Sodic Pyroxene and Sodic Amphibole as Potential Reference Materials for In Situ Lithium Isotope Determinations by SIMS

Two large pegmatitic crystals of sodic pyroxene (aegirine) and sodic amphibole (arfvedsonite) from the agpaitic igneous Ilímaussaq Complex, south Greenland were found to be suitable as reference materials for in situ Li isotope determinations. Lithium concentrations determined by SIMS and micro‐drilled material analysed by MC‐ICP‐MS generally agreed within analytical uncertainty. The arfvedsonite crystal was homogeneous with [Li] = 639 ± 51 μg g^?1 (2s, n = 69, MC‐ICP‐MS and SIMS results). The aegirine crystal shows strongly developed sector zoning, which is a common feature of aegirines. Using qualitative element mapping techniques (EPMA), the homogeneous core of the crystal was easily distinguished from the outermost sectors of the crystals. The core had a mean [Li] of 47.6 ± 3.6 μg g^?1 (2s, n = 33) as determined by SIMS. The seven micro‐drilled regions measured by solution MC‐ICP‐MS returned slightly lower concentrations (41–46 μg g^?1), but still overlap with the SIMS data within uncertainty. Based on MC‐ICP‐MS and SIMS analyses, the variation in δ⁷Li was about 1‰ in each of the two crystals, which is smaller than that in widely used glass reference materials, making these two samples suitable to serve as reference materials. There was, however, a significant offset between the results of MC‐ICP‐MS and SIMS. The latter deviated from the MC‐ICP‐MS results by ?6.0 ± 1.9‰ (2s) for the amphibole and by ?3.9 ± 1.9‰ (2s) for the aegirine. This indicates the presence of a significant matrix effect in SIMS determinations of Li isotopes for amphibole and pyroxene relative to the basalt glasses used for calibration. Based on the MC‐ICP‐MS results, mean δ⁷Li values of +0.7 ± 1.2‰ (2s, n = 10) for the arfvedsonite crystal and of ?3.7 ± 1.2‰ (2s, n = 7) for the core of the aegirine crystal were calculated. Adopting these values, SIMS users can correct for the specific IMF (instrumental mass fractionation) of the ion probe used. We propose that these two crystals serve as reference materials for in situ Li isotope determinations by SIMS and pieces of these two crystals are available from the first author upon request.     

Ca-rich majorite derived from high-temperature melt and thermally stressed hornblende in shock veins of crustal rocks from the Ries impact crater (Germany)

Shock veins up to 1.1 mm thick were found within non-porous lithic clasts from suevite breccia of the Nördlinger Ries impact structure. These veins were studied by optical microscopy in transmitted and reflected light and by scanning electron microscopy. In shocked amphibolites, two types of Ca-rich majorite occur within and adjacent to the veins. The first type crystallized from shock-induced melts within the veins. Si contents of these majorites suggest dynamic pressure of ~15–17 GPa, implying minimum temperatures in the range of ~2,150–2,230°C. The second type of majorite was formed adjacent to the shock veins within pargasitic hornblende. This majorite contains significant amounts of H₂O (0.7–0.9 wt%). Based on the textural setting, the shrinkage cracks and the chemical compositions of both phases, a solid-state mechanism is deduced for the hornblende to majorite phase transition. Both genetic types of Ca-rich majorite are described for the first time from a terrestrial impact crater. Along with stishovite, majorite constitutes the second silicate mineral displaying sixfold coordination of Si at Ries. Using micro-Raman spectroscopy, jadeite + coesite and jadeite + grossular were identified within local melt glasses of alkali feldspar and plagioclase composition, respectively. Stishovite aggregates, produced by solid-state reaction, along with shock-induced high-pressure melt glasses of almandine composition were also detected in shock veins of a garnet-cordierite-sillimanite restite. The quenched, homogeneous almandine glasses point to melting temperatures of more than ~2,500°C for the veins. Our findings demonstrate that terrestrial shock veins can give valuable information on shock-induced mineral transformations and transient high pressures of host rocks during a natural impact event.     

A new U–Pb zircon age and a volcanogenic model for the early Permian Chemnitz Fossil Forest

International Journal of Earth Sciences - The Chemnitz Fossil Forest depicts one of the most completely preserved forest ecosystems in late Paleozoic Northern Hemisphere of tropical Pangaea. Fossil...     

Solar Chemical Abundances Determined with a CO5BOLD 3D Model Atmosphere

In the last decade, the photospheric solar metallicity as determined from spectroscopy experienced a remarkable downward revision. Part of this effect can be attributed to an improvement of atomic data and the inclusion of NLTE computations, but also the use of hydrodynamical model atmospheres seemed to play a role. This “decrease” with time of the metallicity of the solar photosphere increased the disagreement with the results from helioseismology. With a CO ⁵ BOLD 3D model of the solar atmosphere, the CIFIST team at the Paris Observatory re-determined the photospheric solar abundances of several elements, among them C, N, and O. The spectroscopic abundances are obtained by fitting the equivalent width and/or the profile of observed spectral lines with synthetic spectra computed from the 3D model atmosphere. We conclude that the effects of granular fluctuations depend on the characteristics of the individual lines, but are found to be relevant only in a few particular cases. 3D effects are not responsible for the systematic lowering of the solar abundances in recent years. The solar metallicity resulting from this analysis is Z=0.0153, Z/X=0.0209.     

