Kinetic multi-layer model of gas-particle interactions in aerosols and clouds (KM-GAP): linking condensation, evaporation and chemical reactions of organics, oxidants and water

We present a novel kinetic multi-layer model for gas-particle interactions in aerosols and clouds (KM-GAP) that treats explicitly all steps of mass transport and chemical reaction of semi-volatile species partitioning between gas phase, particle surface and particle bulk. KM-GAP is based on the PRA model framework (Pöschl-Rudich-Ammann, 2007), and it includes gas phase diffusion, reversible adsorption, surface reactions, bulk diffusion and reaction, as well as condensation, evaporation and heat transfer. The size change of atmospheric particles and the temporal evolution and spatial profile of the concentration of individual chemical species can be modelled along with gas uptake and accommodation coefficients. Depending on the complexity of the investigated system, unlimited numbers of semi-volatile species, chemical reactions, and physical processes can be treated, and the model shall help to bridge gaps in the understanding and quantification of multiphase chemistry and microphysics in atmo- spheric aerosols and clouds. In this study we demonstrate how KM-GAP can be used to analyze, interpret and design experimental investigations of changes in particle size and chemical composition in response to condensation, evaporation, and chemical reaction. For the condensational growth of water droplets, our kinetic model results provide a direct link between laboratory observations and molecular dynamic simulations, confirming that the accommodation coefficient of water at 270 K is close to unity. Literature data on the evaporation of dioctyl phthalate as a function of particle size and time can be reproduced, and the model results suggest that changes in the experimental conditions like aerosol particle concentration and chamber geometry may influence the evaporation kinetics and can be optimized for eðcient probing of specific physical effects and parameters. With regard to oxidative aging of organic aerosol particles, we illustrate how the formation and evaporation of volatile reaction products like nonanal can cause a decrease in the size of oleic acid particles exposed to ozone.

Kinetic multi-layer model of gas-particle interactions in aerosols and clouds (KM-GAP): linking condensation, evaporation and chemical reactions of organics, oxidants and water

We present a novel kinetic multi-layer model for gas-particle interactions in aerosols and clouds (KMGAP) that treats explicitly all steps of mass transport and chemical reaction of semi-volatile species partitioning between gas phase, particle surface and particle bulk. KMGAP is based on the PRA model framework (P¨oschl-Rudich- Ammann, 2007), and it includes gas phase diffusion, reversible adsorption, surface reactions, bulk diffusion and reaction, as well as condensation, evaporation and heat transfer. The size change of atmospheric particles and the temporal evolution and spatial profile of the concentration of individual chemical species can be modeled along with gas uptake and accommodation coefficients. Depending on the complexity of the investigated system and the computational constraints, unlimited numbers of semi-volatile species, chemical reactions, and physical processes can be treated, and the model shall help to bridge gaps in the understanding and quantification of multiphase chemistry and microphysics in atmospheric aerosols and clouds. In this study we demonstrate how KM-GAP can be used to analyze, interpret and design experimental investigations of changes in particle size and chemical composition in response to condensation, evaporation, and chemical reaction. For the condensational growth of water droplets, our kinetic model results provide a direct link between laboratory observations and molecular dynamic simulations, confirming that the accommodation coefficient of water at 270K is close to unity (Winkler et al., 2006). Literature data on the evaporation of dioctyl phthalate as a function of particle size and time can be reproduced, and the model results suggest that changes in the experimental conditions like aerosol particle concentration and chamber geometry may influence the evaporation kinetics and can be optimized for efficient probing of specific physical effects and parameters. With regard to oxidative aging of organic aerosol particles, we illustrate how the formation and evaporation of volatile reaction products like nonanal can cause a decrease in the size of oleic acid particles exposed to ozone.

The simulation of the opposing fluxes of latent heat and CO2 over various land-use types: coupling a gas exchange model to a mesoscale atmospheric model

