Etude des composés polyaromatiques dans l’atmosphère : caractérisation moléculaire et processus réactionnels en lien avec l’aérosol organique

This PhD work deals with a better characterization, at the molecular level of the organic atmospheric aerosol in relation to polycyclic aromatic compounds (PACs), and has been structured using two different but complementary approaches. Field measurements were conducted in Grenoble (France) and concentration levels, seasonal variability and gas/particle partitioning distribution of polycyclic aromatic hydrocarbons (PAHs), oxy-PAHs (OPAHs) and nitro-PAHs (NPAHs) have been investigated for one whole year. This field study allowed to a better understanding of primary vs secondary sources of OPAHs and NPAHs and specific molecular markers related to different sources have been identified. A complementary study was carried out using an atmospheric smog chamber, in order to investigate the formation of secondary organic aerosol (SOA) from the photooxidation of naphthalene and 2-methylnaphthalene, two of the most abundant PAHs in the gas-phase. The formation of organosulfates and sulfonates, from the oxidation of gaseous PAHs, has been highlighted for the first time in this work and these compounds have been proposed as potential SOA markers of PAH photooxidation. UV-Visible absorption of SOA generated during these experiments was investigated and led to the identification of specific molecules responsible for this absorption. A wide chemical characterization of SOA was performed and emphasized its dependence on many experimental factors (nature of seed particles, relative humidity and seed acidity) and allowed to propose some new chemical reaction pathways.Ce travail de thèse a eu pour objectif une meilleure caractérisation, au niveau moléculaire, de l’aérosol organique atmosphérique, en lien avec les composés polyaromatiques. Cette étude s’est articulée autour de deux approches différentes mais complémentaires. Une étude de terrain conduite à Grenoble a permis d’appréhender les niveaux de concentration, la variabilité saisonnière et la répartition gaz/particule des hydrocarbures aromatiques polycycliques (HAP), oxy-HAP (OHAP) et nitro-HAP (NHAP), pendant une année entière. Ce travail de terrain a aussi permis d’appréhender les sources primaires et secondaires des OHAP et NHAP ainsi que de proposer des molécules marqueurs de ces processus de formation. Une étude complémentaire conduite en chambre de simulation atmosphérique a, quant à elle, eu pour but l’investigation de la formation d’aérosol organique secondaire (AOS), suite à la photooxydation du naphtalène et du 2-méthylnaphtalène. L’identification de la formation de produits organosoufrés de type organosulfates et sulfonates, à partir de la photooxydation de HAP gazeux, a été mise en évidence pour la première fois lors de cette thèse, ce qui a permis de proposer ces composés comme des marqueurs de formation d’AOS à partir des HAP. La capacité de ces AOS à absorber le rayonnement UV-Visible a été appréhendée et les molécules responsables de cette absorption ont été identifiées. Une caractérisation chimique poussée de l’AOS a mis en évidence sa dépendance aux différentes conditions expérimentales (type de particules d’ensemencement, acidité et humidité relative) et a conduit à l’identification et à la proposition de nouvelles voies réactionnelles

Structures and reactivity of peroxy radicals and dimeric products revealed by online tandem mass spectrometry

Organic peroxy radicals (RO2) play a pivotal role in the degradation of hydrocarbons. The autoxidation of atmospheric RO2 radicals produces highly oxygenated organic molecules (HOMs), including low-volatility ROOR dimers formed by bimolecular RO2 + RO2 reactions. HOMs can initiate and greatly contribute to the formation and growth of atmospheric particles. As a result, HOMs have far-reaching health and climate implications. Nevertheless, the structures and formation mechanism of RO2 radicals and HOMs remain elusive. Here, we present the in-situ characterization of RO2 and dimer structure in the gas-phase, using online tandem mass spectrometry analyses. In this study, we constrain the structures and formation pathway of several HOM-RO2 radicals and dimers produced from monoterpene ozonolysis, a prominent atmospheric oxidation process. In addition to providing insights into atmospheric HOM chemistry, this study debuts online tandem MS analyses as a unique approach for the chemical characterization of reactive compounds, e.g., organic radicals.Peer reviewe

Nutrition, atherosclerosis, arterial imaging, cardiovascular risk stratification, and manifestations in COVID-19 framework: a narrative review.

