New approaches for removing the Si-OH layer of biogenic silica before analysing oxygen isotopes - Helium Flow Dehydration (HFD) and Vacuum Bead Melting (VBM) technique

The analysis of oxygen isotopes from diatom silica (&#948;18OSi) in sediment cores has obtained importance for palaeoclimate reconstruction especially where carbonate proxies are either rare or not available. Compared to the widely accepted relation of oxygen isotopes of carbonate origin to climate-relevant parameters, challenges still occur using biogenic silica. These questions arise at sample preparation as well as and the analysis itself, but are especially related to the removal of loosely bound oxygen of the hydrous layer. It is the common view that diatoms consist of an isotopically homogenous inner Si-O-Si layer and a less dense, hydrous layer forming Si-OH bonds, which has to be removed from the sample prior to analysis. Three methods have been accepted so far to perform this step: Controlled Isotopic Exchange (CIE) followed by fluorination, Stepwise Fluorination (SWF) and inductive High-Temperature carbon reduction (iHTR). The former method of vacuum dehydration (VD) proved to be unable to remove all exchangeable oxygen.Here, a new, remotely-operated laser-fluorination based mass spectrometry unit is used for the analysis. The silica is reacted with a CO2 laser in a BrF5 atmosphere and oxygen is then transferred to and analysed in a mass spectrometer (PDZ Europa 20-20). As CIE is both time-consuming and work-intense and SWF is impractical for this setup mainly due to the high pressure increase during dehydration, a new, efficient and fast method should be developed to remove the hydrous layer using the laser-fluorinationprocess.Two approaches were tested to remove the Si-OH layer and the impact on &#948;18OSi was assessed by performing tests on internal standard materials of marine and lacustrine biogenic silica and of quartz. For VBM, a minimum of 1.5 mg of pure sample is melted to a bead with a defocused laser to eliminate the hydrous outer layer and to reduce the surface. After the bead has formed it is transferred into the reaction chamber completely reacted with a focused laser under BrF5 atmosphere and subsequently analysed on-line.The second method, HFD is an improvement of the outdated VD technique. The sample is heated to 1050°C in a He flow transporting away any removed exchangeable oxygen immediately and thus, not allowing it to re-react with the sample. Various tests have been performed considering pre-heating at 200°C, He flow adjustments and the time of the sample exposed to 1050°C.VBM has difficulties to fully remove the hydrous layer, which results in comparatively lower &#948;18O values. The final set-up was not found yet. The HFD generated similar data than SWF in other laboratories with a high reproducibility and accuracy (standard deviation <0.2 ). Best results could be achieved by pre-heating the sample at 200°C and later on expose it for 15 minutes under a Helium counter flow at 1050°C. Experience with both techniques will be discussed and the reliability of the data compared to other methods

Full dimensional (15D) quantum-dynamical simulation of the protonated water-dimer II: infrared spectrum and vibrational dynamics

The infrared absorption spectrum of the protonated water dimer (H5O2+) is simulated in full dimensionality (15D) in the spectral range 0-4000 cm-1. The calculations are performed using the Multiconfiguration Time-Dependent Hartree (MCTDH) method for propagation of wavepackets. All the fundamentals and several overtones of the vibrational motion are computed. The spectrum of H5O2+ is shaped to a large extent by couplings of the proton-transfer motion to large amplitude fluxional motions of the water molecules, water bending and water-water stretch motions. These couplings are identified and discussed, and the corresponding spectral lines assigned. The large couplings featured by H5O2+ do not hinder, however, to describe the coupled vibrational motion by well defined simple types of vibration (stretching, bending, etc.) based on well defined modes of vibration, in terms of which the spectral lines are assigned. Comparison of our results to recent experiments and calculations on the system is given. The reported MCTDH IR-spectrum is in very good agreement to the recently measured spectrum by Hammer et al. [JCP, 122, 244301, (2005)].Comment: 30 pages, 6 figures, submitted to J. Chem. Phy

The nearby population of M dwarfs with WISE: A search for warm circumstellar dust

Circumstellar debris disks are important because of their connection to planetary systems. An efficient way to identify these systems is through their infrared excess. Most studies so far concentrated on early-type or solar-type stars, but less effort has gone into investigating M dwarfs. We characterize the mid-infrared photometric behavior of M dwarfs and search for infrared excess in nearby M dwarfs taken from the volume-limited RECONS sample using data from the WISE satellite and the 2MASS catalog. Our sample consists of 85 sources encompassing 103 M dwarfs. We derive empirical infrared colors from these data and discuss their errors. Based on this, we check the stars for infrared excess and discuss the minimum excess we would be able to detect. Other than the M8.5 dwarf SCR 1845-6357 A, where the excess is produced by a known T6 companion, we detect no excesses in any of our sample stars. The limits we derive for the 22um excess are slightly higher than the usual detection limit of 10-15% for Spitzer studies, but including the [12]-[22] color in our analysis allows us to derive tight constraints on the fractional dust luminosity L_dust/L_star. We show that this result is consistent with M dwarf excesses in the mid-inrared being as frequent as excesses around earlier-type stars. The low detection rate could be an age effect. We also present a tentative excess detection at 22um around the known cold debris disk M dwarf AU Mic, which is not part of our statistical sample. There is still no clear detection of a mid-infrared excess around any old (>30 Myr) main-sequence M dwarf. It is unclear whether this is due to a different dust evolution around M dwarfs or whether this is an age effect combined with the diffculties involved in searching M dwarfs for infrared excesses. A significantly larger sample of well-studied M dwarfs is required to solve this question.Comment: Accepted for publication in A&A, 15 pages, 7 figure

