Redistribution of HFSE elements during rutile replacement by titanite

Titanite growth at the expense of rutile during retrograde hydration of eclogite into amphibolite is a common phenomenon. We investigated an amphibolite sample from the Tromsø eclogite facies terrain in Northern Norway to gain insight into the trace element distribution between rutile and titanite during incomplete resorption of the rutile by titanite. Patchy compositional zoning of Al, Ti, and F in titanite relates to the presence of a fluid with variable Ti/Al and/or F during its growth. Laser ablation ICP–MS and electron microprobe data for high field strength elements (HFSE: Nb, Zr, Ta, and Hf) of rutile resorbed by titanite indicate a pronounced enrichment of these elements in the rim of a large single rutile crystal (~8 mm) and a systematic decrease towards uniform HFSE contents in the large core. HFSE contents of smaller rutile grains (~0.5 mm) and rutile inclusions (<100 μm) in the titanite overgrowth are similar or higher than in the rims of large rutile crystals. Element profiles from the rim inward demonstrate that HFSE enrichment in rutile is controlled by diffusion. HFSE ratios in diffusion-altered rutile show systematic variations compared with the uniform core composition of the large rutile. Modelling of Zr and Nb diffusion in rutile indicates that diffusion coefficients in rutile in fluid-dominated natural systems must be considerably higher than those determined experimentally at 1 bar in dry systems. Variations of HFSE contents in the newly formed titanite show no systematic spatial distribution. HFSE ratios in titanite and the rims of rutile are different, indicating different solid/fluid distribution coefficients in these minerals. Element fractionation by diffusion into the relict rutile and during fluid-mediated growth of new titanite could substantially change the HFSE budget of these minerals and could affect their use for geochemical tracing and other applications, such as Zr-based geothermobarometry.     

Nitrogen isotopes in the recent solar wind from the analysis of Genesis targets: Evidence for large scale isotope heterogeneity in the early solar system

We have analyzed nitrogen, neon and argon abundances and isotopic ratios in target material exposed in space for 27 months to solar wind (SW) irradiation during the Genesis mission. SW ions were extracted by sequential UV (193 nm) laser ablation of gold-plated material, purified separately in a dedicated line, and analyzed by gas source static mass spectrometry. We analyzed gold-covered stainless steel pieces from the Concentrator, a device that concentrated SW ions by a factor of up to 50. Despite extensive terrestrial N contamination, we could identify a non-terrestrial, ¹⁵N-depleted nitrogen end-member that points to a 40% depletion of ¹⁵N in solar-wind N relative to inner planets and meteorites, and define a composition for the present-day Sun (¹⁵N/¹⁴N = [2.26 ± 0.67] × 10⁻³, 2σ), which is indistinguishable from that of Jupiter’s atmosphere. These results indicate that the isotopic composition of nitrogen in the outer convective zone of the Sun has not changed through time, and is representative of the protosolar nebula. Large ¹⁵N enrichments due to e.g., irradiation, low temperature isotopic exchange, or contributions from ¹⁵N-rich presolar components, are therefore required to account for inner planet values.     

Volume diffusion of Ytterbium in YAG: thin-film experiments and combined TEM–RBS analysis

In this study, we address volume diffusion of ytterbium in yttrium aluminum garnet (YAG) using thin-film single crystal diffusion couples. We employ analytical transmission electron microscopy (ATEM) as a tool for combined microstructural and microchemical analysis and compare the results to Rutherford backscattering (RBS) analysis. Given the high spatial resolution of the method, we focus on microstructural changes of the thin-film diffusant source during the diffusion anneal. We evaluate the potential influence of the associated changes in its transport properties on the evolution of concentration profiles in the single crystal substrate. This approach allows us to test the reliability of determination of volume diffusion coefficients from thin-film diffusion experiments. We found that for the chosen experimental setting, the influence of thin-film re-crystallization is small when compared with the experimental uncertainty and good estimates for the volume diffusion coefficients of Yb in YAG can be obtained using standard assumptions. Both Yb-concentration profiles analyzed with ATEM and with RBS give similar results. At 1,450°C and 1 bar, we infer log D _Yb (m²/s) values of −19.37 ± 0.07 (TEM) and −19.84 ± 0.02 (RBS). Although the change in thin-film transport properties associated with successive crystallization during the diffusion anneal does not play a major role for our experimental setup, this effect cannot generally be ignored.     

