Updated national emission inventory and comparison with the Emissions Database for Global Atmospheric Research (EDGAR): case of Lebanon

Physically based computational modeling is an effective tool for estimating and predicting the spatial distribution of pollutant concentrations in complex environments. A detailed and up-to-date emission inventory is one of the most important components of atmospheric modeling and a prerequisite for achieving high model performance. Lebanon lacks an accurate inventory of anthropogenic emission fluxes. In the absence of a clear emission standard and standardized activity datasets in Lebanon, this work serves to fill this gap by presenting the first national effort to develop a national emission inventory by exhaustively quantifying detailed multisector, multi-species pollutant emissions in Lebanon for atmospheric pollutants that are internationally monitored and regulated as relevant to air quality. Following the classification of the Emissions Database for Global Atmospheric Research (EDGAR), we present the methodology followed for each subsector based on its characteristics and types of fuels consumed. The estimated emissions encompass gaseous species (CO, NOx, SO2), and particulate matter (PM2.5 and PM10). We compare totals per sector obtained from the newly developed national inventory with the international EDGAR inventory and previously published emission inventories for the country for base year 2010 presenting current discrepancies and analyzing their causes. The observed discrepancies highlight the fact that emission inventories, especially for data-scarce settings, are highly sensitive to the activity data and their underlying assumptions, and to the methodology used to estimate the emissions.

Closed-Form Formulation of the Thermodynamically Consistent Electrochemical Model Considering Electrochemical Co-Oxidation of CO and H2 for Simulating Solid Oxide Fuel Cells

Achieving efficient solid oxide fuel cell operation and simultaneous prevention of degradation effects calls for the development of precise on-line monitoring and control tools based on predictive, computationally fast models. The originality of the proposed modelling approach originates from the hypothesis that the innovative derivation procedure enables the development of a thermodynamically consistent multi-species electrochemical model that considers the electrochemical co-oxidation of carbon monoxide and hydrogen in a closed-form. The latter is achieved by coupling the equations for anodic reaction rates with the equation for anodic potential. Furthermore, the newly derived model is capable of accommodating the diffusive transport of gaseous species through the gas diffusion layer, yielding a computationally efficient quasi-one-dimensional model. This resolves a persistent knowledge gap, as the proposed modelling approach enables the modelling of multi-species fuels in a closed form, resulting in very high computational efficiency, and thus enable the model’s real-time capability. Multiple validation steps against polarisation curves with different fuel mixtures confirm the capability of the newly developed model to replicate experimental data. Furthermore, the presented results confirm the capability of the model to accurately simulate outside the calibrated variation space under different operating conditions and reformate mixtures. These functionalities position the proposed model as a beyond state-of-the-art tool for model supported development and control applications.

Exploring Methane Emission Drivers in Wetlands: The Cases of Massaciuccoli and Porta Lakes (Northern Tuscany, Italy)

Wetlands are hotspots of CH4 emissions to the atmosphere, mainly sustained by microbial decomposition of organic matter in anoxic sediments. Several knowledge gaps exist on how environmental drivers shape CH4 emissions from these ecosystems, posing challenges in upscaling efforts to estimate global emissions from waterbodies. In this work, CH4 and CO2 diffusive fluxes, along with chemical and isotopic composition of dissolved ionic and gaseous species, were determined from two wetlands of Tuscany (Italy): (i) Porta Lake, a small wetland largely invaded by Phragmites australis reeds experiencing reed die-back syndrome, and (ii) Massaciuccoli Lake, a wide marsh area including open-water basins and channels affected by seawater intrusion and eutrophication. Both wetlands were recognized as net sources of CH4 to the atmosphere. Our data show that the magnitude of CH4 diffusive emission was controlled by CH4 production and consumption rates, being mostly governed by (i) water temperature and availability of labile carbon substrates and (ii) water column depth, wind exposure and dissolved O2 contents, respectively. This evidence suggests that the highest CH4 diffusive fluxes were sustained by reed beds, providing a large availability of organic matter supporting acetoclastic methanogenesis, with relevant implications for global carbon budget and future climate models.

