Size distribution of polycyclic aromatic hydrocarbons in a roadway tunnel in Lisbon, Portugal

Atmospheric aerosols of four aerodynamic size ranges were collected using high volume cascade impactors in an extremely busy roadway tunnel in Lisbon (Portugal). Dust deposited on the tunnel walls and guardrails was also collected. Average particle mass concentrations in the tunnel atmosphere were more than 30 times higher than in the outside urban background air, revealing its origins almost exclusively from fresh vehicle emissions. Most of the aerosol mass was concentrated in submicrometer fractions (65%), and polycyclic aromatic hydrocarbons (PAH) were even more concentrated in the finer particles with an average of 84% of total PAH present in sizes smaller than 0.49 mu m. The most abundant PAH were methylated phenanthrenes, fluoranthene and pyrene. About 46% of the total PAH mass was attributed to lower molecular weight compounds (two and three rings), suggesting a strong influence of diesel vehicle emissions on the production of local particulate PAH. The application of diagnostic ratios confirmed the relevance of this source of PAH in the tunnel ambient air. Deposited dust presented PAH profiles similar to the coarser aerosol size range, in agreement with the predominant origin of coarser aerosol particles from soil dust resuspension and vehicle wear products. (c) 201 1 Elsevier Ltd. All rights reserved.

Dinámica y cinética de los procesos físicos y químicos del radical OH con compuestos orgánicos volátiles (COVs) de relevancia atmosférica. Dynamics and kinetics of the physical and chemical processes of OH radicals with atmospheric relevant volatile organic compounds (VOCs)

El objetivo del presente proyecto es estudiar los procesos físicos y químicos del radical OH con compuestos orgánicos volátiles (COVs), con los cuales sea factible la formación de agregados de van der Waals (vdW) responsables de la curvatura en los gráficos de Arrhenius, empleando técnicas modernas, complementarias entre si y novedosas en el país. El problema será abordado desde tres perspectivas complementarias: 1) estudios cinéticos, 2) estudios mecanísticos y de distribución de productos y 3) estudios de la dinámica de los procesos físicos y químicos. La finalidad es alcanzar una mejor comprensión de los mecanismos que intervienen en el comportamiento químico de especies presentes en la atmósfera y obtener datos cinéticos de alta calidad que puedan alimentar modelos computacionales capaces de describir la composición de la atmósfera, presente y futura. Los objetivos son estudiar: 1) mediante fotólisis láser pulsada con detección por fluorescencia inducida por láser (PLP-LIF), en reactores de flujo, la cinética de reacción del radical OH(v”=0) con COVs que presentan gráficos de Arrhenius curvos con energías de activación negativas, tales como alcoholes insaturados, alquenos halogenados, éteres halogenados, ésteres alifáticos; 2) en una cámara de simulación de condiciones atmosféricas de gran volumen (4500 L), la identidad y el rendimiento de productos de las reacciones mencionadas, a fines de evaluar su impacto atmosférico y dilucidar los mecanismos de reacción; 3) mediante haces moleculares y espectroscopía láser, la estructura y reactividad de complejos de vdW entre alcoholes insaturados o aromáticos (cresoles) y el radical OH, como modelo de los aductos propuestos como responsables de la desviación al comportamiento de Arrhenius de las reacciones mencionadas; 4) mediante PLP-LIF y expansiones supersónicas, las constantes específicas estado a estado (ksts) de relajación/reacción del radical OH(v”=1-4) vibracionalmente excitado con los COVs mencionados. Los resultados experimentales obtenidos serán contrastados con cálculos ab-initio de estructura electrónica, los cuales apoyarán las interpretaciones, permitirán proponer estructuras de estados de transición y aductos colisionales, como así también calcular las frecuencias de vibración de los complejos de vdW para su posterior asignación en los espectros LIF y REMPI. Asimismo, los mecanismos de reacción propuestos y los parámetros cinéticos medidos experimentalmente serán comparados con aquellos obtenidos por cálculos teóricos. The aim of this project is to study the physical and chemical processes of OH radicals with volatile organic compounds (VOCs) with which the formation of van der Waals (vdW) clusters, responsible for the observed curvature in the Arrhenius plots, might be feasible. The problem will be addressed as follow : 1) kinetic studies; 2) products distribution and mechanistic studies and 3) dynamical studies of the physical and chemical processes. The purpose is to obtain a better understanding of the mechanisms that govern the chemical behavior of species present in the atmosphere and to obtain high quality kinetic data to be used as input to computational models. We will study: 1) the reaction kinetics of OH (v”=0) radicals with VOCs such as unsaturated alcohols, halogenated alkenes, halogenated ethers, aliphatic esters, which show curved Arrhenius plots and negative activation energies, by PLP-LIF, in flow systems; 2) in a large volume (4500 L) atmospheric simulation chamber, reaction products yields in order to evaluate their atmospheric impact and reaction mechanisms; 3) using molecular beams and laser spectroscopy, the structure and reactivity of the vdW complexes formed between the unsaturated or aromatic alcohols and the OH radicals as a model of the adducts proposed as responsible for the non-Arrhenius behavior; 4) the specific state-to-state relaxation/reaction rate constants (ksts) of the vibrationally excited OH (v”=1-4) radical with the VOCs by PLP-LIF and supersonic expansions. Ab-initio calculations will be carried out to support the interpretation of the experimental results, to obtain the transition state and collisional adducts structures, as well as to calculate the vibrational frequencies of the vdW complexes to assign to the LIF and REMPI spectra. Also, the proposed reaction mechanisms and the experimentally measured kinetic parameters will be compared with those obtained from theoretical calculations.

