A Simplified Model to Predict Long-Term Ozone Concentrations in Europe

In the preparation process for the Second Sulphur Protocol of the Convention on Long-range Transboundary Air Pollution, integrated assessment models played an important role in identifying cost-effective strategies for reducing SO2 emissions in Europe. Applying this effect-based approach to other environmental problems (e.g., photo-oxidants) seems appealing. In view of the timetable adopted for the current preparation of an updated Protocol on emissions of nitrogen oxides, an integrated assessment tool for ozone is required in the very near future. The paper presents an outline of an integrated assessment model for tropospheric ozone in Europe, with modules on emissions, emission control technologies and costs, ozone formation and environmental impacts. In its central part the paper focuses on the core element of such an approach, i.e., a concise description of the relationships between the precursor emissions (nitrogen oxides and volatile organic compounds) and regional ozone levels, which must be computationally efficient for use in an integrated assessment model. Critical levels, i.e., threshold levels protecting vegetation from damage, have been recently established using long-term exposure measures. Consequently, to be suitable for integrated assessment models, source-receptor relationships should be able to describe the long-term changes of ozone, e.g., over a six-month period. Based on numerous scenario runs of the EMEP ozone model, polynomial source-receptor relationships have been statistically identified. Using national annual emissions of NO, and VOC, the model predicts regional responses of the six-month mean of early afternoon ozone concentrations. From this concentration measure, excess exposure as used in the definition of the critical levels can be derived. The paper introduces the methodology of the approach, evaluates the results and discusses areas of further work. The suggested model formulation can be incorporated into the framework of an integrated assessment model, enabling (i) the assessment of costs and environmental benefits from alternative strategies to reduce precursor emissions and (ii) the identification of cost-optimized strategies to achieve environmental targets

Non-equilibrium phase behavior of confined molecular films at low shear rates

In a recent publication [Maćkowiak et al., J. Chem. Phys. 145, 164704 (2016)] the results of Non-Equilibrium Molecular Dynamics (NEMD) simulations of confined sheared Lennard-Jones molecular films have been presented. The present work builds on that study by focusing on the low wall speed (shear rate) regime. Maps are given of the steady-state structures and corresponding friction coefficients in the region where a transition from static to kinetic friction is observed. The boundary between static and kinetic friction regions is determined as a function of wall speed and applied pressure, which is located for wall speeds up to about 0.8 m s−1. It was found that stick-slip behavior extends to pressures as high as 1000 MPa. The NEMD equations of motion are shown to be consistent with the Prandtl–Tomlinson model in the ‘soft spring’ limit, which leads to a new expression for the friction coefficient. This study provides new details and insights into the nature of anomalous friction behavior in the so-called Plug-Slip part of the nonquilibrium phase diagram regime

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

Alexithymia: a general deficit of interoception

Alexithymia is a sub-clinical construct, traditionally characterized by difficulties identifying and describing one's own emotions. Despite the clear need for interoception (interpreting physical signals from the body) when identifying one's own emotions, little research has focused on the selectivity of this impairment. While it was originally assumed that the interoceptive deficit in alexithymia is specific to emotion, recent evidence suggests that alexithymia may also be associated with difficulties perceiving some non-affective interoceptive signals, such as one's heart rate. It is therefore possible that the impairment experienced by those with alexithymia is common to all aspects of interoception, such as interpreting signals of hunger, arousal, proprioception, tiredness and temperature. In order to determine whether alexithymia is associated with selectively impaired affective interoception, or general interoceptive impairment, we investigated the association between alexithymia and self-reported non-affective interoceptive ability, and the extent to which individuals perceive similarity between affective and non-affective states (both measured using questionnaires developed for the purpose of the current study), in both typical individuals (n = 105 (89 female), mean age = 27.5 years) and individuals reporting a diagnosis of a psychiatric condition (n = 103 (83 female), mean age = 31.3 years). Findings indicated that alexithymia was associated with poor non-affective interoception and increased perceived similarity between affective and non-affective states, in both the typical and clinical populations. We therefore suggest that rather than being specifically associated with affective impairment, alexithymia is better characterized by a general failure of interoception