Effects of He and Ar Heat-Assisted Plasma Treatments on the Adhesion Properties of Polytetrafluoroethylene (PTFE)

Heat-assisted plasma (HAP) treatment using He gas is known to improve the adhesive-bonding and adhesive-free adhesion properties of polytetrafluoroethylene (PTFE). In this study, we investigated the effects of He and Ar gaseous species on the HAP-treated PTFE surface. Epoxy (EP) adhesive-coated stainless steel (SUS304) and isobutylene–isoprene rubber (IIR) were used as adherents for the evaluation of the adhesive-bonding and adhesive-free adhesion properties of PTFE. In the case of adhesive bonding, the PTFE/EP-adhesive/SUS304 adhesion strength of the Ar-HAP-treated PTFE was the same as that of the He-HAP-treated PTFE. In the case of adhesive-free adhesion, the PTFE/IIR adhesion strength of the Ar-HAP-treated PTFE was seven times lower than that of the He-HAP-treated PTFE. The relation among gaseous species used in HAP treatment, adhesion properties, peroxy radical density ratio, surface chemical composition, surface modification depth, surface morphology, surface hardness, and the effect of irradiation with vacuum ultraviolet (VUV) and UV photons were investigated. The different adhesive-free adhesion properties obtained by the two treatments resulted from the changes in surface chemical composition, especially the ratios of oxygen-containing functional groups and C–C crosslinks.

Simulation of Wood Combustion in PATO Using a Detailed Pyrolysis Model Coupled to fireFoam

The numerical simulation of fire propagation requires capturing the coupling between wood pyrolysis, which leads to the production of various gaseous species, and the combustion of these species in the flame, which produces the energy that sustains the pyrolysis process. Experimental and numerical works of the fire community are targeted towards improving the description of the pyrolysis process to better predict the rate of production and the chemical nature of the pyrolysis gases. We know that wood pyrolysis leads to the production of a large variety of chemical species: water, methane, propane, carbon monoxide and dioxide, phenol, cresol, hydrogen, etc. With the idea of being able to capitalize on such developments to study more accurately the physics of fire propagation, we have developed a numerical framework that couples a detailed three-dimensional pyrolysis model and fireFoam. In this article, we illustrate the capability of the simulation tool by treating the combustion of a wood log. Wood is considered to be composed of three phases (cellulose, hemicellulose and lignin), each undergoing parallel degradation processes leading to the production of methane and hydrogen. We chose to simplify the gas mixture for this first proof of concept of the coupling of a multi-species pyrolysis process and a flame. In the flame, we consider two separate finite-rate combustion reactions for methane and hydrogen. The flame evolves during the simulation according to the concentration of the two gaseous species produced from the material. It appears that introducing different pyrolysis species impacts the temperature and behavior of the flame.

Formation Mechanism and Porosity Development in Porous Boron Nitride

In the past decade, porous boron nitride (BN) has proven promising as a novel class of inorganic materials in the field of separations and particularly adsorption. Owing to its high surface area and thermal stability, porous BN has been researched for CO2 capture and water cleaning, for instance. However, most research remains at laboratory scale due to a lack of understanding of the formation mechanism of porous BN, which is still largely a ‘black box’ and prevents scale-up. Partial reaction pathways have been unveiled, but they omit critical steps in the formation, including the porosity development, which is key to adsorption. To unlock the potential of porous BN at a larger scale, we have investigated its formation from the perspective of both chemical formation and porosity development. We have characterised reaction intermediates obtained at different temperatures with a range of analytical and spectroscopic tools. Using these analyses, we propose a mechanism that highlights the key stages of BN formation and its porosity, including the intermediates and gaseous species formed in the process. We identified that the formation of non-porous carbon nitride is crucial to form porous BN with release of porogens, such as HCN and CO2. This work paves the way for scaled-up processes to use porous BN to its full potential at industrial level for gas and liquid separations.

Simultaneous Detection of Dopamine and Serotonin with carbon-based electrodes

Graphite-based materials, like pyrolyzed carbon electrodes, are widely used as implantable electrochemical sensors, for the detection of neurotransmitters, neuromodulators, and gaseous species, thanks to their strong mechanical properties, superior electron-transfer kinetics, and in-vivo stability. Electrochemical properties of graphite can be improved by coating them with carbon nanotubes (CNTs) which improves sensitivity, selectivity, and resistance to biofouling. Although several types of electrodes have been developed to detect biologically relevant targets like monoamines, multiplexed sensing of dopamine and serotonin is not yet widely available. Herein we introduce pyrolyzed carbon electrodes coated with CNTs for fast scan cyclic voltammetry for simultaneous detection of dopamine and serotonin with a sensitivity of 52/microM and 5nA/microM, respectively. Serotonin shows a broad oxidation peak at 0.68V. When dopamine and serotonin are probed simultaneously at 10 Hz, dopamine oxidizes at 0.1V 0.1 and serotonin oxidizes at 0.78V and dopamine reduces at -0.35V and serotonin at 0.1V. Thus the sensors shows discrimination between dopamine and serotonin and are suitable for simultaneous detection of these monoamines. Keywords: Carbon nanotubes, Electrochemistry, Dopamine, Serotonin, Anti-fouling Surfaces

