New Heterogeneous Catalysts for the Selective Reduction of NOx under Lean Conditions. Final Report

The original goal of this program was the identification and design of new noble-metal-based catalysts for the selective catalytic reduction of nitric oxide by hydrocarbons under excess oxygen (i.e., ''lean'') conditions (HC-SCR). Work conducted in the first funding cycle of this award (i.e., 1997-2000) was successful in allowing us to develop an understanding of the fundamental surface chemistry taking place during the adsorption and reaction of nitrogen oxides and propylene on the surface of supported noble metal catalysts. Both experimental results collected in our own group as well as molecular simulation results published by Professor Neurock suggested that in order to improve the performance of the Pt catalysts--in terms of the nitrogen selectivity and the temperature window of operation-- it was necessary to introduce a second metal. However, synthesizing such catalysts with the metals of interest (i.e., Pt-Au, Pt-Ru, Pt-Rh, etc.) with some degree of control of the structure and composition of the resulting supported metal particles is in itself a research challenge. Consequently, the bulk of our efforts during the second funding cycle of this award (covered by this report) was shifted to the use of organometallic cluster precursors for the synthesis on novel bimetallic catalysts. During this time we have also continued to maintain an interest in NOx abatement, but have redirected our efforts from the HC-SCR process to the more promising from a commercial standpoint NOx Storage Reduction (NSR) approach

EXAFS Characterization of Dendrimer-Derived Pt/γ-Al2O3

The various steps involved in the preparation of a Pt/-Al2O3 material using hydroxyl-terminated generation four (G4OH) PAMAM dendrimers as templates were monitored by EXAFS. The results indicate that Cl ligands in the Pt precursors (H2PtCl6 and K2PtCl4) were partially replaced by aquo ligands upon hydrolysis to form [PtCl3(H2O)3]+ and [PtCl2(H2O)2] species. After interaction of such species with G4OH, Cl ligands from the first coordination shell of Pt were further replaced by nitrogen atoms from the dendrimer interior, indicating the complexation of Pt with the dendrimer. This process was accompanied by a transfer of the electron density from the dendrimer to Pt, indicating that the former plays the role of a ligand. Following treatment of the H2PtCl6/G4OH and K2PtCl4/G4OH composites with NaBH4, no substantial changes were detected in the electronic or coordination environment of Pt, and no formation of metal nanoparticles was observed. However, when the reduction treatment was performed with H2, the formation of extremely small Pt clusters incorporating no more than 4 Pt atoms was observed. These Pt species remained strongly bonded to the dendrimer and their nuclearity depends on the length of the H2 treatment. Formation of Pt nanoparticles with an average diameter of approximately 10 Å was finally observed after the deposition of H2PtCl6/G4OH on -Al2O3 and drying, suggesting that their formation may be related to the collapse of the dendrimer structure. The Pt nanoparticles formed appear to have high mobility, since subsequent thermal treatment in O2/H2 led to further sintering

An Assessment of the Efficiency of Dust Regional Modelling to Predict Saharan Dust Transport Episodes

Aerosol levels at Mediterranean Basin are significantly affected by desert dust that is eroded in North Africa and is transported northwards. This study aims to assess the performance of the Dust REgional Atmospheric Model (BSC-DREAM8b) in the prediction of dust outbreaks near the surface in Eastern Mediterranean. For this purpose, model PM10 predictions covering a 7-year period and PM10 observations at five surface monitoring sites in Greece are used. A quantitative criterion is set to select the significant dust outbreaks defined as those when the predicted PM10 surface concentration exceeds 12 μg/m3. The analysis reveals that significant dust transport is usually observed for 1–3 consecutive days. Dust outbreak seasons are spring and summer, while some events are also forecasted in autumn. The seasonal variability of dust transport events is different at Finokalia, where the majority of events are observed in spring and winter. Dust contributes by 19–25% to the near surface observed PM10 levels, which can be increased to more than 50 μg/m3 during dust outbreaks, inducing violations of the air quality standards. Dust regional modeling can be regarded as a useful tool for air quality managers when assessing compliance with air quality limit values