Numerical modeling of two-phase hysteresis combined with an interface condition for heterogeneous porous media

This paper presents a numerical implementation of two-phase capillary hysteresis and its combination with a capillary interface condition for the treatment of heterogeneities. The hysteresis concepts chosen in this work are first implemented in a node-centered FV discretization scheme and subsequently combined with the interface condition that predicts sharp saturation discontinuities at material interfaces, based on a pressure equilibrium concept. This approach allows for the approximation of history-dependent, and at the same time discontinuous, saturations at material interfaces. The resulting model provides a well-defined evolution of the hysteretic capillary pressure–saturation relationships at material interfaces that is independent of the grid spacing. As demonstrated with a simple 1-D example, this concept therefore offers the advantage that the solution of a two-phase flow problem involving hysteresis does not relate to the grid resolution at the material interfaces.     

Alpine overdeepenings and paleo-ice flow changes: an integrated geophysical-sedimentological case study from Tyrol (Austria)

We present a study of the inneralpine basin of Hopfgarten focused on the analysis of basin fill in order to reveal its formation in relation to paleo-ice flow and tectonics. The study is based on geological mapping as well as seismic (reflection and refraction) and geoelectrical surveys. The oldest sequence in the basin, identified by seismic stratigraphy at 400 m below surface, consists of coarse grained sediments of supposedly Oligocene to Miocene age, which subsided along faults linked to the Inn fault. Three superimposed sequences, each displaying baselaps in contact with a subglacially formed unconformity and sigmoid foresets, show pleniglacial conditions followed by a glaciolacustrine environment. The uppermost of these three sequences lies on top of last glacial maximum till (LGM; Würmian Pleniglacial; MIS 2) and represents Termination I. The middle sequence is classified as Termination II following the Rissian Pleniglacial (MIS 6). The oldest glacial sequence cannot be constrained chronostratigraphically but might correlate with Termination V following the major glaciation of MIS 12. Limited glacial erosion during the LGM occurred only during the ice build-up phase. Further overdeepening was impeded due to topographic barrier and mutual blockades of glaciers within this highly dissected landscape. The occurrence and relative timing of the impediment was controlled by the onset of transfluences and thus by the altitude of coles. The higher amount of overdeepening during older glacial periods is explained by longer phases of free ice advance in the ice build up phase due to higher transfluences routes at that time. Thus, the preservation of older Pleistocene sequences within the basin may be the result of the lowering of watersheds from one glaciation to the next. Our model of an inverse relationship between glacial shaping of the surface and the subsurface may apply to similar Alpine landscapes as well.     

Spectrometric analyses in comparison to the physiological condition of heavy metal stressed floodplain vegetation in a standardised experiment

Floodplain ecosystems are affected by flood dynamics, nutrient supply as well as anthropogenic activities. Heavy metal pollution poses a serious environmental challenge. Pollution transfer from the soil to vegetation is still present at the central location of Elbe River, Germany. The goal of this study was to assess and separate the current heavy metal contamination of the floodplain ecosystem, using spectrometric field and laboratory measurements. A standardized pot experiment with floodplain vegetation in differently contaminated soils provided the basis for the measurements. The dominant plant types of the floodplains are: Urtica dioica, Phalaris arundinacea and Alopecurus pratensis, these were also chemically analysed. Various vegetation indices and methods were used to estimate the red edge position, to normalise the spectral curve of the vegetation and to investigate the potential of different methods for separating plant stress in floodplain vegetation. The main task was to compare spectral bands during phenological phases to find a method to detect heavy metal stress in plants. A multi-level algorithm for the curve parameterisation was developed. Chemo-analytical and ecophysiological parameters of plants were considered in the results and correlated with spectral data. The results of this study show the influence of heavy metals on the spectral characteristics of the focal plants. The developed method (depth CR1730) showed significant relationship between the plants and the contamination.     