Emissions distribution in post-Kyoto international negotiations: a policy

An abundant scientific literature about climate change economics points out that the future participation of developing countries in international environmental policies will depend on their amount of pay offs inside and outside specific agreements. These studies are aimed at analyzing coalitions stability typically through a game theoretical approach. Though these contributions represent a corner stone in the research field investigating future plausible international coalitions and the reasons behind the difficulties incurred over time to implement emissions stabilizing actions, they cannot disentangle satisfactorily the role that equality play in inducing poor regions to tackle global warming. If we focus on the Stern Review findings stressing that climate change will generate heavy damages and policy actions will be costly in a finite time horizon, we understand why there is a great incentive to free ride in order to exploit benefits from emissions reduction efforts of others. The reluctance of poor countries in joining international agreements is mainly supported by historical responsibility of rich regions in generating atmospheric carbon concentration, whereas rich countries claim that emissions stabilizing policies will be effective only when developing countries will join them.Scholars recently outline that a perceived fairness in the distribution of emissions would facilitate a wide spread participation in international agreements. In this paper we overview the literature about distributional aspects of emissions by focusing on those contributions investigating past trends of emissions distribution through empirical data and future trajectories through simulations obtained by integrated assessment models. We will explain methodologies used to elaborate data and the link between real data and those coming from simulations. Results from this strand of research will be interpreted in order to discuss future negotiations for post Kyoto agreements that will be the focus of the next. Conference of the Parties in Copenhagen at the end of 2009. A particular attention will be devoted to the role that technological change will play in affecting the distribution of emissions over time and to how spillovers and experience diffusion could influence equality issues and future outcomes of policy negotiations.

Anomalous rainfall and associated atmospheric circulation in the northeast Spanish Mediterranean area and its relationship to sediment fluidization events in a lake

Changes in the dynamics of sediment transport in a Mediterranean lake (sediment fluidization events) are linked to atmospheric circulations patterns (trough monthly precipitation). In the basins of Lake Banyoles, located in the northeast of Spain, water enters mainly through subterranean springs, and associated fluctuations in the vertical migration of sediment distribution (fluidization events) present episodic behavior as a result of episodic rainfall in the area. The initiation of the fluidization events takes place when the monthly rainfall is ∼2.7 times greater than the mean monthly rainfall of the rainiest months in the area, especially in spring (April and May), October, and December. The duration of these events is found to be well correlated with the accumulated rainfall of the preceding 10 months before the process initiation. The rainfall, in turn, is mainly associated with six atmospheric circulation patterns among the 19 fundamental circulations that emerged in an earlier study focused on significant rainfall days in Mediterranean Spain. Among them, accentuated surface lows over the northeast of Spain, general northeasterly winds by low pressure centered to the east of Balearic Islands and short baroclinic waves over the Iberian Peninsula, with easterly flows over the northeastern coast of Spain, are found the most relevant atmospheric circulations that drive heavy rainfall events