EARLINET: towards an advanced sustainable European aerosol lidar network

The European Aerosol Research Lidar Network, EARLINET, was founded in 2000 as a research project for establishing a quantitative, comprehensive, and statistically significant database for the horizontal, vertical, and temporal distribution of aerosols on a continental scale. Since then EARLINET has continued to provide the most extensive collection of ground-based data for the aerosol vertical distribution over Europe. This paper gives an overview of the network's main developments since 2000 and introduces the dedicated EARLINET special issue, which reports on the present innovative and comprehensive technical solutions and scientific results related to the use of advanced lidar remote sensing techniques for the study of aerosol properties as developed within the network in the last 13 years. Since 2000, EARLINET has developed greatly in terms of number of stations and spatial distribution: from 17 stations in 10 countries in 2000 to 27 stations in 16 countries in 2013. EARLINET has developed greatly also in terms of technological advances with the spread of advanced multiwavelength Raman lidar stations in Europe. The developments for the quality assurance strategy, the optimization of instruments and data processing, and the dissemination of data have contributed to a significant improvement of the network towards a more sustainable observing system, with an increase in the observing capability and a reduction of operational costs. Consequently, EARLINET data have already been extensively used for many climatological studies, long-range transport events, Saharan dust outbreaks, plumes from volcanic eruptions, and for model evaluation and satellite data validation and integration. Future plans are aimed at continuous measurements and near-real-time data delivery in close cooperation with other ground-based networks, such as in the ACTRIS (Aerosols, Clouds, and Trace gases Research InfraStructure Network) www.actris.net, and with the modeling and satellite community, linking the research community with the operational world, with the aim of establishing of the atmospheric part of the European component of the integrated global observing system.Peer ReviewedPostprint (published version

Nine years of UV aerosol optical depth measurements at Thessaloniki, Greece

Spectral measurements of the aerosol optical depth (AOD) and the Ångström coefficient were conducted at Thessaloniki, Greece (40.5° N, 22.9° E) between January 1997 and December 2005 with a Brewer MKIII double-monochromator spectroradiometer. The dataset was compared with collocated measurements of a second spectroradiometer (Brewer MKII) and a CIMEL sun-photometer, showing correlations of 0.93 and 0.98, respectively. A seasonal variation of the AOD was observed at Thessaloniki, with AOD values at 340 nm of 0.52 and 0.28 for August and December respectively. Back trajectories of air masses for up to 4 days were used to assess the influence of long-range transport from various regions to the aerosol load over Thessaloniki. It is shown that part of the observed seasonality can be attributed to air masses with high AOD originating from North-Eastern and Eastern directions during summertime. The analysis of the long-term record (9 years) of AOD showed a downward tendency. A similar decreasing tendency was found in the record of the PM$_{10}$ aerosol measurements, which are conducted near the surface at 4 air-quality monitoring stations in the area of the city of Thessaloniki

Effects on surface atmospheric photo-oxidants over Greece during the total solar eclipse event of 29 March 2006

International audienceThis study investigates the effects of the total solar eclipse of 29 March 2006 on surface air-quality levels over Greece based on observations at a number of sites in conjunction with chemical box modelling and 3-D air-quality modelling. Emphasis is given on surface ozone and other photooxidants at four Greek sites Kastelorizo, Finokalia (Crete), Pallini (Athens) and Thessaloniki, which are located at gradually increasing distances from the path of the eclipse totality and are characterized by different air pollution levels. The eclipse offered the opportunity to test our understanding of air pollution build-up and the response of the gas-phase chemistry of photo-oxidants during a photolytical perturbation using both a photochemical box model and a regional air-quality offline model based on the modeling system WRF/CAMx. At the relatively unpolluted sites of Kastelorizo and Finokalia no clear impact of the solar eclipse on surface O3, NO2 and NO concentrations can be deduced from the observations and model simulations as the calculated changes in net ozone production rates between eclipse and non eclipse conditions are rather small compared to the ozone variability and hence the solar eclipse effects on ozone can be easily masked by transport. At the polluted sites of Thessaloniki and Pallini, the solar eclipse effects on O3, NO2 and NO concentrations are clearly revealed from both the measurements and 3-D air-quality modeling with the net effect being a decrease in O3 and NO and an increase in NO2 as NO2 formed from the reaction of O3 with NO while at the same time NO2 is not efficiently photolysed. It is evident from the 3-D air quality modeling over Greece that the maximum effects of the eclipse on O3, NO2 and NO are reflected at the large urban agglomerations of Athens, and Thessaloniki where the maximum of the emissions occur

