term chemical weathering rates, soil formation and erosion rates were assessed by using immobile elements, fine‐earth stocks and meteoric ¹⁰Be. In addition, the weathering index (K + Ca)/Ti, the amount of Fe‐ and Al‐oxyhydroxides and clay minerals characteristics were considered. All methods indicated that the differences between permafrost‐affected and non‐permafrost‐affected soils were small. Furthermore, the soils did not uniformly differ in their weathering behaviour. A tendency towards less intense weathering in soils that were affected by permafrost was noted: at most sites, weathering rates, the proportion of oxyhydroxides and the weathering stage of clay minerals were lower in permafrost soils. In part, erosion rates were higher at the permafrost sites and accounted for 79–97% of the denudation rates. In general, soil formation rates (8.8–86.7 t/km²/yr) were in the expected range for Alpine soils. Independent of permafrost conditions, it seems that the local microenvironment (particularly vegetation and subsequently soil organic matter) has strongly influenced denudation rates. As the climate has varied since the beginning of soil evolution, the conditions for soil formation and weathering were not stable over time. Soil evolution in high Alpine settings is complex owing to, among others, spatio‐temporal variations of permafrost conditions and thus climate. This makes predictions of future behaviour very difficult. Copyright © 2016 John Wiley & Sons, Ltd.     

Constant denudation rates in a high alpine catchment for the last 6 kyrs

Terrestrial cosmogenic nuclides (TCN) have widely been used as proxies in determining denudation rates in catchments. Most studies were limited to samples from modern active streams, thus little is known about the magnitude and causes of TCN variability on millennial time scales. In this work we present a 6 kyrs long, high resolution record of ¹⁰Be concentrations (n = 18), which were measured in sediment cores from an alluvial fan delta at the outlet of the Fedoz Valley in the Swiss Alps. This record is paired with a 3‐year time series (n = 4) of ¹⁰Be measured in sediment from the active stream currently feeding this fan delta. The temporal trend in the ¹⁰Be concentrations after correction for postdepositional production of ¹⁰Be was found to be overall constant and in good agreement with the modern river ¹⁰Be concentration. The calculated mean catchment‐wide denudation rate amounts to 0.73 ± 0.18 mm yr^?1. This fairly constant level of ¹⁰Be concentrations can be caused by a constant denudation rate over time within the catchment or alternatively by a buffered signal. In this contribution we suggest that the large alluvial floodplain in the Fedoz Valley may act as an efficient buffer on Holocene time scales in which sediments with different ¹⁰Be signatures are mixed. Therefore, presumable variations in the ¹⁰Be signals derived from changes in denudation under a fluctuating Holocene climate are only poorly transferred to the catchment outlet and not recorded in the ¹⁰Be record. However, despite the absence of high frequency signals, we propose that the buffered and averaged ¹⁰Be signal could be meaningfully and faithfully interpreted in terms of long‐term catchment‐averaged denudation rate. Our study suggests that alluvial buffers play an important role in regulating the ¹⁰Be signal exported by some alpine settings that needs to be taken into account and further investigated. Copyright © 2016 John Wiley & Sons, Ltd.     

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.     

Isolation and purification of Cu-free methanobactin from Methylosinus trichosporium OB3b

Background  

The isolation of highly pure copper-free methanobactin is a prerequisite for the investigation of the biogeochemical functions of this chalkophore molecule produced by methane oxidizing bacteria. Here, we report a purification method for methanobactin from Methylosinus trichosporium OB3b cultures based on reversed-phase HPLC fractionation used in combination with a previously reported resin extraction. HPLC eluent fractions of the resin extracted product were collected and characterized with UV-vis, FT-IR, and C-1s NEXAFS spectroscopy, as well as with elemental analysis and ESI-MS.     

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.     

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.