The challenge of dating early pleistocene fossil teeth by the combined uranium series–electron spin resonance method: the Venta Micena palaeontological site (Orce,Spain)

The palaeontological site of Venta Micena (Orce, Andalusia, Spain) lies in the eastern sector of the Guadix–Baza basin, one of the best documented areas in Europe for Plio‐Pleistocene biostratigraphy. The combination of biochronological and palaeomagnetic results, combined with the radiometric data obtained for Atapuerca Sima del Elefante, indicated that the Venta Micena stratum was formed between the Jaramillo and Olduvai palaeomagnetic events, most likely between 1.22 and 1.77 Ma. Five fossil teeth from two outcrops (sites A and B) were selected to assess the potential of combined uranium series–electron spin resonance (US‐ESR) dating of Early Pleistocene sites. Although the US‐ESR results of the first outcrop showed a large scatter between the three teeth, the mean age of 1.37 ± 0.24 Ma can be considered a reasonable age estimate for Venta Micena. The mean ESR age of 0.62 ± 0.03 Ma obtained for site B seems to be a severe underestimation when compared with the independent age control. This underestimation is attributed to a relative recent U‐mobilization event that led to some U‐leaching. The results show that any ESR age calculations of old samples are extremely sensitive to variations in the measured ²³⁰Th/²³⁴U ratios in dental tissues. Although the results demonstrate that ESR can in principle be applied to Early Pleistocene sites, they also reveal the complexity of dating such old teeth. It is necessary to continue research in several directions, such as study of the behaviour of ESR signals in old teeth and understanding recent U‐mobilization processes, to improve the reliability of the combined US‐ESR dating method applied to Early Pleistocene times, a period for which the number of available numerical dating techniques is very limited. Copyright © 2011 John Wiley & Sons, Ltd.     

Northwest Africa 1500: Plagioclase‐bearing monomict ureilite or ungrouped achondrite?

Abstract— Northwest Africa (NWA) 1500 is an ultramafic meteorite dominated by coarse (?100–500 μm) olivine (95–96%), augite (2–3%), and chromite (0.6–1.6%) in an equilibrated texture. Plagioclase (0.7–1.8%) occurs as poikilitic grains (up to ?3 mm) in vein‐like areas that have concentrations of augite and minor orthopyroxene. Other phases are Cl‐apatite, metal, sulfide, and graphite. Olivine ranges from Fo 65–73, with a strong peak at Fo 68–69. Most grains are reversezoned, and also have ?10–30 μm reduction rims. In terms of its dominant mineralogy and texture, NWA 1500 resembles the majority of monomict ureilites. However, it is more ferroan than known ureilites (Fo ≥75) and other mineral compositional parameters are out of the ureilite range as well. Furthermore, neither apatite nor plagioclase have ever been observed, and chromite is rare in monomict ureilites. Nevertheless, this meteorite may be petrologically related to the rare augite‐bearing ureilites and represent a previously unsampled part of the ureilite parent body (UPB). The Mn/Mg ratio of its olivine and textural features of its pyroxenes are consistent with this interpretation. However, its petrogenesis differs from that of known augite‐bearing ureilites in that: 1) it formed under more oxidized conditions; 2) plagioclase appeared before orthopyroxene in its crystallization sequence; and 3) it equilibrated to significantly lower temperatures (800–1000 °C, from two‐pyroxene and olivine‐chromite thermometry). Formation under more oxidized conditions and the appearance of plagioclase before orthopyroxene could be explained if it formed at a greater depth on the UPB than previously sampled. However, its significantly different thermal history (compared to ureilites) may more plausibly be explained if it formed on a different parent body. This conclusion is consistent with its oxygen isotopic composition, which suggests that it is an ungrouped achondrite. Nevertheless, the parent body of NWA 1500 may have been compositionally and petrologically similar to the UPB, and may have had a similar differentiation history.     