A mesoscale meteorological model (FOOT3DK) is coupled with a gas exchange model to simulate surface fluxes of CO2 and H2O under field conditions. The gas exchange model consists of a C3 single leaf photosynthesis sub-model and an extended big leaf (sun/shade) sub-model that divides the canopy into sunlit and shaded fractions. Simulated CO2 fluxes of the stand-alone version of the gas exchange model correspond well to eddy-covariance measurements at a test site in a rural area in the west of Germany. The coupled FOOT3DK/gas exchange model is validated for the diurnal cycle at singular grid points, and delivers realistic fluxes with respect to their order of magnitude and to the general daily course. Compared to the Jarvis-based big leaf scheme, simulations of latent heat fluxes with a photosynthesis-based scheme for stomatal conductance are more realistic. As expected, flux averages are strongly influenced by the underlying land cover. While the simulated net ecosystem exchange is highly correlated with leaf area index, this correlation is much weaker for the latent heat flux. Photosynthetic CO2 uptake is associated with transpirational water loss via the stomata, and the resulting opposing surface fluxes of CO2 and H2O are reproduced with the model approach. Over vegetated surfaces it is shown that the coupling of a photosynthesis-based gas exchange model with the land-surface scheme of a mesoscale model results in more realistic simulated latent heat fluxes.

Characterizing sampling bias in the trace gas climatologies of the SPARC Data Initiative

Monthly zonal mean climatologies of atmospheric measurements from satellite instruments can have biases due to the nonuniform sampling of the atmosphere by the instruments. We characterize potential sampling biases in stratospheric trace gas climatologies of the Stratospheric Processes and Their Role in Climate (SPARC) Data Initiative using chemical fields from a chemistry climate model simulation and sampling patterns from 16 satellite-borne instruments. The exercise is performed for the long-lived stratospheric trace gases O3 and H2O. Monthly sampling biases for O3 exceed 10% for many instruments in the high-latitude stratosphere and in the upper troposphere/lower stratosphere, while annual mean sampling biases reach values of up to 20% in the same regions for some instruments. Sampling biases for H2O are generally smaller than for O3, although still notable in the upper troposphere/lower stratosphere and Southern Hemisphere high latitudes. The most important mechanism leading to monthly sampling bias is nonuniform temporal sampling, i.e., the fact that for many instruments, monthly means are produced from measurements which span less than the full month in question. Similarly, annual mean sampling biases are well explained by nonuniformity in the month-to-month sampling by different instruments. Nonuniform sampling in latitude and longitude are shown to also lead to nonnegligible sampling biases, which are most relevant for climatologies which are otherwise free of biases due to nonuniform temporal sampling.

A comparison of greenhouse gas emissions in the residential sector of major Canadian cities

One of the most significant sources of greenhouse gas (GHG) emissions in Canada is the buildings sector, with over 30% of national energy end-use occurring in buildings. Energy use must be addressed to reduce emissions from the buildings sector, as nearly 70% of all Canada’s energy used in the residential sector comes from fossil sources. An analysis of GHG emissions from the existing residential building stock for the year 2010 has been conducted for six Canadian cities with different climates and development histories: Vancouver, Edmonton, Winnipeg, Toronto, Montreal, and Halifax. Variation across these cities is seen in their 2010 GHG emissions, due to climate, characteristics of the building stock, and energy conversion technologies, with Halifax having the highest per capita emissions at 5.55 tCO2e/capita and Montreal having the lowest at 0.32 tCO2e/capita. The importance of the provincial electricity grid’s carbon intensity is emphasized, along with era of construction, occupancy, floor area, and climate. Approaches to achieving deep emissions reductions include innovative retrofit financing and city level residential energy conservation by-laws; each region should seek location-appropriate measures to reduce energy demand within its residential housing stock, as well as associated GHG emissions.

Cities reducing their greenhouse gas emissions

The study asks how well are cities doing in reducing their greenhouse gas emissions. Data from six cities with repeat GHG emission inventories for the period 2004–2009 is examined: Berlin, Boston, Greater Toronto, London, New York City and Seattle. All of the cities are reducing their per capita GHG emissions, primarily through changes to stationary combustion. On average the cities are reducing per capita emissions by 0.27 t CO2e/capita per year; this is about the same average rate as the cities nation states, although the cities are reducing emissions faster in percentage terms.

Robust future changes in temperature variability under greenhouse gas forcing and the relationship with thermal advection

Recent temperature extremes have highlighted the importance of assessing projected changes in the variability of temperature as well as the mean. A large fraction of present day temperature variance is associated with thermal advection, as anomalous winds blow across the land-sea temperature contrast for instance. Models project robust heterogeneity in the 21st century warming pattern under greenhouse gas forcing, resulting in land-sea temperature contrasts increasing in summer and decreasing in winter, and the pole-to-equator temperature gradient weakening in winter. In this study, future monthly variability changes in the 17 member ensemble ESSENCE are assessed. In winter, variability in midlatitudes decreases while in very high latitudes and the tropics it increases. In summer, variability increases over most land areas and in the tropics, with decreasing variability in high latitude oceans. Multiple regression analysis is used to determine the contributions to variability changes from changing temperature gradients and circulation patterns. Thermal advection is found to be of particular importance in the northern hemisphere winter midlatitudes, where the change in mean state temperature gradients alone could account for over half the projected changes. Changes in thermal advection are also found to be important in summer in Europe and coastal areas, although less so than in winter. Comparison with CMIP5 data shows that the midlatitude changes in variability are robust across large regions, particularly high northern latitudes in winter and mid northern latitudes in summer.

