Tecnical Note: Analysis of non-regulated vehicular emissions by extractive FTIR spectrometry: tests on a hybrid car in Mexico City

International audienceA methodology to acquire valuable information on the chemical composition and evolution of vehicular emissions is presented. The analysis of the gases is performed by passing a constant flow of a sample gas from the tail-pipe into a 10 L multi-pass cell. The absorption spectra within the cell are obtained using an FTIR spectrometer at 0.5 cm?1 resolution along a 13.1 m optical path. Additionally, the total flow from the exhaust is continuously measured from a differential pressure sensor on a \textit{Pitot} tube installed at the exit of the exhaust. This configuration aims to obtain a good speciation capability by coadding spectra during 30 s and reporting the emission (in g/km) of both criteria and non-regulated pollutants, such as CO2, CO, NO, SO2, NH3, HCHO and some NMHC, during predetermined driving cycles. The advantages and disadvantages of increasing the measurement frequency, as well as the effect of other parameters such as spectral resolution, cell volume and flow rate, are discussed. To test and evaluate the proposed technique, experiments were performed on a dynamometer running FTP-75 and typical driving cycles for the Mexico City Metropolitan Area (MCMA) on a Toyota Prius hybrid vehicle. This car is an example of recent marketed automotive technology dedicated to reduced emissions, increasing the need for sensitive detection techniques. This study shows the potential of the proposed technique to measure and report in real time the emissions of a large variety of pollutants, even from a super ultra-low emission vehicle (SULEV). The emissions of HC's, NOx, CO and CO2 obtained here were compared to experiments performed in other locations with the same model vehicle. The proposed technique provides a tool for future studies comparing in detail the emissions of vehicles using alternative fuels and emission control systems

Predicting diurnal variability of fine inorganic aerosols and their gas-phase precursors near downtown Mexico City

International audiencePartitioning of semi-volatile nitrate and ammonium between the gas and particulate phases is studied combining two thermodynamic models that explicitly include crustal elements and simulate both branches (deliquescence, efflorescence) of aerosol behavior and measurements taken near downtown Mexico City during a field campaign conducted in February?March, 2005. Overall, no significant differences between model predictions (within 30% of error) are observed for particulate ammonium (PM2.5, PM1). In cases of moderate to high RH (40?70%), mostly occurring during the 1st and 2nd daily sampling periods (06:00?10:00 h, 10:00?14:00 h, LST), 4 h PM2.5 nitrate measurements are predicted within 30%. When RH drops below 30%, characteristic of the afternoon sampling periods (14:00-18:00 h), the efflorescence branch is most consistent with observed PM nitrate. Residual error analysis of these low RH cases suggest that aerosol nitrate loading or sulfate-to-nitrate molar ratio control phase behavior, hence the partitioning of semi-volatile PM2.5 nitrate in gas and particulate phases. Finally, inclusion of crustal elements in the modeling framework reduces the error in predicted PM2.5 ammonium by 25%. These findings, if generally applicable, can help improve air quality modeling in nitrate deficient environments

Energy levels of few electron quantum dots imaged and characterized by atomic force microscopy

Strong confinement of charges in few electron systems such as in atoms, molecules and quantum dots leads to a spectrum of discrete energy levels that are often shared by several degenerate quantum states. Since the electronic structure is key to understanding their chemical properties, methods that probe these energy levels in situ are important. We show how electrostatic force detection using atomic force microscopy reveals the electronic structure of individual and coupled self-assembled quantum dots. An electron addition spectrum in the Coulomb blockade regime, resulting from a change in cantilever resonance frequency and dissipation during tunneling events, shows one by one electron charging of a dot. The spectra show clear level degeneracies in isolated quantum dots, supported by the first observation of predicted temperature-dependent shifts of Coulomb blockade peaks. Further, by scanning the surface we observe that several quantum dots may reside on what topologically appears to be just one. These images of grouped weakly and strongly coupled dots allow us to estimate their relative coupling strengths.Comment: 11 pages, 6 figure