The influence of Hall drift on the magnetic fields of neutron stars

We consider the evolution of magnetic fields under the influence of Hall drift and Ohmic decay. The governing equation is solved numerically, in a spherical shell with   r _i / r _o = 0.75  . Starting with simple free-decay modes as initial conditions, we then consider the subsequent evolution. The Hall effect induces so-called helicoidal oscillations, in which energy is redistributed among the different modes. We find that the amplitude of these oscillations can be quite substantial, with some of the higher harmonics becoming comparable with the original field. Nevertheless, this transfer of energy to the higher harmonics is not sufficient to accelerate significantly the decay of the original field, at least not at the   R _B = O (100)  parameter values accessible to us, where this Hall parameter   R _B   measures the ratio of the Ohmic time-scale to the Hall time-scale. We do find clear evidence though of increasingly fine structures developing for increasingly large   R _B   , suggesting that perhaps this Hall-induced cascade to ever-shorter length-scales is eventually sufficiently vigorous to enhance the decay of the original field. Finally, the implications for the evolution of neutron star magnetic fields are discussed.     

The effect of long-term low-temperature exposure on apatite fission track stability: A natural annealing experiment in the deep ocean

Since studies on deep-sea cores were carried out in the early 1990s it has been known that ambient temperature may have a marked affect on apatite fission track annealing. Due to sluggish annealing kinetics, this effect cannot be quantified by laboratory annealing experiments. The unknown amount of low-temperature annealing remains one of the main uncertainties for extracting thermal histories from fission track data, particularly for samples which experienced slow cooling in shallow crustal levels. To further elucidate these uncertainties, we studied volcanogenic sediments from five deep-sea drill cores, that were exposed to maximum temperatures between ∼10° and 70 °C over geological time scales of ∼15-120 Ma. Mean track lengths (MTL) and etch pit diameters (Dpar) of all samples were measured, and the chemical composition of each grain analysed for age and track length measurements was determined by electron microprobe analysis. Thermal histories of the sampled sites were independently reconstructed, based on vitrinite reflectance measurements and/or 1D numerical modelling. These reconstructions were used to test the most widely used annealing models for their ability to predict low-temperature annealing. Our results show that long-term exposure to temperatures below the temperature range of the nominal apatite fission track partial annealing zone results in track shortening ranging between 4 and 11%. Both chlorine content and Dpar values explain the downhole annealing patterns equally well. Low chlorine apatite from one drill core revealed a systematic relation between Si-content and Dpar value. The question whether Si-substitution in apatite has direct and systematic effects on annealing properties however, cannot be addressed by our data. For samples, which remained at temperatures <30 °C, and which are low in chlorine, the Laslett et al. [Laslett G., Green P., Duddy I. and Gleadow A. (1987) Thermal annealing of fission tracks in apatite. Chem. Geol. 65, 1-13] annealing model predicts MTL up to 0.6 μm longer than those actually measured, whereas for apatites with intermediate to high chlorine content, which experienced temperatures >30 °C, the predictions of the Laslett et al. (1987) model agree with the measured MTL data within error levels. With few exceptions, predictions by the Ketcham et al. [Ketcham R., Donelick R. and Carlson W. (1999) Variability of apatite fission-track annealing kinetics. III: Extrapolation to geological time scales. Am. Mineral. 84/9, 1235-1255] annealing model are consistent with the measured data for samples which remained at temperatures below ∼30 °C. For samples which experienced maximum temperatures between ∼30 and 70 °C, and which are rich in chlorine, the Ketcham et al. (1999) model overestimates track annealing.