Gas streaming motions towards the nucleus of M81

We present two-dimensional stellar and gaseous kinematics of the inner 120 x 250 pc2 of the LINER/Seyfert 1 galaxy M81, from optical spectra obtained with the Gemini Multi-Object Spectrograph (GMOS) integral field spectrograph on the Gemini-North telescope at a spatial resolution of approximate to 10 pc. The stellar velocity field shows circular rotation and, overall, is very similar to the published large-scale velocity field, but deviations are observed close to the minor axis which can be attributed to stellar motions possibly associated with a nuclear bar. The stellar velocity dispersion of the bulge is 162 +/- 15 km s-1, in good agreement with previous measurements and leading to a black hole mass of M(BH) = 5.5+3.6(-2.0) x 107 M(circle dot) based on the M(BH)-Sigma relationship. The gas kinematics is dominated by non-circular motions and the subtraction of the stellar velocity field reveals blueshifts of approximate to-100 km s-1 on the far side of the galaxy and a few redshifts on the near side. These characteristics can be interpreted in terms of streaming towards the centre if the gas is in the plane. On the basis of the observed velocities and geometry of the flow, we estimate a mass inflow rate in ionized gas of approximate to 4.0 x 10-3 M(circle dot) yr-1, which is of the order of the accretion rate necessary to power the LINER nucleus of M81. We have also applied the technique of principal component analysis (PCA) to our data, which reveals the presence of a rotating nuclear gas disc within approximate to 50 pc from the nucleus and a compact outflow, approximately perpendicular to the disc. The PCA combined with the observed gas velocity field shows that the nuclear disc is being fed by gas circulating in the galaxy plane. The presence of the outflow is supported by a compact jet seen in radio observations at a similar orientation, as well as by an enhancement of the [O i]/H alpha line ratio, probably resulting from shock excitation of the circumnuclear gas by the radio jet. With these observations we are thus resolving both the feeding - via the nuclear disc and observed gas inflow, and the feedback - via the outflow, around the low-luminosity active nucleus of M81.

Cloning and characterization of a zebrafish homologue of human AQP1: a bifunctional water and gas channel

Chen LM, Zhao J, Musa-Aziz R, Pelletier MF, Drummond IA, Boron WF. Cloning and characterization of a zebrafish homologue of human AQP1: a bifunctional water and gas channel. Am J Physiol Regul Integr Comp Physiol 299: R1163-R1174, 2010. First published August 25, 2010; doi:10.1152/ajpregu.00319.2010.-The mammalian aquaporins AQP1, AQP4, and AQP5 have been shown to function not only as water channels but also as gas channels. Zebrafish have two genes encoding an AQP1 homologue, aqp1a and aqp1b. In the present study, we cloned the cDNA that encodes the zebrafish protein Aqp1a from the 72-h postfertilization (hpf) embryo of Danio rerio, as well as from the swim bladder of the adult. The deduced amino-acid sequence of aqp1a consists of 260 amino acids and is 59% identical to human AQP1. By analyzing the genomic DNA sequence, we identified four exons in the aqp1a gene. By in situ hybridization, aqp1a is expressed transiently in the developing vasculature and in erythrocytes from 16 to 48 h of development. Later, at 72 hpf, aqp1a is expressed in dermal ionocytes and in the swim bladder. Western blot analysis of adult tissues reveals that Aqp1a is most highly expressed in the eye and swim bladder. Xenopus oocytes expressing aqp1a have a channel-dependent (*) osmotic water permeability (P(f)*) that is indistinguishable from that of human AQP1. On the basis of the magnitude of the transient change in surface pH (Delta pHS) that were recorded as the oocytes were exposed to either CO(2) or NH(3), we conclude that zebrafish Aqp1a is permeable to both CO(2) and NH(3). The ratio (Delta pHS*)CO2/P(f)* is about half that of human AQP1, and the ratio (Delta pHS*)NH3/P(f)* is about one-quarter that of human AQP1. Thus, compared with human AQP1, zebrafish Aqp1a has about twice the selectivity for CO(2) over NH(3).