Precipitating Ordered Skyrmion Lattices from Helical Spaghetti

Magnetic skyrmions have been the focus of intense research due to their potential applications in ultra-high density data and logic technologies, as well as for the unique physics arising from their antisymmetric exchange term and topological protections. In this work we prepare a chiral jammed state in chemically disordered (Fe, Co)Si consisting of a combination of randomly-oriented magnetic helices, labyrinth domains, rotationally disordered skyrmion lattices and/or isolated skyrmions. Using small angle neutron scattering, (SANS) we demonstrate a symmetry-breaking magnetic field sequence which disentangles the jammed state, resulting in an ordered, oriented skyrmion lattice. The same field sequence was performed on a sample of powdered Cu2OSeO3 and again yields an ordered, oriented skyrmion lattice, despite relatively non-interacting nature of the grains. Micromagnetic simulations confirm the promotion of a preferred skyrmion lattice orientation after field treatment, independent of the initial configuration, suggesting this effect may be universally applicable. Energetics extracted from the simulations suggest that approaching a magnetic hard axis causes the moments to diverge away from the magnetic field, increasing the Dzyaloshinskii-Moriya energy, followed subsequently by a lattice re-orientation. The ability to facilitate an emergent ordered magnetic lattice with long-range orientation in a variety of materials despite overwhelming internal disorder enables the study of skyrmions even in imperfect powdered or polycrystalline systems and greatly improves the ability to rapidly screen candidate skyrmion materials

Analysis of non-regulated vehicular emissions by extractive FTIR spectrometry: tests on a hybrid car in Mexico City

International audienceA methodology to acquire valuable information on the chemical composition and evolution of vehicular emissions is presented. The analysis of the gases is performed by passing a constant flow of a sample gas from the tail-pipe into a 10 L multi-pass cell. The absorption spectra within the cell are obtained using an FTIR spectrometer at 0.5 cm-1 resolution along a 13.1 m optical path. Additionally, the total flow from the exhaust is continuously measured from a differential pressure sensor on a Pitot tube installed at the exit of the exhaust. This configuration aims to obtain a good speciation capability by coadding spectra during 30 s and reporting the emission (in g/km) of key and non-regulated pollutants, such as CO2, CO, NO, SO2, NH3, HCHO, NMHC, during predetermined driving routines. The advantages and disadvantages of increasing the acquisition frequency, as well as the effect of other parameters such as spectral resolution, cell volume and flow rate, are discussed. With the aim of testing and evaluating the proposed technique, experiments were performed on a dynamometer running FTP-75 and typical driving cycles of the Mexico City Metropolitan Area (MCMA) on a Toyota Prius hybrid vehicle. This car is an example of recent automotive technology to reach the market dedicated to reduce emissions and therefore pressing the need of low detection techniques. This study shows the potential of the proposed technique to measure and report in real time the emissions of a large variety of pollutants, even from a super ultra-low emission vehicle (SULEV). The emissions of HC's, NOx, CO and CO2 obtained here are similar to experiments performed in other locations with the same vehicle model. Some differences suggest that an inefficient combustion process and type of gasoline used in the MCMA may be partly responsible for lower CO2 and higher CO and NO emission factors. Also, a fast reduction of NO emission to very low values is observed after cold ignition, giving rise to moderate N2O and eventually NH3 emissions. The proposed technique provides a tool for future studies comparing in detail the emissions of different technologies using alternative fuels and emission control systems

Role of van der Waals forces in the adsorption and diffusion of organic molecules on an insulating surface

The adsorption and diffusion of 3,4,9,10-perylene-tetracarboxylic-dianhydride (PTCDA) molecules on a nanostructured KBr (001) surface were investigated by combining noncontact atomic force microscopy (NC-AFM) and first-principles calculations. Atomically resolved measurements demonstrate trapping of PTCDA molecules in intentionally created rectangular monolayer-deep substrate pits and a preferential adsorption at kink sites. In order to understand the experimental results, we found that it was essential to include a first-principles treatment of the van der Waals interactions. We show that at some sites on the surface, 85% of the molecular binding is provided by van der Waals interactions, and in general it is always the dominant contribution to the adsorption energy. It also qualitatively changes molecular diffusion on the surface. Based on the specificity of the molecular interaction at kink sites, the species of the imaged ionic sublattice in the NC-AFM measurements could be identified.Peer reviewe