USE OF A LOW-COST TEMPLATE-FREE ZSM-5 FOR ATMOSPHERIC PETROLEUM RESIDUE PYROLYSIS

To understand the physicochemical properties and catalytic activity during the pyrolysis of atmospheric petroleum residue, a template-free ZSM-5 zeolite was synthesized using a direct method without additional seeds or an organic structure director and compared with conventionally synthesized ZSM-5. The crystallinities of the two zeolites were evaluated by XRD and FTIR and were quite similar; however, structural analyses using SEM and argon physisorption revealed that the zeolites diverged in particle diameter and in the external surface area of the micropores. The synthesis procedure without a template incorporated additional aluminum into the crystalline network, according to ICP-AES and TPD NH3 experiments. The catalytic pyrolysis performed over the template-free ZSM-5 generated results comparable to those for pyrolysis performed over the conventional ZSM-5 according to its hydrocarbon distribution. The selectivity to aromatics compounds was exactly the same for both ZSM-5 zeolites, and these values stand out compared to thermal pyrolysis. The template-free ZSM-5 produced 20% of light hydrocarbons (C4-C6), where such compounds are olefins and paraffins of great interest to the petrochemical industry. Therefore, template-free ZSM-5 is promising for industrial use due to its lowered synthesis time, low-cost and significant distribution to light hydrocarbons.

Genesis and distribution of Mississippi Valley-type ore assemblages in Middle Silurian strata, Niagara Peninsula, Ontario /

Presently non-commercial occurrences of Mississippi Valley-type ore assemblages in the Middle Silurian strata of the Niagara Peninsula have been studied. Based on this detailed study, a new poly-stage genetic model is proposed which relates ore mineralization in carbonate environments to the evolution of the sedimentary basin. Sulphide ore mineralization occurred during two episodes: 1. During the late diagenesis stage, which is characterized by compaction-maturation of the sediments, the initial mineralization took place by upward and outward movement of connate waters. Metals were probably supplied from all the sediments regardless of their specific lithologies. However, clay minerals were possibly the main contributors. The possible source of sulphur was from petroleum-type hydrocarbons presently mixed with the sediments at the site of ore deposition. Evidence for this is the fact that the greatest abundance of ore minerals is in petroliferous carbonates. The hydrocarbons probably represent liquids remaining after upward migration to the overlying Guelph-Salina reservoirs. The majority of sphalerite and galena formed during this period, as well as accessory pyrite, marcasite, chalcopyrite, chalcocite, arsenopyrite, and pyrrhotite; and secondary dolomite, calcite, celestite, and gypsum. 2. During the presently ongoing surface erosion and weathering phase, which is marked by the downward movement of groundwater, preexisting sulphides were probably remobilized, and trace amounts of lead and zinc were leached from the host material, by groundwaters. Metal sulphides precipitated at, or below, the water table, or where atmospheric oxygen could raise the Eh of groundwaters to the point where soluble metal complexes are unstable and native sulphur co-precipitates with sphalerite and galena. This process, which can be observed today, also results in the transport and deposition of the host rock material. Breakdown of pre-existing sulphide and sulphate, as well as hydrocarbon present in the host rock, provided sulphur necessary for sulphide precipitation. The galena and sphalerite are accompanied by dolomite, calcite, gypsum, anglesite, native sulphur and possibly zincite.

Studies on the paratial and temporal distribution of surface meteorological parameters over Indian subcontinent

The intention of the present thesis work is to understand the physical processes responsible for climatic variability and predictability of the Indian subcontinent. The study is expected to delineate and emphasize the various boundaries and areas of transition and bring out the regional and temporal characteristics of the meteorological distribution of the country. The results obtained from the study is expected to provide a better understanding the physics of Indian cl imate, which can be incorporated for numerical weather prediction. The results obtained from the present study can be incorporated for climate modelling and long-term prediction of the meteorological parameters over Indian subcontinent

Spatio-temporal Variability of Atmospheric Ozone over Indian Subcontinent and its Relation to Meteorological Parameters

Ozone present in the atmosphere not only absorbs the biologically harmful ultraviolet radiation but also is an important ingredient of the climate system. The radiative absorption properties of ozone make it a determining factor in the structure of the atmosphere. Ozone in the troposphere has many negative impacts on humans and other living beings. Another significant aspect is the absorption of outgoing infrared radiation by ozone thus acting as a greenhouse gas. The variability of ozone in the atmosphere involves many interconnections with the incoming and outgoing radiation, temperature circulation etc. Hence ozone forms an important part of chemistry-climate as well as radiative transfer models. This aspect also makes the quantification of ozone more important. The discovery of Antarctic ozone hole and the role of anthropogenic activities in causing it made it possible to plan and implement necessary preventive measures. Continuous monitoring of ozone is also necessary to identify the effect of these preventive steps. The reactions involving the formation and destruction of ozone are influenced significantly by the temperature fluctuations of the atmosphere. On the other hand the variations in ozone can change the temperature structure of the atmosphere. Indian subcontinent is a region having large weather and climate variability which is evident from the large interannual variability of monsoon system over the region. Nearly half of Indian region comprises the tropical region. Most of ozone is formed in the tropical region and transported to higher latitudes. The formation and transport of ozone can be influenced by changes in solar radiation and various atmospheric circulation features. Besides industrial activities and vehicular traffic is more due to its large population. This may give rise to an increase in the production of tropospheric ozone which is greenhouse gas. Hence it becomes necessary to monitor the atmospheric ozone over this region. This study probes into the spatial distribution and temporal evolution of ozone over Indian subcontinent and discusses the contributing atmospheric parameters.

