The VLT-FLAMES survey of massive stars: evolution of surface N abundances and effective temperature scales in the Galaxy and Magellanic Clouds

We present an analysis of high resolution VLT-FLAMES spectra of 61 B-type stars with relatively narrow-lined spectra located in 4 fields centered on the Milky Way clusters; NGC 3293 and NGC 4755 and the Large and Small Magellanic cloud clusters; NGC 2004 and NGC 330. For each object a quantitative analysis was carried out using the non-LTE model atmosphere code TLUSTY; resulting in the determination of their atmospheric parameters and photospheric abundances of the dominant metal species (C, N, O, Mg, Si, Fe). The results are discussed in relation to our earlier work on 3 younger clusters in these galaxies; NGC 6611, N11 and NGC 346 paying particular attention to the nitrogen abundances which are an important probe of the role of rotation in the evolution of stars. This work along with that of the younger clusters provides a consistent dataset of abundances and atmospheric parameters for over 100 B-type stars in the three galaxies. We provide effective temperature scales for B-type dwarfs in all three galaxies and for giants and supergiants in the SMC and LMC. In each galaxy a dependence on luminosity is found between the three classes with the unevolved dwarf objects having significantly higher effective temperatures. A metallicity dependence is present between the SMC and Galactic dwarf objects, and whilst the LMC stars are only slightly cooler than the SMC stars, they are significantly hotter than their Galactic counterparts.

Molecular Hydrogen Emission from Protoplanetary Disks: Effects of X-ray Irradiation and Dust Evolution

Detailed models for the density and temperature profiles of gas and dust in protoplanetary disks are constructed by taking into account X-ray and UV irradiation from a central T Tauri star, as well as dust size growth and settling toward the disk midplane. The spatial and size distributions of dust grains are numerically computed by solving the coagulation equation for settling dust particles, with the result that the mass and total surface area of dust grains per unit volume of the gas in the disks are very small, except at the midplane. The H2 level populations and line emission are calculated using the derived physical structure of the disks. X-ray irradiation is the dominant heating source of the gas in the inner disk and in the surface layer, while the UV heating dominates otherwise. If the central star has strong X-ray and weak UV radiation, the H2 level populations are controlled by X-ray pumping, and the X-rayinduced transition lines could be observable. If the UV irradiation is strong, the level populations are controlled by thermal collisions or UV pumping, depending on the dust properties. As the dust particles evolve in the disks, the gas temperature at the disk surface drops because the grain photoelectric heating becomes less efficient. This makes the level populations change from LTE to non-LTE distributions, which results in changes to the line ratios. Our results suggest that dust evolution in protoplanetary disks could be observable through the H2 line ratios. The emission lines are strong from disks irradiated by strong UV and X-rays and possessing small dust grains; such disks will be good targets in which to observe H2 emission.

Hydrochemical and isotopic tracing of mixing dynamics and water quality evolution under pumping conditions in the mine shaft of the abandoned Frances Colliery, Scotland.

Since 1995, when pumps were withdrawn from deep mines in East Fife (Scotland), mine waters have been rebounding throughout the coalfield. Recently, it has become necessary to pump and treat these waters to prevent their uncontrolled emergence at the surface. However, even relatively shallow pumping to surface treatment lagoons of the initially chemically-stratified mine water from a shaft in the coastal Frances Colliery during two dynamic step-drawdown tests to establish the hydraulic characteristics of the system resulted in rapid breakdown of the stratification within 24 h and a poor pumped water quality with high dissolved Fe loading. Further, data are presented here of hydrochemical and isotopic sampling of the extended pump testing lasting up to several weeks. The use in particular of the environmental isotopes d18O, d2H, d34S, 3H, 13C and 14C alongside hydrochemical and hydraulic pump test data allowed characterisation of the Frances system dynamics, mixing patterns and water quality sources feeding into this mineshaft under continuously pumped conditions. The pumped water quality reflects three significant components of mixing: shallow freshwater, seawater, and leakage from the surface treatment lagoons. In spite of the early impact of recirculating lagoon waters on the hydrochemistries, the highest Fe loadings in the longer-term pumped waters are identified with a mixed freshwater–seawater component affected by pyrite oxidation/melanterite dissolution in the subsurface system.

