The NO+O3 reaction: a triple oxygen isotope perspective on the reaction dynamics and atmospheric implications for the transfer of the ozone isotope anomaly

Atmospheric nitrate shows a large oxygen isotope anomaly (Delta 17 O), characterized by an excess enrichment of 17 O over 18 O, similar to the ozone molecule. Modeling and observations assign this specific isotopic composition mainly to the photochemical steady state that exists in the atmosphere between ozone and nitrate precursors, namely, the nitrogen oxides (NOx=NO+NO2). However, this transfer is poorly quantified and is built on unverified assumptions about which oxygen atoms of ozone are transferred to NO(x), greatly weakening any interpretation of the nitrate oxygen isotopic composition in terms of chemical reaction pathways and the oxidation state of the atmosphere. With the aim to improve our understanding and quantify how nitrate inherits this unusual isotopic composition, we have carried out a triple isotope study of the reaction NO+O3. Using ozone intramolecular isotope distributions available in the literature, we have found that the central atom of the ozone is abstracted by NO with a probability of (8+/-5)%(+/-2 sigma) at room temperature. This result is at least qualitatively supported by dynamical reaction experiments, the non-Arrhenius behavior of the kinetic rate of this reaction, and the kinetic isotope fractionation factor. Finally, we have established the transfer function of the isotope anomaly of O3 to NO2, which is described by the linear relationship Delta 17 O(NO2)=A x Delta 17 O(O3)+B, with A=1.18+/-0.07(+/-1 sigma) and B=(6.6+/-1.5)[per thousand](+/-1 sigma). Such a relationship can be easily incorporated into models dealing with the propagation of the ozone isotope anomaly among oxygen-bearing species in the atmosphere and should help to better interpret the oxygen isotope anomaly of atmospheric nitrate in terms of its formation reaction pathways.     

Diffusive diffraction phenomenon in a porous polymer material observed by NMR using radio-frequency field gradients

Pulsed field gradient NMR diffusion experiments can, in principle, lead to the "diffusive diffraction" phenomenon. In practice, its observation by gradients of the static magnetic field is difficult in real systems because they involve internal gradients due to the static magnetic field (necessary for polarizing nuclear spins). This latter drawback can be circumvented by using gradients of the radio-frequency (rf) field (the other magnetic field used in any NMR experiment). For the first time, by means of rf gradients, a so-called diffusive diffraction peak has been observed in a real porous system and its position provides a value of the mean distance between pores; this can be further complemented by the mean pore size determined from the dependence of the apparent diffusion coefficient with respect to the diffusion interval.     

Influence of the intercalated cations on the surface energy of montmorillonites: consequences for the morphology and gas barrier properties of polyethylene/montmorillonites nanocomposites

Organically modified montmorillonites obtained by cation exchange from the same natural layered silicate were studied. The surface properties of the pristine and a series of organically modified clays were determined by inverse gas chromatography and the water adsorption mechanisms were studied by a gravimetric technique coupled with a microcalorimeter. A significant increase of the specific surface area, a decrease of the water adsorption, and a decrease of the dispersive component of the surface energy were observed when the sodium cations of the natural montmorillonite were exchanged for a quaternary ammonium. Slighter differences in surface properties were observed, on the other hand, between the different types of organically modified montmorillonites. Indeed, similar dispersive components of the surface energy were determined on the organoclays. Nevertheless, the specific surface area increased in the range 48-80 m(2)/g with increasing d-spacing values and the presence of specific groups attached to the quaternary ammonium, such as phenyl rings or hydroxyl groups, led to some specific behaviors, i.e., a more pronounced base character and a higher water adsorption at high activity, respectively. Differences in interlayer cation chain organization, denoted as crystallinity, were also observed as a function of the nature of the chains borne by the quaternary ammonium. In a later step, polyethylene-based nanocomposites were prepared with those organically modified montmorillonites. The clay dispersion and the barrier properties of the nanocomposites were discussed as a function of the montmorillonite characteristics and of the matrix/montmorillonite interactions expected from surface energy characterization.     

Observation of WZ production

We report the first observation of the associated production of a W boson and a Z boson. This result is based on 1.1 fb;-1 of integrated luminosity from pp collisions at sqrt[s]=1.96 TeV collected with the CDF II detector at the Fermilab Tevatron. We observe 16 WZ candidates passing our event selection with an expected background of 2.7+/-0.4 events. A fit to the missing transverse energy distribution indicates an excess of events compared to the background expectation corresponding to a significance equivalent to 6 standard deviations. The measured cross section is sigma(pp-->WZ)=5.0(-1.6)(+1.8) pb, consistent with the standard model expectation.     