Reconstruction of the late Quaternary paleoenvironments of the Nussloch loess paleosol sequence,Germany, using n-alkane biomarkers

This study contributes to the paleoenvironmental reconstruction of the loess–paleosol sequence of Nussloch, Germany, by using n-alkanes as plant leaf-wax-derived lipid biomarkers. We found that n-alkane patterns and concentrations in the Saalian loess and the last interglacial Eemian paleosol of Nussloch point to very strong degradation and prevailing deciduous vegetation. Degradation effects in the overlying paleosols and loess layers are less pronounced and allow for the application of an end-member mixing model to estimate vegetation changes semi-quantitatively. Our findings highlight the potential for the interpretation of degradation-corrected n-alkane ratios. n-Alkane modelling results for loess layers, paleosols and an in-filled paleochannel dated to ~ 60–32 ka suggest that up to ~ 50% of the n-alkanes were derived from deciduous trees or shrubs. This finding is in agreement with the abundant occurrence of wood fragments and indicates a highly variable and dynamic landscape dominated by tundra shrubland. On the other hand, deciduous trees or shrubs did not contribute significantly to the soil organic matter in the late Weichselian loess layers and the intercalated Gelic Gleysols (~ 32–18 ka).     

Differential UVB‐sensitivities of five New Zealand freshwater zooplankton species

Abstract

The ultraviolet (UV) sensitivity of five species of freshwater zooplankton (three Cladocera, two Copepoda) were investigated. The animals were exposed to varying levels of UV‐radiation in a sunshine‐simulator and the UV doses for 10 and 50% mortality (LD₁₀, LD₅₀) were estimated using a dose‐response model. To place these doses in context they were compared with modelled clear‐sky surface UV irradiances in New Zealand. The cladocerans Daphnia carinata and Ceriodaphnia dubia were sensitive to levels of UVB irradiance of LD₁₀ = 18–25 kJ m^?2 and LD₅₀ = 35–37 kJ m^?2. These sensitivities are consistent with published values for other cladocera. In contrast a third cladoceran, Bosmina meridionalis, exhibited no higher mortality over the full range of the cumulative UVB‐doses used (3–40 kJ m^?2) than controls receiving no UV exposure. The copepod Boeckella delicata showed the highest UV‐sensitivity of all organisms tested (LD10 = 7 kJ m^?2, LD50 = 33 kJ m^?2) whereas for Boeckella triarticulata, which was more heavily pigmented than B. delicata, no UV‐induced mortality was observed. Under natural conditions UV irradiances of up to 100 kJ m^?2 day^?1 can fall on the surface of New Zealand lakes. Although this is attenuated in natural waters, these data suggest that UVB irradiance may be a significant ecological variable to some zooplankton species.     

Errors of isotope ratios acquired by double interpolation

Measurement of isotope ratios via double interpolation of cyclic peak jumping produces error correlations between time-adjacent ratios which, if ignored, result in underestimated errors of their means. Equations that incorporate the error correlations are derived, and an example given for a typical U–Pb/zircon analysis via ion microprobe showing that isotope-ratio uncertainties for a single spot are usually underestimated by factors of 1.2–1.3.     

Effect of water on the fluorine and chlorine partitioning behavior between olivine and silicate melt

Halogens show a range from moderate (F) to highly (Cl, Br, I) volatile and incompatible behavior, which makes them excellent tracers for volatile transport processes in the Earth’s mantle. Experimentally determined fluorine and chlorine partitioning data between mantle minerals and silicate melt enable us to estimate Mid Ocean Ridge Basalt (MORB) and Ocean Island Basalt (OIB) source region concentrations for these elements. This study investigates the effect of varying small amounts of water on the fluorine and chlorine partitioning behavior at 1280?°C and 0.3 GPa between olivine and silicate melt in the Fe-free CMAS+F–Cl–Br–I–H₂O model system. Results show that, within the uncertainty of the analyses, water has no effect on the chlorine partitioning behavior for bulk water contents ranging from 0.03 (2) wt% H₂O (D_Cl ^ol/melt = 1.6?±?0.9 × 10^?4) to 0.33 (6) wt% H₂O (D_Cl ^ol/melt = 2.2?±?1.1 × 10^?4). Consequently, with the effect of pressure being negligible in the uppermost mantle (Joachim et al. Chem Geol 416:65–78, 2015), temperature is the only parameter that needs to be considered for the determination of chlorine partition coefficients between olivine and melt at least in the simplified iron-free CMAS+F–Cl–Br–I–H₂O system. In contrast, the fluorine partition coefficient increases linearly in this range and may be described at 1280?°C and 0.3 GPa with (R ²?=?0.99): \(D_{F}^{\text{ol/melt}}\ =\ 3.6\pm 0.4\ \times \ {{10}^{-3}}\ \times \ {{X}_{{{\text{H}}_{\text{2}}}\text{O}}}\left( \text{wt }\!\!\%\!\!\text{ } \right)\ +\ 6\ \pm \ 0.4\times \,{{10}^{-4}}\). The observed fluorine partitioning behavior supports the theory suggested by Crépisson et al. (Earth Planet Sci Lett 390:287–295, 2014) that fluorine and water are incorporated as clumped OH/F defects in the olivine structure. Results of this study further suggest that fluorine concentration estimates in OIB source regions are at least 10% lower than previously expected (Joachim et al. Chem Geol 416:65–78, 2015), implying that consideration of the effect of water on the fluorine partitioning behavior between Earth’s mantle minerals and silicate melt is vital for a correct estimation of fluorine abundances in OIB source regions. Estimates for MORB source fluorine concentrations as well as chlorine abundances in both mantle source regions are within uncertainty not affected by the presence of water.