Studies on the horizontal and vertical distribution of clouds and their impact on energetics of the Atmosphere over the Indian Region

Motivation for the present study is to improve the scienti c understanding on the prominent gap areas in the average three-dimensional distribution of clouds and their impact on the energetics of the earth-atmosphere system. This study is focused on the Indian subcontinent and the surrounding oceans bound within the latitude-longitude bands of 30 S to 30 N and 30 E to 110 E. Main objectives of this study are to : (i) estimate the monthly and seasonal mean vertical distributions of clouds and their spatial variations (which provide the monthly and seasonal mean 3-dimensional distributions of clouds) using multi-year satellite data and investigate their association with the general circulation of the atmosphere, (ii) investigate the characteristics of the `pool of inhibited cloudiness' that appear over the southwest Bay of Bengal during the Asian summer monsoon season (revealed by the 3-dimensional distribution of clouds) and identify the potential mechanisms for its genesis, (iii) investigate the role of SST and atmospheric thermo-dynamical parameters in regulating the vertical development and distribution of clouds, (iv) investigate the vertical distribution of tropical cirrus clouds and their descending nature using lidar observations at Thiruvananthapuram (8.5 N, 77 E), a tropical coastal station at the southwest Peninsular India, and (v) assessment of the impact of clouds on the energetics of the earth-atmosphere system, by estimating the regional seasonal mean cloud radiative forcing at top-of-the-atmosphere (TOA) and latent heating of the atmosphere by precipitating clouds using satellite data

Modeled and observed atmospheric radiation balance during the West African dry season: role of mineral dust, biomass burning aerosol, and surface albedo

The global radiation balance of the atmosphere is still poorly observed, particularly at the surface. We investigate the observed radiation balance at (1) the surface using the ARM Mobile Facility in Niamey, Niger, and (2) the top of the atmosphere (TOA) over West Africa using data from the Geostationary Earth Radiation Budget (GERB) instrument on board Meteosat-8. Observed radiative fluxes are compared with predictions from the global numerical weather prediction (NWP) version of the Met Office Unified Model (MetUM). The evaluation points to major shortcomings in the NWP model's radiative fluxes during the dry season (December 2005 to April 2006) arising from (1) a lack of absorbing aerosol in the model (mineral dust and biomass burning aerosol) and (2) a poor specification of the surface albedo. A case study of the major Saharan dust outbreak of 6–12 March 2006 is used to evaluate a parameterization of mineral dust for use in the NWP models. The model shows good predictability of the large-scale flow out to 4–5 days with the dust parameterization providing reasonable dust uplift, spatial distribution, and temporal evolution for this strongly forced dust event. The direct radiative impact of the dust reduces net downward shortwave (SW) flux at the surface (TOA) by a maximum of 200 W m−2 (150 W m−2), with a SW heating of the atmospheric column. The impacts of dust on terrestrial radiation are smaller. Comparisons of TOA (surface) radiation balance with GERB (ARM) show the “dusty” forecasts reduce biases in the radiative fluxes and improve surface temperatures and vertical thermodynamic structure.

Can the dynamical impact of the stratosphere on the troposphere be described by large-scale adjustment to the stratospheric PV distribution?

Recent numerical experiments have demonstrated that the state of the stratosphere has a dynamical impact on the state of the troposphere. To account for such an effect, a number of mechanisms have been proposed in the literature, all of which amount to a large-scale adjustment of the troposphere to potential vorticity (PV) anomalies in the stratosphere. This paper analyses whether a simple PV adjustment suffices to explain the actual dynamical response of the troposphere to the state of the stratosphere, the actual response being determined by ensembles of numerical experiments run with an atmospheric general-circulation model. For this purpose, a new PV inverter is developed. It is shown that the simple PV adjustment hypothesis is inadequate. PV anomalies in the stratosphere induce, by inversion, flow anomalies in the troposphere that do not coincide spatially with the tropospheric changes determined by the numerical experiments. Moreover, the tropospheric anomalies induced by PV inversion are on a larger scale than the changes found in the numerical experiments, which are linked to the Atlantic and Pacific storm-tracks. These findings imply that the impact of the stratospheric state on the troposphere is manifested through the impact on individual synoptic-scale systems and their self-organization in the storm-tracks. Changes in these weather systems in the troposphere are not merely synoptic-scale noise on a larger scale tropospheric response, but an integral part of the mechanism by which the state of the stratosphere impacts that of the troposphere.