The VLT-FLAMES Survey of massive stars: Rotation and nitrogen enrichment as the key to understanding massive star evolution

Rotation has become an important element in evolutionary models of massive stars, specifically via the prediction of rotational mixing. Here we study a sample of stars, including rapid rotators, to constrain such models and use nitrogen enrichments as a probe of the mixing process. Chemical compositions (C, N, O, Mg, and Si) have been estimated for 135 early B-type stars in the Large Magellanic Cloud with projected rotational velocities up to similar to 300 km s(-1) using a non-LTE TLUSTY model atmosphere grid. Evolutionary models, including rotational mixing, have been generated attempting to reproduce these observations by adjusting the overshooting and rotational mixing parameters and produce reasonable agreement with 60% of our core hydrogen burning sample. We find (excluding known binaries) a significant population of highly nitrogen-enriched intrinsic slow rotators (nu sin i less than or similar to 50 km s(-1)) incompatible with our models (similar to 20% of the sample). Furthermore, while we find fast rotators with enrichments in agreement with the models, the observation of evolved (dex) fast rotators (log g < 3.7 dex) that are relatively unenriched (a further similar to 20% of the sample) challenges the concept of rotational mixing. We also find that 70% of our blue supergiant sample cannot have evolved directly from the hydrogen-burning main sequence. We are left with a picture where invoking binarity and perhaps fossil magnetic fields is required to understand the surface properties of a population of massive main- sequence stars.

Evolution of Clay Morphology in Polypropylene/Montmorillonite Nanocomposites upon Equi-biaxial Stretching: A Solid-State NMR and TEM Approach

Solid-state NMR and TEM were used to quantitatively examine the evolution of clay morphology upon equibiaxial stretching of polypropylene/montmorillonite (PP-MMT) nanocomposites up to a stretch ratio (?= final length/initial length) of 3.5. 1 H spin-lattice relaxation times were measured by the saturation-recovery sequence. For the nanocomposites, initial portions of the magnetization recovery
curves (e~20 ms) were found to depend on v t, indicative of diffusion-limited relaxation and in agreement with calculations based on estimates of the spin-diffusion barrier radius surrounding the paramagnetic centers in the clay, the electron-nucleus coupling constant, and the spin-diffusion coefficient. Initial slopes of these magnetization recovery curves directly correlated with the fraction of clay/polymer interface. New clay surface was exposed as a near linear function of strain. Long-time portions of the magnetization recovery curves yielded information on the average interparticle separations, which decreased slowly before reaching a plateau at ?=~2.5 as particles aligned. TEM images supported these findings and were used to define and quantify degrees of exfoliation and homogeneity from the NMR data. Exfoliation, defined as (platelets/ stack)-1, increased from 0.38 (unstretched) to 0.80 at ? = 3.5 for PP-MMT nanocomposites stretched at
150 C and 16 s-1. A lower stretch temperature, 145 C, which is slightly below melting onset, led to an exfoliation degree of 0.87 at ?= 2.8, consistent with the ability of higher melt viscosities to allow for higher shear stress transfer. Exposure of new clay surface is attributed to aggregate breakup and orientation at low strains (? e ~2) and to platelets sliding apart at higher strains.

High density mangrove plantation enhances surface accretion, surface elevation change, and tree survival in coastal areas susceptible to sea-level rise