Background: Atherosclerosis is the primary cause of the cardiovascular disease (CVD). Several risk factors lead to atherosclerosis, and altered nutrition is one among those. Nutrition has been ignored quite often in the process of CVD risk assessment. Altered nutrition along with carotid ultrasound imaging-driven atherosclerotic plaque features can help in understanding and banishing the problems associated with the late diagnosis of CVD. Artificial intelligence (AI) is another promisingly adopted technology for CVD risk assessment and management. Therefore, we hypothesize that the risk of atherosclerotic CVD can be accurately monitored using carotid ultrasound imaging, predicted using AI-based algorithms, and reduced with the help of proper nutrition. Layout: The review presents a pathophysiological link between nutrition and atherosclerosis by gaining a deep insight into the processes involved at each stage of plaque development. After targeting the causes and finding out results by low-cost, user-friendly, ultrasound-based arterial imaging, it is important to (i) stratify the risks and (ii) monitor them by measuring plaque burden and computing risk score as part of the preventive framework. Artificial intelligence (AI)-based strategies are used to provide efficient CVD risk assessments. Finally, the review presents the role of AI for CVD risk assessment during COVID-19. Conclusions: By studying the mechanism of low-density lipoprotein formation, saturated and trans fat, and other dietary components that lead to plaque formation, we demonstrate the use of CVD risk assessment due to nutrition and atherosclerosis disease formation during normal and COVID times. Further, nutrition if included, as a part of the associated risk factors can benefit from atherosclerotic disease progression and its management using AI-based CVD risk assessment

Hyperoxemia and excess oxygen use in early acute respiratory distress syndrome : Insights from the LUNG SAFE study

Publisher Copyright: © 2020 The Author(s). Copyright: Copyright 2020 Elsevier B.V., All rights reserved.Background: Concerns exist regarding the prevalence and impact of unnecessary oxygen use in patients with acute respiratory distress syndrome (ARDS). We examined this issue in patients with ARDS enrolled in the Large observational study to UNderstand the Global impact of Severe Acute respiratory FailurE (LUNG SAFE) study. Methods: In this secondary analysis of the LUNG SAFE study, we wished to determine the prevalence and the outcomes associated with hyperoxemia on day 1, sustained hyperoxemia, and excessive oxygen use in patients with early ARDS. Patients who fulfilled criteria of ARDS on day 1 and day 2 of acute hypoxemic respiratory failure were categorized based on the presence of hyperoxemia (PaO2 > 100 mmHg) on day 1, sustained (i.e., present on day 1 and day 2) hyperoxemia, or excessive oxygen use (FIO2 ≥ 0.60 during hyperoxemia). Results: Of 2005 patients that met the inclusion criteria, 131 (6.5%) were hypoxemic (PaO2 < 55 mmHg), 607 (30%) had hyperoxemia on day 1, and 250 (12%) had sustained hyperoxemia. Excess FIO2 use occurred in 400 (66%) out of 607 patients with hyperoxemia. Excess FIO2 use decreased from day 1 to day 2 of ARDS, with most hyperoxemic patients on day 2 receiving relatively low FIO2. Multivariate analyses found no independent relationship between day 1 hyperoxemia, sustained hyperoxemia, or excess FIO2 use and adverse clinical outcomes. Mortality was 42% in patients with excess FIO2 use, compared to 39% in a propensity-matched sample of normoxemic (PaO2 55-100 mmHg) patients (P = 0.47). Conclusions: Hyperoxemia and excess oxygen use are both prevalent in early ARDS but are most often non-sustained. No relationship was found between hyperoxemia or excessive oxygen use and patient outcome in this cohort. Trial registration: LUNG-SAFE is registered with ClinicalTrials.gov, NCT02010073publishersversionPeer reviewe

Diversité des agricultures familiales

Dans un contexte d’interrogation sur les modèles agricoles et de profondes transformations des agricultures et des marchés, cet ouvrage s’attache à revisiter la diversité des formes familiales de production et leurs mutations de par le monde. Dès lors, l’analyse intègre les liens aux marchés, aux territoires et à l’Ailleurs — par le fait migratoire — les enjeux d’autonomie et de sécurité alimentaire, les stratégies de survie et d’accumulation ainsi que les formes d’action collective et politique. L’ouvrage est construit autour de dix-huit études de cas, menées dans les cinq continents. Elles ont toutes été conduites avec un cadre méthodologique, identique et original, inspiré du Sustainable Rural Livehoods (cadre d’identification des moyens de subsistance durables en milieu rural). Revisitée pour cet ouvrage, cette méthode d’observations et d’analyses permet aux auteurs de préciser finement « ce qui fait famille », d’analyser les adaptations du travail des actifs familiaux et les mettre en perspective avec le contexte territorial et les politiques publiques de chaque pays. Écrit à plusieurs mains, par un réseau de chercheurs, cet ouvrage contribue autant à l’approfondissement des savoirs scientifiques sur les agricultures familiales dans le monde qu’à la mise à l’épreuve d’un cadre méthodologique d’analyse et d’observations en milieu rural. Il vise un public de chercheurs, d’enseignants et d’étudiants, agronomes, économistes, sociologues et historiens. Les experts du développement agricole et rural y trouveront un grand intérêt. Plus largement, toute personne qui s’intéresse aux agricultures familiales et à leurs évolutions dans divers contextes sociaux trouvera avantage à cette lecture. Les chercheurs qui ont coordonné cet ouvrage sont agronomes, économistes et géographes, au Cirad ou à l’Inra où ils mènent des recherches sur les systèmes agricoles familiaux à des échelles locales, nationales ou internationales. Cet ouvrage est le fruit d’une démarche de recherche collective et partagée permettant à de nombreux scientifiques des pays du Sud d’exprimer la diversité des réalités agraires contemporaines. Certains coordinateurs ou auteurs de cet ouvrage ont également collaboré à Agricultures familiales et mondes à venir, titre paru en 2014 chez Quae. Ce livre est également disponible en anglais sous le titreDiversity of Family Farming Around the Worldauprès des éditions Springer -www.springer.co