The Total Solar Eclipse of March 2006: overview

International audienceThis paper provides an overview of integrated, multi-disciplinary effort to study the effects of a total solar eclipse on the environment, with special focus on the atmosphere. On the occasion of the 29 March 2006 total solar eclipse, visible over the Eastern Mediterranean, several research and academic institutes organised co-ordinated experimental campaigns, at different distances from the totality and in various environments in terms of air quality. The detailed results are presented in a number of scientific papers included in a Special Issue of Atmospheric Chemistry and Physics. The effects of the eclipse on the meteorology and the spectral solar radiation, the chemical response of the atmosphere to the abrupt "switch off" of the sun and the induced changes in the stratosphere and the ionosphere, have been among the issues covered. The rare event of a total solar eclipse provided the opportunity to evaluate 1-D and 3-D radiative transfer models (in the atmosphere and underwater), mesoscale meteorological, regional air quality and photochemical box models, against measurements. Within the challenging topics of this effort has been the investigation of eclipse impacts on ecosystems (field crops and marine plankton) and the identification of eclipse induced gravity waves, for the first time with simultaneous measurements at three altitudes namely the troposphere, the stratosphere and the ionosphere

Study of the effect of different type of aerosols on UV-B radiation from measurements during EARLINET

Routine lidar measurements of the vertical distribution of the aerosol extinction coefficient and the extinction-to-backscatter ratio have been performed at Thessaloniki, Greece using a Raman lidar system in the frame of the EARLINET project since 2000. Co-located spectral and broadband solar UV-B irradiance measurements, as well as total ozone observations, were available whenever lidar measurements were obtained. From the available measurements several cases could be identified that allowed the study of the effect of different types of aerosol on the levels of the UV-B solar irradiance at the Earth's surface. The TUV radiative transfer model has been used to simulate the irradiance measurements, using total ozone and the lidar aerosol data as input. From the comparison of the model results with the measured spectra the effective single scattering albedo was determined using an iterative procedure, which has been verified against results from the 1998 Lindenberg Aerosol Characterization Experiment. It is shown that for the same aerosol optical depth and for the same total ozone values the UV-B irradiances at the Earth's surface can show differences up to 10%, which can be attributed to differences in the aerosol type. It is shown that the combined use of the estimated single scattering albedo and of the measured extinction-to-backscatter ratio leads to a better characterization of the aerosol type probed

EARLINET: 12-year of aerosol profiling over Europe

EARLINET has been collecting high quality aerosol optical profiles over Europe since 2000. The comparison with automatic collected dataset of aerosol optical depth (AOD) from AERONET and MODIS demonstrates the effectiveness of EARLINET regular measurement schedule for climatological studies. The analysis of optical properties in the local boundary layer indicates that the general decrease of AOD observed by different platforms over Europe in the last decade could be due to the modification of aerosol properties (towards less absorbing and larger particles) in the lower troposphere

EARLINET: Towards an advanced sustainable European aerosol lidar network

The European Aerosol Research Lidar Network, EARLINET, was founded in 2000 as a research project for establishing a quantitative, comprehensive, and statistically significant database for the horizontal, vertical, and temporal distribution of aerosols on a continental scale. Since then EARLINET has continued to provide the most extensive collection of ground-based data for the aerosol vertical distribution over Europe. This paper gives an overview of the network's main developments since 2000 and introduces the dedicated EARLINET special issue, which reports on the present innovative and comprehensive technical solutions and scientific results related to the use of advanced lidar remote sensing techniques for the study of aerosol properties as developed within the network in the last 13 years. Since 2000, EARLINET has developed greatly in terms of number of stations and spatial distribution: from 17 stations in 10 countries in 2000 to 27 stations in 16 countries in 2013. EARLINET has developed greatly also in terms of technological advances with the spread of advanced multiwavelength Raman lidar stations in Europe. The developments for the quality assurance strategy, the optimization of instruments and data processing, and the dissemination of data have contributed to a significant improvement of the network towards a more sustainable observing system, with an increase in the observing capability and a reduction of operational costs. Consequently, EARLINET data have already been extensively used for many climatological studies, long-range transport events, Saharan dust outbreaks, plumes from volcanic eruptions, and for model evaluation and satellite data validation and integration. Future plans are aimed at continuous measurements and near-real-time data delivery in close cooperation with other ground-based networks, such as in the ACTRIS (Aerosols, Clouds, and Trace gases Research InfraStructure Network) www.actris.net, and with the modeling and satellite community, linking the research community with the operational world, with the aim of establishing of the atmospheric part of the European component of the integrated global observing system