A spectroscopic cell for fast pressure jumps across the glass transition line

We present a new experimental protocol for the spectroscopic study of the dynamics of glasses in the aging regime induced by sudden pressure jumps (crunches) across the glass transition line. The sample, initially in the liquid state, is suddenly brought in the glassy state, and therefore out of equilibrium, in a four-window optical crunch cell which is able to perform pressure jumps of 3 kbar in a time interval of ~10 ms. The main advantages of this setup with respect to previous pressure-jump systems is that the pressure jump is induced through a pressure transmitting fluid mechanically coupled to the sample stage through a deformable membrane, thus avoiding any flow of the sample itself in the pressure network and allowing to deal with highly viscous materials. The dynamics of the sample during the aging regime is investigated by Brillouin Light Scattering (BLS). For this purpose the crunch cell is used in conjunction with a high resolution double monochromator equipped with a CCD detector. This system is able to record a full spectrum of a typical glass forming material in a single 1 s shot. As an example we present the study of the evolution toward equilibrium of the infinite frequency longitudinal elastic modulus (M_infinity) of a low molecular weight polymer (Poly(bisphenol A-co-epichlorohydrin), glycidyl end capped). The observed time evolution of M_infinity, well represented by a single stretched exponential, is interpreted within the framework of the Tool-Narayanaswamy theory.Comment: 9 pages, 11 figure

An Optical Readout TPC (O-TPC) for Studies in Nuclear Astrophysics With Gamma-Ray Beams at HIgS

We report on the construction, tests, calibrations and commissioning of an Optical Readout Time Projection Chamber (O-TPC) detector operating with a CO2(80%) + N2(20%) gas mixture at 100 and 150 Torr. It was designed to measure the cross sections of several key nuclear reactions involved in stellar evolution. In particular, a study of the rate of formation of oxygen and carbon during the process of helium burning will be performed by exposing the chamber gas to intense nearly mono-energetic gamma-ray beams at the High Intensity Gamma Source (HIgS) facility. The O-TPC has a sensitive target-drift volume of 30x30x21 cm^3. Ionization electrons drift towards a double parallel grid avalanche multiplier, yielding charge multiplication and light emission. Avalanche induced photons from N2 emission are collected, intensified and recorded with a Charge Coupled Device (CCD) camera, providing two-dimensional track images. The event's time projection (third coordinate) and the deposited energy are recorded by photomultipliers and by the TPC charge-signal, respectively. A dedicated VME-based data acquisition system and associated data analysis tools were developed to record and analyze these data. The O-TPC has been tested and calibrated with 3.183 MeV alpha-particles emitted by a 148Gd source placed within its volume with a measured energy resolution of 3.0%. Tracks of alpha and 12C particles from the dissociation of 16O and of three alpha-particles from the dissociation of 12C have been measured during initial in-beam test experiments performed at the HIgS facility at Duke University. The full detection system and its performance are described and the results of the preliminary in-beam test experiments are reported.Comment: Supported by the Richard F. Goodman Yale-Weizmann Exchange Program, ACWIS, NY, and USDOE grant Numbers: DE-FG02-94ER40870 and DE-FG02-97ER4103

Constraining the uncertainty in emissions over India with a regional air quality model evaluation

