A new multi-scale model of urban air pollution is presented. This model combines a chemistry–transport model (CTM) that includes a comprehensive treatment of atmospheric chemistry and transport on spatial scales down to 1 km and a street-network model that describes the atmospheric concentrations of pollutants in an urban street network. The street-network model is the Model of Urban Network of Intersecting Canyons and Highways (MUNICH), which consists of two main components: a street-canyon component and a street-intersection component. MUNICH is coupled to the Polair3D CTM of the Polyphemus air quality modeling platform to constitute the Street-in-Grid (SinG) model. MUNICH is used to simulate the concentrations of the chemical species in the urban canopy, which is located in the lowest layer of Polair3D, and the simulation of pollutant concentrations above rooftops is performed with Polair3D. Interactions between MUNICH and Polair3D occur at roof level and depend on a vertical mass transfer coefficient that is a function of atmospheric turbulence. SinG is used to simulate the concentrations of nitrogen oxides (NO_x) and ozone (O₃) in a Paris suburb. Simulated concentrations are compared to NO_x concentrations measured at two monitoring stations within a street canyon. SinG shows better performance than MUNICH for nitrogen dioxide (NO₂) concentrations. However, both SinG and MUNICH underestimate NO_x. For the case study considered, the model performance for NO_x concentrations is not sensitive to using a complex chemistry model in MUNICH and the Leighton NO–NO₂–O₃ set of reactions is sufficient.

Particles are emitted by different sources and are also formed in the atmosphere. Despite the large impact of atmospheric particles on health and climate, large uncertainties remain concerning their representation in models. To reduce these uncertainties as much as possible, a representation of the main processes involved in aerosol dynamics and chemistry is necessary. For that purpose, SSH-aerosol was developed to represent the evolution of the mass and number concentrations of primary and secondary particles, across different scales, using state-of-the-art modules, taking into account processes that are usually not considered in air-quality or climate modelling. For example, the particle mixing state and the growth of ultra-fine particles are taken into account in the aerosol dynamics, the affinity of semi-volatile organic compounds with water and viscosity are taken into account in the partitioning between the gas and particle phases of organics and the formation of extremely low-volatility organic compounds from biogenic precursors is represented. SSH-aerosol is modular and can be used with different levels of complexity. It may be used as standalone to analyse chamber measurements. It is also designed to be easily coupled to 3D models, adapting the level of complexity to the spatial scale studied.

A secondary organic aerosol (SOA) model, H²O (Hydrophilic/Hydrophobic Organic), is evaluated over the Paris area. This model treats the formation of SOA with two kinds of surrogate species: hydrophilic species (which condense preferentially on an aqueous phase) and hydrophobic species (which condense only on an organic phase). These surrogates species are formed from the oxidation in the atmosphere of volatile organic compounds (VOC) by radicals (HO and NO₃) and ozone. These VOC are either biogenic (isoprene, monoterpenes and sesquiterpenes) or anthropogenic (mainly aromatic compounds). This model includes the formation of aerosols from different precursors (biogenic precursors, aromatics), and semi-volatile organic compounds (SVOC) from traffic. The H²O aerosol model was incorporated into the Polyphemus air quality modeling platform and applied to the Paris area and evaluated by comparison to measurements performed during the Megapoli campaign in July 2009. The comparison to measurements in the suburbs and in the city center of Paris shows that the model gives satisfactory results for both elemental carbon (EC) and organic carbon (OC). However, the model gives a peak of OC concentrations in the morning due to high emissions from traffic, which does not appear in measurements. Uncertainties in the modeled temperature, which can affect the gas-particle partitioning, in the partitioning of primary SVOC or underestimation of primary organic aerosol (POA) evaporation by the model could explain the differences between model and measurements. Moreover, using a theoretical mechanism for the oxidation of primary SVOC and intermediate volatility organic compounds (IVOC), POA concentrations were found to be likely overestimated by models due to the use of simple partitioning constants (which do not take into account the affinity of a compound with the liquid aerosol solution) or due to the assumption that the organic aerosol solution is a one-phase ideal solution. The organic aerosol in the city center of Paris was found to be originating mostly from distant sources with only 30 to 38% due to local sources.