Survival, growth, above ground biomass accumulation, soil surface elevation dynamics and nitrogen accumulation in accreted sediments were studied in experimental treatments planted with four different densities (6.96, 3.26, 1.93 and 0.95 seedlings m-2) of the mangrove Rhizophora mucronata in Puttalam Lagoon, Sri Lanka. Measurements were taken over a period of 1171 days and were compared with those from unplanted controls. Trees at the lowest density showed significantly reduced survival, whilst measures of individual tree growth did not differ significantly among treatments. Rates of surface sediment accretion (means ± S.E.) were 13.0 (±1.3), 10.5 (±0.9), 8.4 (±0.3), 6.9 (±0.5) and 5.7 (±0.3) mm yr-1 at planting densities of 6.96, 3.26, 1.93, 0.95, and 0 (unplanted control) seedlings m-2, respectively, showing highly significant differences among treatments. Mean (± S.E.) rates of surface elevation change were much lower than rates of accretion at 2.8 (±0.2), 1.6 (±0.1), 1.1 (±0.2), 0.6 (±0.2) and -0.3 (±0.1) mm yr-1 for 6.96, 3.26, 1.93, 0.95, and 0 seedlings m-2, respectively. All planted treatments appeared to accumulate greater nitrogen concentrations in the sediment compared to the unplanted control, and suggests one potential causal mechanism for the facilitatory effects observed; high densities of plants potentially contribute to the accretion of greater amounts of nutrient rich sediment. While this potential process needs further study, this study demonstrated how higher densities of mangroves enhance rates of sediment accretion and surface elevation, processes that may be crucial in mangrove ecosystem adaptation to sea level rise. There was no evidence that increasing plant density evoked a trade-off with growth and survival of the planted trees. Rather facilitatory effects enhanced survival at high densities, suggesting that local land managers may be able to take advantage of plantation densities to help mitigate sea-level rise effects by encouraging positive soil surface elevation increment, and perhaps even greater nutrient retention to promote mangrove growth and ameliorate nearshore eutrophication in tropical island environments.

Dynamical instability in surface permeability characteristics of building sandstones in response to salt accumulation over time

This paper explores how the surface permeability of sandstone blocks changes over time in response to repeated salt weathering cycles. Surface permeability controls the amount of moisture and dissolved salt that can penetrate in and facilitate decay. Connected pores permit the movement of moisture (and hence soluble salts) into the stone interior, and where areas are more or less permeable soluble salts may migrate along preferred pathways at differential rates. Previous research has shown that salts can accumulate in the near-surface zone and lead to partial pore blocking which influences subsequent moisture ingress and causes rapid salt accumulation in the near-surface zone.

Two parallel salt weathering simulations were carried out on blocks of Peakmoor Sandstone of different volumes. Blocks were removed from simulations after 2, 5, 10, 20 and 60 cycles. Permeability measurements were taken for these blocks at a resolution of 20 mm, providing a grid of 100 permeability values for each surface. The geostatistical technique of ordinary kriging was applied to the data to produce a smoothed interpolation of permeability for these surfaces, and hence improve understanding of the evolution of permeability over time in response to repeated salt weathering cycles.

Results illustrate the different responses of the sandstone blocks of different volumes to repeated salt weathering cycles. In both cases, after an initial subtle decline in the permeability (reflecting pore blocking), the permeability starts to increase — reflected in a rise in mean, maximum and minimum values. However, between 10 and 20 cycles, there is a jump in the mean and range permeability of the group A block surfaces coinciding with the onset of meaningful debris release. After 60 cycles, the range of permeability in the group A block surface had increased markedly, suggesting the development of a secondary permeability. The concept of dynamic instability and divergent behaviour is applied at the scale of a single block surface, with initial small-scale differences across a surface having larger scale consequences as weathering progresses.

After cycle 10, group B blocks show a much smaller increase in mean permeability, and the range stays relatively steady — this may be explained by the capillary conditions set up by the smaller volume of the stone, allowing salts to migrate to the ‘back’ of the blocks and effectively relieving stress at the ‘front’ face.

Chemical evolution of protoplanetary disks - the effects of viscous accretion, turbulent mixing and disk winds

We calculate the chemical evolution of protoplanetary disks considering radial viscous accretion, vertical turbulent mixing, and vertical disk winds. We study the effects on the disk chemical structure when different models for the formation of molecular hydrogen on dust grains are adopted. Our gas-phase chemistry is extracted from the UMIST Database for Astrochemistry (Rate06) to which we have added detailed gas-grain interactions. We use our chemical model results to generate synthetic near- and mid-infrared local thermodynamic equilibrium line emission spectra and compare these with recent Spitzer observations. Our results show that if H2 formation on warm grains is taken into consideration, the H2O and OH abundances in the disk surface increase significantly. We find that the radial accretion flow strongly influences the molecular abundances, with those in the cold midplane layers particularly affected. On the other hand, we show that diffusive turbulent mixing affects the disk chemistry in the warm molecular layers, influencing the line emission from the disk and subsequently improving agreement with observations. We find that NH3, CH3OH, C2H2, and sulfur-containing species are greatly enhanced by the inclusion of turbulent mixing. We demonstrate that disk winds potentially affect the disk chemistry and the resulting molecular line emission in a manner similar to that found when mixing is included.