To evaluate uncertainty in the spatial distribution of air emissions over India, we compare satellite and surface observations with simulations from the U.S. Environmental Protection Agency (EPA) Community Multi-Scale Air Quality (CMAQ) model. Seasonally representative simulations were completed for January, April, July, and October 2010 at 36 km × 36 km using anthropogenic emissions from the Greenhouse Gas-Air Pollution Interaction and Synergies (GAINS) model following version 5a of the Evaluating the Climate and Air Quality Impacts of Short-Lived Pollutants project (ECLIPSE v5a). We use both tropospheric columns from the Ozone Monitoring Instrument (OMI) and surface observations from the Central Pollution Control Board (CPCB) to closely examine modeled nitrogen dioxide (NO2) biases in urban and rural regions across India. Spatial average evaluation with satellite retrievals indicate a low bias in the modeled tropospheric column (-63.3%), which reflects broad low-biases in majority non-urban regions (-70.1% in rural areas) across the sub-continent to slightly lesser low biases reflected in semi-urban areas (-44.7%), with the threshold between semi-urban and rural defined as 400 people per km2. In contrast, modeled surface NO2 concentrations exhibit a slight high bias of +15.6% when compared to surface CPCB observations predominantly located in urban areas. Conversely, in examining extremely population dense urban regions with more than 5000 people per km2 (dense-urban), we find model overestimates in both the column (+57.8) and at the surface (+131.2%) compared to observations. Based on these results, we find that existing emission fields for India may overestimate urban emissions in densely populated regions and underestimate rural emissions. However, if we rely on model evaluation with predominantly urban surface observations from the CPCB, comparisons reflect model high biases, contradictory to the knowledge gained using satellite observations. Satellites thus serve as an important emissions and model evaluation metric where surface observations are lacking, such as rural India, and support improved emissions inventory development

Control-volume representation of molecular dynamics

A Molecular Dynamics (MD) parallel to the Control Volume (CV) formulation of fluid mechanics is developed by integrating the formulas of Irving and Kirkwood, J. Chem. Phys. 18, 817 (1950) over a finite cubic volume of molecular dimensions. The Lagrangian molecular system is expressed in terms of an Eulerian CV, which yields an equivalent to Reynolds' Transport Theorem for the discrete system. This approach casts the dynamics of the molecular system into a form that can be readily compared to the continuum equations. The MD equations of motion are reinterpreted in terms of a Lagrangian-to-Control-Volume (\CV) conversion function $\vartheta_{i}$, for each molecule $i$. The \CV function and its spatial derivatives are used to express fluxes and relevant forces across the control surfaces. The relationship between the local pressures computed using the Volume Average (VA, Lutsko, J. Appl. Phys 64, 1152 (1988)) techniques and the Method of Planes (MOP, Todd et al, Phys. Rev. E 52, 1627 (1995)) emerges naturally from the treatment. Numerical experiments using the MD CV method are reported for equilibrium and non-equilibrium (start-up Couette flow) model liquids, which demonstrate the advantages of the formulation. The CV formulation of the MD is shown to be exactly conservative, and is therefore ideally suited to obtain macroscopic properties from a discrete system.Comment: 19 pages, 15 figure

Global radiative effects of solid fuel cookstove aerosol emissions

We apply the NCAR CAM5-Chem global aerosol–climate model to quantify the net global radiative effects of black and organic carbon aerosols from global and Indian solid fuel cookstove emissions for the year 2010. Our updated assessment accounts for the direct radiative effects, changes to cloud albedo and lifetime (aerosol indirect effect, AIE), impacts on clouds via the vertical temperature profile (semi-direct effect, SDE), and changes in the surface albedo of snow and ice (surface albedo effect). In addition, we provide the first estimate of household solid fuel black carbon emission effects on ice clouds. Anthropogenic emissions are from the IIASA GAINS ECLIPSE V5a inventory. A global dataset of black carbon (BC) and organic aerosol (OA) measurements from surface sites and aerosol optical depth (AOD) from AERONET is used to evaluate the model skill. Compared with observations, the model successfully reproduces the spatial patterns of atmospheric BC and OA concentrations, and agrees with measurements to within a factor of 2. Globally, the simulated AOD agrees well with observations, with normalized mean bias close to zero. However, the model tends to underestimate AOD over India and China by ~ 19 % but overestimate it over Africa by ~ 25 %. Without BC serving as ice nuclei (IN), global and Indian solid fuel cookstove aerosol emissions have a net cooling impact on global climate of −141 ± 4 mW m−2 and −12 ± 4 mW m−2, respectively. The net radiative impacts are dominated by the AIE and SDE mechanisms, which originate from enhanced cloud condensation nuclei concentrations for the formation of liquid and mixed-phase clouds, and a suppression of convective transport of water vapor from the lower troposphere to the upper troposphere/lower stratosphere that in turn leads to reduced ice cloud formation. When BC is allowed to behave as a source of IN, the net global climate impacts of the global and Indian solid fuel cookstove emissions range from −260 to +135 mW m−2 and −33 to +24 mW m−2, with globally averaged values −51 ± 210 and 0.3 ± 29 mW m−2 respectively. The uncertainty range is calculated from sensitivity simulations that alter the maximum freezing efficiency of BC across a plausible range: 0.01, 0.05 and 0.1. BC–ice cloud interactions lead to substantial increases in high cloud (< 500 hPa) fractions. Thus, the net sign of the impacts of carbonaceous aerosols from solid fuel cookstoves on global climate (warming or cooling) remains ambiguous until improved constraints on BC interactions with mixed-phase and ice clouds are available