A really quick easy cheap effective rugged and safe (QuEChERS) extraction procedure for the analysis of particle-bound PAHs in ambient air and emission samples

International audienceA quick easy cheap effective rugged and safe (QuEChERS) like extraction procedure is presented for the measurement of polycyclic aromatic hydrocarbons (PAHs) associated to particulate matter from ambient air or combustion process. The procedure is based on a short mechanical agitation (vortex during 90 s) using a small volume of acetonitrile (7 ml) as extraction solvent. Equivalent extraction efficiencies were obtained when comparing the QuEChERS and the traditional pressurized solvent extraction (ASE) procedures for ambient air and emission (wood combustion) filter samples. The developed QuEChERS extraction protocol was validated with the analysis of a standard reference material (NIST SRM 1649a, urban dust). By comparison to other extraction methods including ASE, the simplicity of the QuEChERS protocol allows to minimize experimental errors, to decrease about a factor 5 the cost per extraction and to increase the productivity per working day by a 10-fold factor. This paper constitutes the first report on the applicability of a QuEChERS-like approach for the quantification of PAHs or other organic compounds in atmospheric particulate matter

Study of polycyclic aromatic compounds in the atmosphere : molecular characterization and chemical processes related to organic aerosols

Ce travail de thèse a eu pour objectif une meilleure caractérisation, au niveau moléculaire, de l’aérosol organique atmosphérique, en lien avec les composés polyaromatiques. Cette étude s’est articulée autour de deux approches différentes mais complémentaires. Une étude de terrain conduite à Grenoble a permis d’appréhender les niveaux de concentration, la variabilité saisonnière et la répartition gaz/particule des hydrocarbures aromatiques polycycliques (HAP), oxy-HAP (OHAP) et nitro-HAP (NHAP), pendant une année entière. Ce travail de terrain a aussi permis d’appréhender les sources primaires et secondaires des OHAP et NHAP ainsi que de proposer des molécules marqueurs de ces processus de formation. Une étude complémentaire conduite en chambre de simulation atmosphérique a, quant à elle, eu pour but l’investigation de la formation d’aérosol organique secondaire (AOS), suite à la photooxydation du naphtalène et du 2-méthylnaphtalène. L’identification de la formation de produits organosoufrés de type organosulfates et sulfonates, à partir de la photooxydation de HAP gazeux, a été mise en évidence pour la première fois lors de cette thèse, ce qui a permis de proposer ces composés comme des marqueurs de formation d’AOS à partir des HAP. La capacité de ces AOS à absorber le rayonnement UV-Visible a été appréhendée et les molécules responsables de cette absorption ont été identifiées. Une caractérisation chimique poussée de l’AOS a mis en évidence sa dépendance aux différentes conditions expérimentales (type de particules d’ensemencement, acidité et humidité relative) et a conduit à l’identification et à la proposition de nouvelles voies réactionnelles.This PhD work deals with a better characterization, at the molecular level of the organic atmospheric aerosol in relation to polycyclic aromatic compounds (PACs), and has been structured using two different but complementary approaches. Field measurements were conducted in Grenoble (France) and concentration levels, seasonal variability and gas/particle partitioning distribution of polycyclic aromatic hydrocarbons (PAHs), oxy-PAHs (OPAHs) and nitro-PAHs (NPAHs) have been investigated for one whole year. This field study allowed to a better understanding of primary vs secondary sources of OPAHs and NPAHs and specific molecular markers related to different sources have been identified. A complementary study was carried out using an atmospheric smog chamber, in order to investigate the formation of secondary organic aerosol (SOA) from the photooxidation of naphthalene and 2-methylnaphthalene, two of the most abundant PAHs in the gas-phase. The formation of organosulfates and sulfonates, from the oxidation of gaseous PAHs, has been highlighted for the first time in this work and these compounds have been proposed as potential SOA markers of PAH photooxidation. UV-Visible absorption of SOA generated during these experiments was investigated and led to the identification of specific molecules responsible for this absorption. A wide chemical characterization of SOA was performed and emphasized its dependence on many experimental factors (nature of seed particles, relative humidity and seed acidity) and allowed to propose some new chemical reaction pathways