Using the surface profiles of modern ice masses to inform palaeo-glacier reconstructions

Morphometric study of modern ice masses is useful because many reconstructions of glaciers traditionally draw on their shape for guidance Here we analyse data derived from the surface profiles of 200 modern ice masses-valley glaciers icefields ice caps and ice sheets with length scales from 10º to 10³ km-from different parts of the world Four profile attributes are investigated relief span and two parameters C* and C that result from using Nye s (1952) theoretical parabola as a profile descriptor C* and C respectively measure each profile s aspect ratio and steepness and are found to decrease in size and variability with span This dependence quantifies the competing influences of unconstrained spreading behaviour of ice flow and bed topography on the profile shape of ice masses which becomes more parabolic as span Increases (with C* and C tending to low values of 2.5-3.3 m ½) The same data reveal coherent minimum bounds in C* and C for modern ice masses that we develop into two new methods of palaeo glacier reconstruction In the first method glacial limits are known from moraines and the bounds are used to constrain the lowest palaeo ice surface consistent with modern profiles We give an example of applying this method over a three-dimensional glacial landscape in Kamchatka In the second method we test the plausibility of existing reconstructions by comparing their C* and C against the modern minimum bounds Of the 86 published palaeo ice masses that we put to this test 88% are found to be plausible The search for other morphometric constraints will help us formalise glacier reconstructions and reduce their uncertainty and subjectiveness

A late-Middle Pleistocene (Marine Isotope Stage 6) vegetated surface buried by Old Crow tephra at the Palisades, interior Alaska

A 40 cm thick primary bed of Old Crow tephra (131 ± 11 ka), an important stratigraphic marker in eastern Beringia, directly overlies a vegetated surface at Palisades West, on the Yukon River in central Alaska. Analyses of insect, bryophyte, and vascular plant macrofossils from the buried surface and underlying organic-rich silt suggest the local presence of an aquatic environment and mesic shrub-tundra at the time of tephra deposition. Autochthonous plant and insect macrofossils from peat directly overlying Old Crow tephra suggest similar aquatic habitats and hydric to mesic tundra environments, though pollen counts indicate a substantial herbaceous component to the regional tundra vegetation. Trace amounts of arboreal pollen in sediments associated with the tephra probably reflect reworking from older deposits, rather than the local presence of trees. The revised glass fission-track age for Old Crow tephra places its deposition closer to the time of the last interglaciation than earlier age determinations, but stratigraphy and paleoecology of sites with Old Crow tephra indicate a late Marine Isotope Stage 6 age. Regional permafrost degradation and associated thaw slumping are responsible for the close stratigraphic and paleoecological relations between Old Crow tephra and last interglacial deposits at some sites in eastern Beringia. © 2009 Elsevier Ltd.

Measuring oxygen reduction/evolution reactions on the nanoscale

The efficiency of fuel cells and metal-air batteries is significantly limited by the activation of oxygen reduction and evolution reactions. Despite the well-recognized role of oxygen reaction kinetics on the viability of energy technologies, the governing mechanisms remain elusive and until now have been addressable only by macroscopic studies. This lack of nanoscale understanding precludes optimization of material architecture. Here, we report direct measurements of oxygen reduction/evolution reactions and oxygen vacancy diffusion on oxygen-ion conductive solid surfaces with sub-10 nm resolution. In electrochemical strain microscopy, the biased scanning probe microscopy tip acts as a moving, electrocatalytically active probe exploring local electrochemical activity. The probe concentrates an electric field in a nanometre-scale volume of material, and bias-induced, picometre-level surface displacements provide information on local electrochemical processes. Systematic mapping of oxygen activity on bare and platinum-functionalized yttria-stabilized zirconia surfaces is demonstrated. This approach allows direct visualization of the oxygen reduction/evolution reaction activation process at the triple-phase boundary, and can be extended to a broad spectrum of oxygen-conductive and electrocatalytic materials.