Long-legged flies and dance flies (Diptera: Empidoidea: Dolichopodidae, Empididae, Hybotidae) of wet grassland, managed with different land use intensity, in the valley of the river Schwentine near Raisdorf (Schleswig-Holstein, North Germany)

Feucht- und Nasswiesen mit intaktem Wasserhaushalt, die früher typisch für Niederungen an Flüssen und Seen in Norddeutschland waren, sind in den letzten Jahrzehnten durch Entwässerung von Niederungen sowie durch Veränderungen in der Nutzungsintensität stark in ihrem Bestand zurückgegangen (IRMLER ET AL. 1998). Sowohl eine Nutzungsintensivierung mit verstärkter Düngung, erhöhter Viehdichte und Schnitthäufigkeit, Vorverlegung der ersten Mahd als auch die Nutzungsaufgabe mit übermäßiger Extensivierung und Wiedervernässung durch überhöhte Stauhaltung sind problematisch für den Erhalt artenreicher Feuchtwiesen (Calthion palustris), die ursprünglich durch eine traditionelle Zweischnittnutzung entstanden sind (HELLBERG ET AL. 2003). Artenreiches Feuchtgrünland hat sich gegenwärtig vorwiegend in kleinen, schwer zu entwässernden Niederungen wie z.B. im Schwentinetal mit seinen nassen und tiefen Niedermoorböden, die sich von jeher einer intensiven landwirtschaftlichen Nutzung entzogen haben, großflächig erhalten können (SCHUHMANN 2003). Im Rahmen eines Naturschutzprojektes zur Extensivierung von Grünland wurde 1986-1988 die Insektenfauna im Schwentinetal von Feucht- und Nasswiesen auf mäßig entwässerten Niedermoorböden, mit unterschiedlicher Bewirtschaftungsintensität untersucht. Hauptkriterien waren der Einfluss von Grundwasserpegelständen und Beweidung auf die Abundanz der Langbein- und Tanzfliegen sowie die Verteilung der ökologischen Artengruppen auf die einzelnen Grünlandtypen. Weitere Kriterien beinhalteten Dominanz- und Geschlechtsverhältnis, Phänologie und den Gefährdungsstatus der Arten.The insect fauna, emerging from different dry and wet grasslands had been investigated by photoeklector samples 1986-1988. In total 86 species of Empidoidea out of 2615 specimens were registrated. Wet grassland was dominated by 18 praticolous and 24 ripicolous species whereas silvicolous species (25) were most dominant in dry grassland. Maximal abundance of species and specimens occurred predominantly in May and June before cutting. Differences between the groundwater table, of the sites investigated, seem to be the most important environmental factor to explain the variance of species (Canoco-analysis: 77.8% on axis 1) between different sites. The influence of grazing intensity resulted in a further differentiation of sites with a similar groundwater table and explained 22.2% of species variance (axis 2)

Die Stauchendmoränen der Rehburger Eisrandlage und ihre Entstehung

Anhand morphologischer und struktureller Befunde werden die Glieder der Rehburger Eisrandlage als Stauchendmoränen gedeutet. Die Aufstauchung erfolgte im Zuge eines kontinuierlichen Eisvorstoßes während der Saale-Eiszeit (Drenthe-Stadium) durch sog. Stirnoder Frontalstauchung. Es wird ein Modell dieser Stauchung vorgestellt ("Modell Kellenberg"). Als Steuerungsfaktoren der Stauchungsprozesse werden angenommen: 1. das dynamische Verhalten des Inlandeises (Vorschub, Belastungsdruck); 2. die bodenmechanischen Eigenschaften des gestauchten Substrates (Plastizität, Scherfestigkeit, Permafrost-Zementierung, Schmiermitteleffekt); 3. das präexistente Relief (Widerlager- oder Rampeneffekt). Nach der Aufstauchung wurde die Stau ehzone vom Eis der "Hamelner Phase" überfahren und in unbekanntem Ausmaß erniedrigt (eingerumpft). Im periglaziären Milieu der späten Saale-Eiszeit (Warthe-Stadium) und der Weichsel-Eiszeit erfolgte durch selektive Erosion eine Akzentuierung der Mesoformen (Bildung von Härtlingsrükken); gleichzeitig wurde die Prägnanz der Makroformen durch das gegenläufige Nebeneinander von subaerischer Abtragung auf den Höhenrücken und periglazialablualer Aufschüttung in den Niederungen (Talsande) verringert.The push endmoraines of the "Rehburger Eisrandlage" and their genesis. On the base of morphological and structural evidences the ridges of the "Rehburger Eisrandlage" are interpreted as push endmoraines. The glacial thrusting happened during a continuous advance of the Saalian ice in the Drenthe stage. It was caused by "Stirn-/Frontalstauchung". The supposed sequence of processes Lsintroduced by a model of push endmoraine genesis, "type Kellenberg" . As influencing factors are assumed: 1) ice dynamics (horizontal and vertical pressure of the advancing ice mass); 2) the soilmechanic properties of the substratum (plasticity, shearing strength, cementation by ground-ice/permafrost,lubrication effect); 3) the preglacial morphology (iceward sloping surface, = threshold-/ramp-effect). Following the glacial distortion the push zone was overridden and truncated by the glacier of the "Hameln phase". The quantitative amount of erosion during this event remains uncertain and contradictory . In the Late Saalian (Warthe stage) and the Weichselian the mesorelief was accentuated by selective erosion in a periglacial environment (formation of gravel ridges); at the same time the macrorelief was flattened by subaerial denudation on the moraines and by sedimentation of periglacial-ablual sands ("Talsande") in the low Iying foreland