This work aims at quantifying the relative contribution of secondary organic aerosol (SOA) precursors emitted by wildfires to organic aerosol (OA) formation during summer of 2007 over the Euro-Mediterranean region, where intense wildfires occurred. A new SOA formation mechanism, H²O_aro, including recently identified aromatic volatile organic compounds (VOCs) emitted from wildfires, is developed based on smog chamber experiment measurements under low- and high-NO_x regimes. The aromatic VOCs included in the mechanism are toluene, xylene, benzene, phenol, cresol, catechol, furan, naphthalene, methylnaphthalene, syringol, guaiacol, and structurally assigned and unassigned compounds with at least six carbon atoms per molecule (USC>6). This mechanism H²O_aro is an extension of the H²O (hydrophilic–hydrophobic organic) aerosol mechanism: the oxidation of the precursor forms surrogate species with specific thermodynamic properties (volatility, oxidation degree and affinity to water). The SOA concentrations over the Euro-Mediterranean region in summer of 2007 are simulated using the chemistry transport model (CTM) Polair3D of the air-quality platform Polyphemus, where the mechanism H²O_aro was implemented. To estimate the relative contribution of the aromatic VOCs, intermediate volatility, semi-volatile and low-volatility organic compounds (I/S/L-VOCs), to wildfires OA concentrations, different estimations of the gaseous I/S/L-VOC emissions (from primary organic aerosol – POA – using a factor of 1.5 or from non-methanic organic gas – NMOG – using a factor of 0.36) and their ageing (one-step oxidation vs. multi-generational oxidation) are also tested in the CTM. Most of the particle OA concentrations are formed from I/S/L-VOCs. On average during the summer of 2007 and over the Euro-Mediterranean domain, they are about 10 times higher than the OA concentrations formed from VOCs. However, locally, the OA concentrations formed from VOCs can represent up to 30 % of the OA concentrations from biomass burning. Amongst the VOCs, the main contributors to SOA formation are phenol, benzene and catechol (CAT; 47 %); USC>6 compounds (23 %); and toluene and xylene (12 %). Sensitivity studies of the influence of the VOCs and the I/S/L-VOC emissions and chemical ageing mechanisms on PM_2.5 concentrations show that surface PM_2.5 concentrations are more sensitive to the parameterization used for gaseous I/S/L-VOC emissions than for ageing. Estimating the gaseous I/S/L-VOC emissions from POA or from NMOG has a high impact on local surface PM_2.5 concentrations (reaching −30 % in the Balkans, −8 % to −16 % in the fire plume and +8 % to +16 % in Greece). Considering the VOC as SOA precursors results in a moderate increase in PM_2.5 concentrations mainly in the Balkans (up to 24 %) and in the fire plume (+10 %).

With the growing evidence that high particle number concentrations may impact health, modelling their emissions and understanding formation processes is necessary, especially in cities where many people are exposed. As emission inventories of particle numbers and size distribution over cities are usually not available, a methodology is defined to estimate them from PM_2.5 emissions and ratios of PM₁ $/$ PM_2.5 and PM_0.1 $/$ PM_2.5 by activity sector. In this methodology, a fitting parameter α_em is used to redistribute the number concentrations in the lowest emission diameter range. This parameter is chosen by comparing measured and simulated number concentrations during non-nucleation days. The emission size distribution is then finely discretised by conserving both mass and number in each of the size ranges where emissions are specified. The methodology is applied over Greater Paris during the MEGAPOLI campaign (July 2009). Three-dimensional simulations are performed using the chemistry transport model Polair3D/Polyphemus coupled to the aerosol module SSH-aerosol to represent the evolution of particles by condensation, evaporation, coagulation, and nucleation, with a sectional approach for the size distribution. The model is first compared to measurements during non-nucleation days, and the influence over the month of July 2009 of three different nucleation parameterisations is assessed, i.e. binary (sulfuric acid, water), ternary (sulfuric acid, ammonia, water), and heteromolecular (extremely low-volatility organic compounds (ELVOCs) from monoterpenes and sulfuric acid). The modelled number concentrations compare very well to measurements, with an average normalised mean error of 42 % for the daily number concentrations of particles larger than 10 nm and 37 % for the number concentrations of particles larger than 100 nm. The influence of the binary nucleation is low, and the ternary nucleation scheme leads to better simulated number concentrations (in terms of bias and error) at only one site out of three, but it systematically reduces the model to measurement correlation, suggesting that ternary nucleation may not be the dominant process in new particle formation. However, the relative bias and error, as well as the correlation at suburban sites, are systematically improved using the heteromolecular nucleation scheme involving sulfuric acid and ELVOCs from monoterpenes. This suggests that heteromolecular nucleation may be important in cities, especially at suburban sites in summer, and that a better characterisation of the emissions of ELVOC precursors from traffic is needed.

In the urban environment, gas and particles impose adverse impacts on the health of pedestrians. The conventional computational fluid dynamics (CFD) methods that regard pollutants as passive scalars cannot reproduce the formation of secondary pollutants and lead to uncertain prediction. In this study, SSH-aerosol, a modular box model that simulates the evolution of gas, primary and secondary aerosols, is coupled with the CFD software, OpenFOAM and Code_Saturne. The transient dispersion of pollutants emitted from traffic in a street canyon is simulated using the unsteady Reynolds-averaged Navier–Stokes equations (RANS) model. The simulated concentrations of NO₂, PM₁₀, and black carbon (BC) are compared with field measurements on a street of Greater Paris. The simulated NO₂ and PM₁₀ concentrations based on the coupled model achieved better agreement with measurement data than the conventional CFD simulation. Meanwhile, the black carbon concentration is underestimated, probably partly because of the underestimation of non-exhaust emissions (tire and road wear). Aerosol dynamics lead to a large increase of ammonium nitrate and anthropogenic organic compounds from precursor gas emitted in the street canyon.