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Organic nitrates (RONO2) are secondary compounds whose fate is closely related to the transport and removal of NOx in the atmosphere. Despite their ubiquitous presence in submicron aerosols, the photochemistry of RONO2 has only been investigated in the gas phase, leaving their reactivity in condensed phases poorly explored. This work aims to address this gap by investigating, for the first time, the reaction products, and the mechanisms of aqueous-phase photolysis of four RONO2 (i.e., isopropyl nitrate, isobutyl nitrate, α-nitrooxyacetone, and 1-nitrooxy-2-propanol). The results show that the reactivity of RONO2 in the aqueous phase differs significantly from that in the gas phase. In contrast to the gas phase, where RONO2 releases NOx upon photolysis, the aqueous phase photolysis of RONO2 leads primarily to the direct formation of HONO, which was confirmed by quantum chemistry calculations. Hence, the aqueous-phase photolysis of RONO2 represents both a NOx sink and a source of atmospheric HONO, a significant precursor of ∙OH and ∙NO. These secondary radicals (·OH and ·NO) are efficiently trapped in the aqueous phase, leading to the formation of HNO3 and functionalized RONO2. This reactivity can thus potentially contribute to the aging of Secondary Organic Aerosol (SOA) and serve as an additional source of aqueous-phase SOA.

International audience; In this paper we focus on airborne hyperspectral imaging methodology to characterize PM (Particulate Matter) near industrial emission sources. Two short-term intensive campaigns were carried out in the vicinity of a refinery in the South of France, in September 2015 and February 2016. Different protocols of in-situ PM measurements were performed, at stack measurements (flow rate and offline chemical analysis) and on-line measurement at the refinery border (size distribution, concentration and chemistry of aerosols). A multi temporal methodology to retrieve aerosol type, to map the aerosol concentration and to quantify mass flow rate from airborne hyperspectral data is described in this paper. This method applied to the refinery detected plume from the main stack yields a black carbon to sulfate ratio of 10/90 in mass inside the plume, with an average size distribution smaller than 100 nm. These results are in a good agreement with on-line analysis of aerosols at refinery border. The resulting quantitative map with a metric spatial resolution leads to a flow rate estimated of about 1g/s and is in a good agreement with in-situ stack measurements and modelling.; Ce papier propose une méthodologie de caractérisation des PM (Particulate Matter) proches des sources industrielles par imagerie hyperspectrale aéroportée. Il s’appuie sur deux campagnes de mesures réalisées autour d’une raffinerie dans le sud de la France en Septembre 2015 et Février 2016. Différents protocoles de mesures in-situ des PM ont été réalisées dans ce cadre, mesures au niveau de l’émissaire principal (debit et analyse chimique) et mesures on-line au voisinage de la raffinerie (distribution en taille, concentration et analyse chimique). Une méthodologie multi-temporelle dédiée à l’inversion des types d’aérosols présents dans le panache permettant de fournir une carte en concentration d’aérosols et d’estimer le débit est décrite dans ce papier. Appliquée à ce cas d’étude, les resultats hyperspectraux ont permis d’estimer un rapport suie/sulfate de 10/90 en masse dans le panache avec une distribution en taille inférieure à 100nm. Ces résultats sont en bon accord avec les mesures in-situ. Les cartes en concentration obtenue à une resolution métrique permettent d’estimer un debit de l’ordre de 1g/s en bon accord avec les mesures in-situ au niveau de l’émissaire et avec les résultats de modélisation de dispersion des aerosols.

International audience; The persistent organic pollutants (POPs) due to their physicochemical properties can be widely spread all over the globe; as such they represent a serious threat to both humans and wildlife. According to Stockholm convention out of 24 officially recognized POPs, 16 are pesticides. The atmospheric life times of pesticides, up to now were estimated based on their gas-phase reactivity. It has been only speculated that sorption to aerosol particles may increase significantly the half-lives of pesticides in the atmosphere. The results presented here challenge the current view of the half-lives of pesticides in the lower boundary layer of the atmosphere and their impact on air quality and human health. We demonstrate that semivolatile pesticides which are mostly adsorbed on atmospheric aerosol particles are very persistent with respect to the highly reactive hydroxyl radicals (OH) that is the self-cleaning agent of the atmosphere. The half-lives in particulate phase of difenoconazole, tetraconazole, fipronil, oxadiazon, deltamethrin, cyprodinil, permethrin, and pendimethalin are in order of several days and even higher than one month, implying that these pesticides can be transported over long distances, reaching the remote regions all over the world; hence these pesticides shall be further evaluated prior to be confirmed as POPs.