Lagrangian temperature, velocity, and local heat flux measurement in Rayleigh-Bénard convection

We have developed a small, neutrally buoyant, wireless temperature sensor. Using a camera for optical tracking, we obtain simultaneous measurements of position and temperature of the sensor as it is carried along by the flow in Rayleigh-Bénard convection, at Ra approximately 10;{10}. We report on statistics of temperature, velocity, and heat transport in turbulent thermal convection. The motion of the sensor particle exhibits dynamics close to that of Lagrangian tracers in hydrodynamic turbulence. We also quantify heat transport in plumes, revealing self-similarity and extreme variations from plume to plume.     

Subcritical dynamo bifurcation in the Taylor-Green flow

We report direct numerical simulations of dynamo generation for flow generated using a Taylor-Green forcing. We find that the bifurcation is subcritical and show its bifurcation diagram. We connect the associated hysteretic behavior with hydrodynamics changes induced by the action of the Lorentz force. We show the geometry of the dynamo magnetic field and discuss how the dynamo transition can be induced when an external field is applied to the flow.     

Recurrence plots and Shannon entropy for a dynamical analysis of asynchronisms in noninvasive mechanical ventilation

Recurrence plots were introduced to quantify the recurrence properties of chaotic dynamics. Hereafter, the recurrence quantification analysis was introduced to transform graphical interpretations into statistical analysis. In this spirit, a new definition for the Shannon entropy was recently introduced in order to have a measure correlated with the largest Lyapunov exponent. Recurrence plots and this Shannon entropy are thus used for the analysis of the dynamics underlying patient assisted with a mechanical noninvasive ventilation. The quality of the assistance strongly depends on the quality of the interactions between the patient and his ventilator which are crucial for tolerance and acceptability. Recurrence plots provide a global view of these interactions and the Shannon entropy is shown to be a measure of the rate of asynchronisms as well as the breathing rhythm.     

Structure, morphology and interface properties of ultrathin SnTTBPP(OH)2-films adsorbed on Ag(100)

The molecular interaction of dihydroxo[5,10,15,20-tetrakis(4-tert-butyl-phenyl)porphyrinato]-tin(IV) (SnTTBPP(OH)(2)), the structural order and growth of ultrathin films on Ag(100) have been studied by means of low-energy electron diffraction (LEED) and synchrotron based photoelectron spectroscopy, i.e., X-ray photoemission (XPS) and near-edge X-ray absorption fine structure (NEXAFS/XANES) spectroscopy. For the first time, monolayer adsorption of a metalloporphyrin with octahedral coordination of the metal center by two additional axial hydroxo ligands is investigated in a multi-technique study. The delicate balance of molecule-substrate interactions and intermolecular interactions leads to the formation of a densely-packed organic monolayer which is commensurate with the Ag(100) substrate. From NEXAFS linear dichroism an almost coplanar orientation of the porphyrin system is derived. XPS and NEXAFS clearly indicate that the axial hydroxo ligands are cleaved in monolayer films, i.e., upon adsorption to the Ag substrate. With increasing film thickness orientational order gets lost and leads to polycrystalline growth for thicker films as confirmed by scanning X-ray transmission microscopy (STXM).     

Polarity patterns of stress fibers

Stress fibers are contractile actomyosin bundles commonly observed in the cytoskeleton of metazoan cells. The spatial profile of the polarity of actin filaments inside contractile actomyosin bundles is either monotonic (graded) or periodic (alternating). In the framework of linear irreversible thermodynamics, we write the constitutive equations for a polar, active, elastic one-dimensional medium. An analysis of the resulting equations for the dynamics of polarity shows that the transition from graded to alternating polarity patterns is a nonequilibrium Lifshitz point. Active contractility is a necessary condition for the emergence of sarcomeric, alternating polarity patterns.     

Search for Z' --> e+ e- using dielectron mass and angular distribution

We search for Z' bosons in dielectron events produced in pp collisions at square root of s = 1.96 TeV, using 0.45 fb(-1) of data accumulated with the Collider Detector at Fermilab II detector at the Fermilab Tevatron. To identify the Z' --> e+ e- signal, both the dielectron invariant mass distribution and the angular distribution of the electron pair are used. No evidence of a signal is found, and 95% confidence level lower limits are set on the Z' mass for several models. Limits are also placed on the mass and gauge coupling of a generic Z', as well as on the contact-interaction mass scales for different helicity structure scenarios.