De l’importance des composés organiques nitrés dans l’atmosphère. Caractérisation moléculaire et études de sources en air ambiant

A detailed study of the nitrogen content organic compounds in PM, including source apportionment, has been performed over a one-year period (2013) in Grenoble (France) as well as at the SIRTA station, representing the suburban background air quality conditions of the Paris area, during an intense PM pollution event in March 2015 (PM10 > 50 μg m-3 for several days). For Grenoble, the results obtained indicated that concentrations of nitro-PAHs (polycyclic aromatic hydrocarbons) were affected by secondary processes in summer but also in cold period under specific conditions, allowing for significant nitrate chemistry and secondary nitro-PAH formation processes. For the SIRTA dataset, a novel methodology has been developed and applied to refine the sources of organic aerosol (OA) combining dataset from ACSM (aerosol chemical speciation monitor) mass spectra and specific primary and secondary organic molecular markers from PM10 filters. The results showed the deconvolution of 10 OA factors including 3 primary OA (POA) and 7 secondary OA (biogenic and anthropogenic SOA) factors. The developed methodology allowed the clear identification of about half of the total SOA mass (75% of OA) observed during the sampling campaign and highlighted that 4 OA factors were linked to biomass burning emission with 2 primary sources (biomass burning OA (BBOA) and oxidized POA (OPOA)) and 2 secondary ones (from the oxidation of phenolic compounds and toluene). Furthermore, nitrated anthropogenic SOA, related to the oxidation of PAHs (characterized by nitro-PAHs), toluene, and phenolic compounds (methoxy-phenols), accounted for about 12% of total OA and exhibited a clear diurnal pattern with high concentrations during the night indicating the prominent role of night-time chemistry (nitrate radical). Future studies will focus on the organonitrate aerosol fraction starting by an intercomparison exercise of ACSM instruments end 2018 led by the ACMCC within the ACTRIS network activities.La pollution due aux particules atmosphériques (aérosols, PM) est à l’origine d’importantes problématiques sanitaires et climatiques. La connaissance et l’évaluation de la contribution de leurs sources constituent ainsi un enjeu capital en termes de politiques de gestion de la qualité de l’air. Parmi ces particules, la fraction organique est d’un intérêt majeur notamment car elle contient des composés toxiques tels que les nitro-HAP (hydrocarbures aromatiques polycycliques) dont les effets sur la santé sont encore mal connus. De plus, ces composés organiques absorbent une partie du rayonnement solaire et ont un effet sur le bilan radiatif, dont l’importance reste mal évaluée. Les travaux menés par l’Ineris ont permis de réaliser une évaluation approfondie des sources des PM et notamment d’une partie de la fraction organique nitrée. Une meilleure connaissance de l’origine des aérosols organiques (AO), qui représentent une part importante de la masse totale des particules fines dans l’atmosphère (de 20 à 90 % dans la basse troposphère), a pu être obtenue à l’aide de marqueurs organiques moléculaires quantifiés sur des échantillons collectés in situ et par couplage avec des données de mesures en temps réel par spectrométrie de masse aérosol

Molecular chemical characterization of organic aerosols using QuEChERS-like extraction approach : application to PAHs and their nitrated and oxygenated derivatives (NPAHs and OPAHs)

Alternative extraction procedures based on a QuEChERS approach (Quick Easy Cheap Effective Rugged and Safe) were developed for the measurement of PAHs and PAH derivatives (nitrated and oxygenated PAHs) associated to particulate matter from ambient air or combustion processes. The procedures are based on a short mechanical agitation (vortex) using a small volume of solvent (< 10 ml) and including, if necessary, a purification step by solid phase extraction (SPE) or dispersive-SPE (d-SPE). Different extraction parameters were optimized such as agitation time, solvent nature, adsorbent for clean-up. Equivalent extraction efficiencies were obtained when comparing the QuEChERS-like and the commonly used pressurized solvent extraction procedures (PLE) for ambient air and emission (wood combustion) filter samples