A further exploration of a nucleophilicity index based on the gas-phase ionization potentials

An empirical nucleophilicity index based on the gas-phase ionization potentials has been recently shown to be useful categorizing and settling the nucleophilicity power of a series of captodative ethylenes reacting in cycloaddition reactions (L.R. Domingo, E. Chamorro, P. Perez, Journal of Organic Chemistry 73 (2008) 4615-4624). In the present work, the applicability of such model is tested within a broader series of substituted alkenes, substituted aromatic compounds and simple nucleophilic molecules. This index obtained within a Koopman`s theorem framework has been evaluated here in both gas and solution phases for several well-known nucleophiles. These results are found to be linearly correlated. Finally, the feasibility of the predictive character of this index has been discussed in comparison to the available experimental nucleophilicities of some amines in water. These results further support and validate the usefulness of such approximation in the modeling of the global nucleophilicity. (C) 2008 Elsevier B.V. All rights reserved.

Gas-Phase Nucleophilic and Elimination Reactions in Simple Alkyl Nitrates

There has been increasing interest in the gas-phase reactivity of alkyl nitrates because of their well-known applications as explosives and because of then role in atmospheric and in marine processes This manuscript describes an experimental study by FT-ICR techniques of the gas-phase reactions of OH(-) and F(-) with methyl and ethyl Innate For methyl nitrate, the main reaction channel is found to be an elimination process promoted by abstraction of an a proton from the methyl group. Nucleophilic displacement of nitrate anion through an S(N)2 process at the carbon center Is also found to he an important reaction channel with methyl nitrate In ethyl nitrate, Ruination of NO(3)(-) is greatly enhanced and this is attributed to the ease of an E2-type elimination process promoted by proton abstraction at the beta position of the ethyl group. Theoretical calculations at the MP2/6-311+G(3df,2p)//MP2/6-31+G(d) level of theory ale consistent with the relative importance of the reaction channels and suggest that these reactions proceed through a double well potential The calculations also predict that nucleophilic attack by OH(-) at the nitrogen center (Sn2@N) is energetically the rueful ad pathway but experiments with (18)OH(-) showed no evidence for this channel. Single-point calculations reveal a strong preference for approach to the emboli center and may explain the lack of reactivity at the nitrogen center. Calculations were also carried out or NH(2)(-) and SH(-) to establish the reactivity pattern to provide a better understanding of environmentally relevant nitrate esters.

Identification of lift-off mechanism failure for salt drill-in drilling fluid containing polymer filter cake through adsorption/desorption studies

Drilling fluid`s contact with the productive zone of horizontal or complex wells can reduce well productivity by fluid invasion in the borehole wall. Salted drilling drill-in fluid containing polymers has often been applied in horizontal or complex petroleum wells in the poorly consolidated sandstone reservoirs of the Campos basin, Rio de Janeiro, Brazil. This fluid usually consists of natural polymers such as starch and xanthan gum, which are deposited as a filter cake on the wellbore wall during the drilling. Therefore, the identification of a lift-off mechanism failure, which can be detachment or blistering and pinholing, will enable formulation improvements. increasing the chances of success during filter cake removal in open hole operations. Likewise, knowledge of drill-in drilling fluid adsorption/desorption onto sand can help understand the filter cake-rock adhesion mechanism and consequently filter cake lift-off mechanism failures. The present study aimed to identify the lift-off failure mechanism for this type of fluid filter cake studying adsorption/desorption onto SiO(2) using solutions of natural polymers, lubricants, besides the fluid itself. Ellipsometry was employed to measure this process. The adsorption/desorption studies showed that the adsorbed layer of drilling fluid onto the walls of the rock pores is made up of clusters of polymers, linked by hydrogen bonds, which results in a force of lower cohesion compared to the electrostatic interaction between silica and polymers. Consequently, it was found that the most probable filter cake failure mechanism is rupture (blistering and pinholing), which results in the formation of ducts within the filter cake. (C) 2009 Elsevier B.V. All rights reserved.