Machine Learning Clifford Invariants of ADE Coxeter Elements

There has been recent interest in novel Clifford geometric invariants of linear transformations. This motivates the investigation of such invariants for a certain type of geometric transformation of interest in the context of root systems, reflection groups, Lie groups and Lie algebras: the Coxeter transformations. We perform exhaustive calculations of all Coxeter transformations for A8, D8 and E8 for a choice of basis of simple roots and compute their invariants, using high-performance computing. This computational algebra paradigm generates a dataset that can then be mined using techniques from data science such as supervised and unsupervised machine learning. In this paper we focus on neural network classification and principal component analysis. Since the output—the invariants—is fully determined by the choice of simple roots and the permutation order of the corresponding reflections in the Coxeter element, we expect huge degeneracy in the mapping. This provides the perfect setup for machine learning, and indeed we see that the datasets can be machine learned to very high accuracy. This paper is a pump-priming study in experimental mathematics using Clifford algebras, showing that such Clifford algebraic datasets are amenable to machine learning, and shedding light on relationships between these novel and other well-known geometric invariants and also giving rise to analytic results

Modulation of ligand-heme reactivity by binding pocket residues demonstrated in cytochrome c' over the femtosecond-second temporal range

The ability of hemoproteins to discriminate between diatomic molecules, and the subsequent affinity for their chosen ligand, is fundamental to the existence of life. These processes are often controlled by precise structural arrangements in proteins, with heme pocket residues driving reactivity and specificity. One such protein is cytochrome c', which has the ability to bind nitric oxide (NO) and carbon monoxide (CO) on opposite faces of the heme, a property that is shared with soluble guanylate cycle. Like soluble guanylate cyclase, cytochrome c' also excludes O completely from the binding pocket. Previous studies have shown that the NO binding mechanism is regulated by a proximal arginine residue (R124) and a distal leucine residue (L16). Here, we have investigated the roles of these residues in maintaining the affinity for NO in the heme binding environment by using various time-resolved spectroscopy techniques that span the entire femtosecond-second temporal range in the UV-vis spectrum, and the femtosecond-nanosecond range by IR spectroscopy. Our findings indicate that the tightly regulated NO rebinding events following excitation in wild-type cytochrome c' are affected in the R124A variant. In the R124A variant, vibrational and electronic changes extend continuously across all time scales (from fs-s), in contrast to wild-type cytochrome c' and the L16A variant. Based on these findings, we propose a NO (re)binding mechanism for the R124A variant of cytochrome c' that is distinct from that in wild-type cytochrome c'. In the wider context, these findings emphasize the importance of heme pocket architecture in maintaining the reactivity of hemoproteins towards their chosen ligand, and demonstrate the power of spectroscopic probes spanning a wide temporal range. © 2013 FEBS.

fMRI evidence of ‘mirror’ responses to geometric shapes

Mirror neurons may be a genetic adaptation for social interaction [1]. Alternatively, the associative hypothesis [2], [3] proposes that the development of mirror neurons is driven by sensorimotor learning, and that, given suitable experience, mirror neurons will respond to any stimulus. This hypothesis was tested using fMRI adaptation to index populations of cells with mirror properties. After sensorimotor training, where geometric shapes were paired with hand actions, BOLD response was measured while human participants experienced runs of events in which shape observation alternated with action execution or observation. Adaptation from shapes to action execution, and critically, observation, occurred in ventral premotor cortex (PMv) and inferior parietal lobule (IPL). Adaptation from shapes to execution indicates that neuronal populations responding to the shapes had motor properties, while adaptation to observation demonstrates that these populations had mirror properties. These results indicate that sensorimotor training induced populations of cells with mirror properties in PMv and IPL to respond to the observation of arbitrary shapes. They suggest that the mirror system has not been shaped by evolution to respond in a mirror fashion to biological actions; instead, its development is mediated by stimulus-general processes of learning within a system adapted for visuomotor control