Extension of a gaseous dry deposition algorithm to oxidized volatile organic compounds and hydrogen cyanide for application in chemistry transport models

The dry deposition process refers to flux loss of an atmospheric pollutant due to uptake of the pollutant by the Earth's surfaces, including vegetation, underlying soil, and any other surface types. In chemistry transport models (CTMs), the dry deposition flux of a chemical species is typically calculated as the product of its surface layer concentration and its dry deposition velocity (Vd); the latter is a variable that needs to be highly empirically parameterized due to too many meteorological, biological, and chemical factors affecting this process. The gaseous dry deposition scheme of Zhang et al. (2003) parameterizes Vd for 31 inorganic and organic gaseous species. The present study extends the scheme of Zhang et al. (2003) to include an additional 12 oxidized volatile organic compounds (oVOCs) and hydrogen cyanide (HCN), while keeping the original model structure and formulas, to meet the demand of CTMs with increasing complexity. Model parameters for these additional chemical species are empirically chosen based on their physicochemical properties, namely the effective Henry's law constants and oxidizing capacities. Modeled Vd values are compared against field flux measurements over a mixed forest in the southeastern US during June 2013. The model captures the basic features of the diel cycles of the observed Vd. Modeled Vd values are comparable to the measurements for most of the oVOCs at night. However, modeled Vd values are mostly around 1 cm s−1 during daytime, which is much smaller than the observed daytime maxima of 2–5 cm s−1. Analysis of the individual resistance terms and uptake pathways suggests that flux divergence due to fast atmospheric chemical reactions near the canopy was likely the main cause of the large model–measurement discrepancies during daytime. The extended dry deposition scheme likely provides conservative Vd values for many oVOCs. While higher Vd values and bidirectional fluxes can be simulated by coupling key atmospheric chemical processes into the dry deposition scheme, we suggest that more experimental evidence of high oVOC Vd values at additional sites is required to confirm the broader applicability of the high values studied here. The underlying processes leading to high measured oVOC Vd values require further investigation.

African anthropogenic emissions inventory for gases and particles from 1990 to 2015

There are very few African regional inventories providing biofuel and fossil fuel emissions. Within the framework of the DACCIWA project, we have developed an African regional anthropogenic emission inventory including the main African polluting sources (wood and charcoal burning, charcoal making, trucks, cars, buses and two-wheeled vehicles, open waste burning, and flaring). To this end, a database on fuel consumption and emission factors specific to Africa was established using the most recent measurements. New spatial proxies (road network, power plant geographical coordinates) were used to convert national emissions into gridded inventories at a 0.1∘ × 0.1∘ spatial resolution. This inventory includes carbonaceous particles (black and organic carbon) and gaseous species (CO, NOx, SO2 and NMVOCs) for the period 1990–2015 with a yearly temporal resolution. We show that all pollutant emissions are globally increasing in Africa during the period 1990–2015 with a growth rate of 95 %, 86 %, 113 %, 112 %, 97 % and 130 % for BC, OC, NOx, CO, SO2 and NMVOCs, respectively. We also show that Western Africa is the highest emitting region of BC, OC, CO and NMVOCs, followed by Eastern Africa, largely due to domestic fire and traffic activities, while Southern Africa and Northern Africa are the highest emitting regions of SO2 and NOx due to industrial and power plant sources. Emissions from this inventory are compared to other regional and global inventories, and the emissions uncertainties are quantified by a Monte Carlo simulation. Finally, this inventory highlights key pollutant emission sectors in which mitigation scenarios should focus on. The DACCIWA inventory (https://doi.org/10.25326/56, Keita et al., 2020) including the annual gridded emission inventory for Africa for the period 1990–2015 is distributed by the Emissions of atmospheric Compounds and Compilation of Ancillary Data (ECCAD) system (https://eccad.aeris-data.fr/, last access: 19 July 2021​​​​​​​). For review purposes, ECCAD has set up an anonymous repository where subsets of the DACCIWA data can be accessed directly through https://www7.obs-mip.fr/eccad/essd-surf-emis-dacciwa/ (last access: 19 July 2021).