REPETRO - Regime Aduaneiro Especial de Importação e Exportação de Bens Destinados à Pesquisa e Lavra de Petróleo e Gás: análise dos entraves e propostas de soluções

REPETRO, the special tax regime for importing and exporting goods for the exploration and drilling of oil and gas, aims at bringing foreign assets to Brazil enjoying a suspension or even an exemption of taxes, so that Brazilian industry may profit from about 8 billion American dollars in investments. The creation of normative devices as well as the management of the REPETRO model are under the exclusive responsibility of the Brazilian Internal Revenue Services. REPETRO was created in 1999 and is composed of the following customs treatments: importation of goods with suspension of taxes by use of the drawback special regime, suspension mode for national exporting industry; exportation with fictitious exit for the national industry; temporary admission of goods or assets used in oil exploration and production, attending to the needs of both the national and foreign market. Considering the inability of the Brazilian government in restructuring its foreign trade model so that a strong investment in technology could provide for the sector¿s needs, we must ask how we can change REPETRO to help the various companies in the oil business? The issue is very important for one of our main economic activities, though not enough studied. The energy sector has a strategic importance for the development and the economic independence of any country. The winds of globalization lead Brazil to open its economy in the last decade and the national policy for exploration and drilling (E&D) was altered. The government created a new agency dedicated to market control and energy policies, the National Agency for Oil and Biofuels (ANP). With the opening of the market, Petróleo Brasileiro S.A. - Petrobras, the Brazilian giant, lost the monopoly of the oil business. The P-50 Platform, with a capacity for 180,000 barrels per day, was imported based on REPETRO. When it began operating on April 21st, 2006, Brazil achieved self-sufficiency in oil production. The present work intends to estimate the main variables affecting the importation and exportation of goods and assets for E&D, showing how REPETRO works. We also intend to look at the results yielded by the REPETRO model for the development of the production of oil and gas in Brazil, as well as show proposals for its modernization. It has been established that even though since its implementation the REPETRO model has brought fiscal advantages through the reduction of tax costs relating to foreign commerce operations and the incentive of investments in the E&D area with the increase in the national oil production there remain the following limitations: lack of preparation and of knowledge of the model; lack of adjustement of the model to the reality of actitity of E&D of oil and gas; taxes over the pre-operational stage or investment in oil production stage; non-allowance of full access by the national industry to the supply of goods and products relating to the industrialization of goods allowed by REPETRO; other fiscal and administrative difficulties. We conclude that the REPETRO model is important for the development of the area of E&D of oil and gas, but not completely effective. It is necessary to change it or create a new model based on a new perspective of the customs treatment of the activities of exploration and production, minimizing administrative procedures relating to the operations of exportation and importation.

Da revolução do gás não convencional nos EUA tendo como substrato uma interferência governamental persistente no estímulo a atividade econômica e no fomento as inovações tecnológicas afetas ao setor

O presente estudo versa sobre os fatores tecnológicos e ambientais que vêm resultando no crescimento da produção de gás natural não convencional nos EUA. Os objetos de analise principais serão as políticas públicas, assim como a dinâmica entre os atores sociais e o ambiente propício que fora criado para que houvesse o adensamento do fomento e do estímulo às inovações tecnológicas sucedidas no setor.

O impacto da melhoria de um processo operacional na lucratividade e competitividade: um estudo de caso na subsidiária brasileira de uma empresa do ramo de petróleo

Após uma sequência histórica de ciclos econômicos no Brasil, desde o final da década de 90, o país presencia a abertura do setor do Petróleo ligado à descoberta do pré-sal e o volume imensurável das reservas naturais. Esse marco pôde determinar o início de um dos mais relevantes e diversificados ciclos de industrialização na história econômica do Brasil. Mesmo nesse ramo de negócio, um mercado de gigantes, de multinacionais, de grandes players com estratégias inovadoras e múltiplos know-how's insubstituíveis, é fato conhecido, principalmente para os profissionais dessa seara, que muitas empresas de petróleo possuem inúmeros fatores críticos com urgente necessidade de melhoria. O objetivo principal desta dissertação é fazer inicialmente uma breve análise estratégica e mercadológica da subsidiária brasileira de um grupo multinacional do ramo de Petróleo e Gás especializado em tecnologia de fluidos de perfuração de poços de petróleo, com presença em mais de vinte países. Após imersão no contexto, realizar a análise detalhada de um processo em especial, a primeira vista sem importância, que ao ser estudado, monitorado e mapeado, pôde ser ajustado, redesenhado e implementado, apresentando ganhos substanciais para a corporação relacionados à competitividade e lucratividade.