Social network analysis shows direct evidence for social transmission of tool use in wild chimpanzees

The authors are grateful to the Royal Zoological Society of Scotland for providing core funding for the Budongo Conservation Field Station. The fieldwork of CH was funded by the Leverhulme Trust, the Lucie Burgers Stichting, and the British Academy. TP was funded by the Canadian Research Chair in Continental Ecosystem Ecology, and received computational support from the Theoretical Ecosystem Ecology group at UQAR. The research leading to these results has received funding from the People Programme (Marie Curie Actions) and from the European Research Council under the European Union's Seventh Framework Programme (FP7/2007–2013) REA grant agreement n°329197 awarded to TG, ERC grant agreement n° 283871 awarded to KZ. WH was funded by a BBSRC grant (BB/I007997/1).Social network analysis methods have made it possible to test whether novel behaviors in animals spread through individual or social learning. To date, however, social network analysis of wild populations has been limited to static models that cannot precisely reflect the dynamics of learning, for instance, the impact of multiple observations across time. Here, we present a novel dynamic version of network analysis that is capable of capturing temporal aspects of acquisition-that is, how successive observations by an individual influence its acquisition of the novel behavior. We apply this model to studying the spread of two novel tool-use variants, "moss-sponging'' and "leaf-sponge re-use,'' in the Sonso chimpanzee community of Budongo Forest, Uganda. Chimpanzees are widely considered the most "cultural'' of all animal species, with 39 behaviors suspected as socially acquired, most of them in the domain of tool-use. The cultural hypothesis is supported by experimental data from captive chimpanzees and a range of observational data. However, for wild groups, there is still no direct experimental evidence for social learning, nor has there been any direct observation of social diffusion of behavioral innovations. Here, we tested both a static and a dynamic network model and found strong evidence that diffusion patterns of moss-sponging, but not leaf-sponge re-use, were significantly better explained by social than individual learning. The most conservative estimate of social transmission accounted for 85% of observed events, with an estimated 15-fold increase in learning rate for each time a novice observed an informed individual moss-sponging. We conclude that group-specific behavioral variants in wild chimpanzees can be socially learned, adding to the evidence that this prerequisite for culture originated in a common ancestor of great apes and humans, long before the advent of modern humans.Publisher PDFPeer reviewe

A new molecular model for water adsorption on graphitized carbon black

Adsorption of water on graphitized carbon black at various temperatures has been studied with a new molecular model of graphitized carbon black using Monte Carlo simulation. The model is a collection of graphene layers, modelled by the Steele potential, and a number of phenol groups forming clusters of various sizes which are placed randomly at the graphene edge sites to give an O/C ratio of 0.006. The results are compared with experimental data reported by Kiselev et al. [1] in 1968 for a range of temperatures, and for the first time a reconciliation between the experimental data and simulation has been successfully achieved. The simulation results show that water adsorbs preferentially around the functional groups to form clusters, which then grow and merge at the edges of the graphene layers, rather than adsorbing onto the basal planes of the graphene because the electrostatic interactions (hydrogen bonding) between water molecules are stronger than the basal plane-water dispersion interactions