The influence of the atmospheric boundary layer on nocturnal layers of noctuids and other moths migrating over southern Britain

Insects migrating at high altitude over southern Britain have been continuously monitored by automatically-operating, vertical-looking radars over a period of several years. During some occasions in the summer months, the migrants were observed to form well-defined layer concentrations, typically at heights of 200-400 m, in the stable night-time atmosphere. Under these conditions, insects are likely to have control over their vertical movements and are selecting flight heights which are favourable for long-range migration. We therefore investigated the factors influencing the formation of these insect layers by comparing radar measurements of the vertical distribution of insect density with meteorological profiles generated by the UK Met. Office’s Unified Model (UM). Radar-derived measurements of mass and displacement speed, along with data from Rothamsted Insect Survey light traps provided information on the identity of the migrants. We present here three case studies where noctuid and pyralid moths contributed substantially to the observed layers. The major meteorological factors influencing the layer concentrations appeared to be: (a) the altitude of the warmest air, (b) heights corresponding to temperature preferences or thresholds for sustained migration and (c), on nights when air temperatures are relatively high, wind-speed maxima associated with the nocturnal jet. Back-trajectories indicated that layer duration may have been determined by the distance to the coast. Overall, the unique combination of meteorological data from the UM and insect data from entomological radar described here show considerable promise for systematic studies of high-altitude insect layering.

REMOTE SENSING OF AEOLIAN DUST PRODUCTION AND DISTRIBUTION

Airborne dust is of concern due to hazards in the localities affected by erosion, transport and deposition, but it is also of global concern due to uncertainties over its role in radiative forcing of climate. In order to model the environmental impact of dust, we need a better knowledge of sources and transport processes. Satellite remote sensing has been instrumental in providing this knowledge, through long time series of observations of atmospheric dust transport. Three remote sensing methodologies have been used, and are reviewed briefly in this paper. Firstly the use of observations from the Total Ozone Mapping Spectrometer (TOMS), secondly the use of the Infrared Difference Dust Index (IDDI) from Meterosat infrared data, thirdly the use of MODIS images from the rapid response system. These data have highlighted the major global sources of dust, mist of which are associated with endoreic drainage basins in deserts, which held lakes during Quaternary humid climate phases, and identified the Bodele Depression in Tchad as the dustiest place on Earth.

Atmosphere feedbacks during ENSO in a coupled GCM with a modified atmospheric convection scheme

The too diverse representation of ENSO in a coupled GCM limits one’s ability to describe future change of its properties. Several studies pointed to the key role of atmosphere feedbacks in contributing to this diversity. These feedbacks are analyzed here in two simulations of a coupled GCM that differ only by the parameterization of deep atmospheric convection and the associated clouds. Using the Kerry–Emanuel (KE) scheme in the L’Institut Pierre-Simon Laplace Coupled Model, version 4 (IPSL CM4; KE simulation), ENSO has about the right amplitude, whereas it is almost suppressed when using the Tiedke (TI) scheme. Quantifying both the dynamical Bjerknes feedback and the heat flux feedback in KE, TI, and the corresponding Atmospheric Model Intercomparison Project (AMIP) atmosphere-only simulations, it is shown that the suppression of ENSO in TI is due to a doubling of the damping via heat flux feedback. Because the Bjerknes positive feedback is weak in both simulations, the KE simulation exhibits the right ENSO amplitude owing to an error compensation between a too weak heat flux feedback and a too weak Bjerknes feedback. In TI, the heat flux feedback strength is closer to estimates from observations and reanalysis, leading to ENSO suppression. The shortwave heat flux and, to a lesser extent, the latent heat flux feedbacks are the dominant contributors to the change between TI and KE. The shortwave heat flux feedback differences are traced back to a modified distribution of the large-scale regimes of deep convection (negative feedback) and subsidence (positive feedback) in the east Pacific. These are further associated with the model systematic errors. It is argued that a systematic and detailed evaluation of atmosphere feedbacks during ENSO is a necessary step to fully understand its simulation in coupled GCMs.