Etude simultanée de la composition chimique de la fraction organique des particules secondaires et de la phase gazeuse atmosphériques en site réel et en atmosphère simulée

National audienceSecondary Organic Aerosols (SOAs) are formed in the atmosphere by gas-to-particle conversion of oxygenated Semi-Volatile Organic Compounds (SVOCs). However, the community currently lacks data to describe these multiphase phenomena and assess their climate and health impacts. This analytical work intends to improve our understanding of SOA by an original study based on the development of a simultaneous sampling method for gaseous and particulate phases. Both phases are analyzed by the same sensitive and rapid analytical technique coupling thermal-desorption, gas chromatography and mass spectrometry (TD-GC-MS). The method involves derivatization of oxygenated SVOCs, in gas and particulate phases, on a solid support fitting with TD, to improve their analytical response and facilitate their identification. This work presents this development performed combining smog chamber experiments and the MEGAPOLI field campaign.Les Aérosols Organiques Secondaires (AOS) sont formés dans l'atmosphère par conversion de gaz organiques en particules ; ils sont issus de l'oxydation en phase gazeuse de Composés Organiques Volatils (COV) précurseurs, menant à la formation de Composés Organiques Semi-Volatils (COSV) oxygénés se partageant entre les phases gazeuse et particulaire. La communauté manque actuellement de données pour décrire ces phénomènes multiphasiques et évaluer leurs impacts climatiques et sanitaires. Ce travail analytique se propose ainsi d'améliorer notre connaissance des AOS par une étude originale basée sur la mise au point d'une méthode de prélèvement simultané des phases gazeuse et particulaire et leur analyse par une même technique analytique sensible et rapide, le couplage thermo-désorption/chromatographie en phase gazeuse/spectrométrie de masse (TD-GCMS). La méthode consiste en une dérivatisation indispensable des COSV oxygénés, prélevés en phase gazeuse comme en phase particulaire, sur un support solide thermo-désorbable afin d'améliorer leur réponse analytique et de faciliter leur identification. Ce travail présente le développement réalisé à partir d'expériences en chambres de simulation atmosphérique - dont CESAM, chambre spécialement conçue pour l'étude des phénomènes multiphasiques - et de la campagne de terrain du projet européen MEGAPOLI

SOA formation study from limonene ozonolysis in indoor environment : gas and particulate phases chemical characterization and toxicity prediction

International audienceLimonene is widely employed in scented products used in indoor environments such as fresheners and household cleaners (Nazaroff 2004). It also displays one of the highest potential for the formation of Secondary Organic Aerosols (SOAs) following ozonolysis (Jaoui 2006; Chen 2010). Besides, indoor ozone concentration, influenced by outdoor concentration and indoor sources, can be quite important to initiate gas phase chemistry (Weschler 2000) and possibly lead to secondary products formation. This work investigates SOAs formation from the ozonolysis of limonene as emitted from a detergent, in order to gather information on aerosols that are an important source of exposure for people using household products

European climate optimum and enhanced Greenland melt during the Last Interglacial

The Last Interglacial climatic optimum, ca. 128 ka, is the most recent climate interval signifi cantly warmer than present, providing an analogue (albeit imperfect) for ongoing global warming and the effects of Greenland Ice Sheet (GIS) melting on climate over the coming millennium. While some climate models predict an Atlantic meridional overturning circulation (AMOC) strengthening in response to GIS melting, others simulate weakening, leading to cooling in Europe. Here, we present evidence from new proxy-based paleoclimate and ocean circulation reconstructions that show that the strongest warming in western Europe coincided with maximum GIS meltwater runoff and a weaker AMOC early in the Last Interglacial. By performing a series of climate model sensitivity experiments, including enhanced GIS melting, we were able to simulate this confi guration of the Last Interglacial climate system and infer information on AMOC slowdown and related climate effects. These experiments suggest that GIS melt inhibited deep convection off the southern coast of Greenland, cooling local climate and reducing AMOC by ~24% of its present strength. However, GIS melt did not perturb overturning in the Nordic Seas, leaving heat transport to, and thereby temperatures in, Europe unaffected. © 2012 Geological Society of America

Proteomic and Mechanistic Analysis of Spironolactone in Patients at Risk for HF.

OBJECTIVES: This study sought to further understand the mechanisms underlying effect of spironolactone and assessed its impact on multiple plasma protein biomarkers and their respective underlying biologic pathways. BACKGROUND: In addition to their beneficial effects in established heart failure (HF), mineralocorticoid receptor antagonists may act upstream on mechanisms, preventing incident HF. In people at risk for developing HF, the HOMAGE (Heart OMics in AGEing) trial showed that spironolactone treatment could provide antifibrotic and antiremodeling effects, potentially slowing the progression to HF. METHODS: Baseline, 1-month, and 9-month (or last visit) plasma samples of HOMAGE participants were measured for protein biomarkers (n = 276) by using Olink Proseek-Multiplex cardiovascular and inflammation panels (Olink, Uppsala, Sweden). The effect of spironolactone on biomarkers was assessed by analysis of covariance and explored by knowledge-based network analysis. RESULTS: A total of 527 participants were enrolled; 265 were randomized to spironolactone (25 to 50 mg/day) and 262 to standard care ("control"). The median (interquartile range) age was 73 years (69 to 79 years), and 26% were female. Spironolactone reduced biomarkers of collagen metabolism (e.g., COL1A1, MMP-2); brain natriuretic peptide; and biomarkers related to metabolic processes (e.g., PAPPA), inflammation, and thrombosis (e.g., IL17A, VEGF, and urokinase). Spironolactone increased biomarkers that reflect the blockade of the mineralocorticoid receptor (e.g., renin) and increased the levels of adipokines involved in the anti-inflammatory response (e.g., RARRES2) and biomarkers of hemostasis maintenance (e.g., tPA, UPAR), myelosuppressive activity (e.g., CCL16), insulin suppression (e.g., RETN), and inflammatory regulation (e.g., IL-12B). CONCLUSIONS: Proteomic analyses suggest that spironolactone exerts pleiotropic effects including reduction in fibrosis, inflammation, thrombosis, congestion, and vascular function improvement, all of which may mediate cardiovascular protective effects, potentially slowing progression toward heart failure. (HOMAGE [Bioprofiling Response to Mineralocorticoid Receptor Antagonists for the Prevention of Heart Failure]; NCT02556450)

The effect of spironolactone on cardiovascular function and markers of fibrosis in people at increased risk of developing heart failure: the heart 'OMics' in AGEing (HOMAGE) randomized clinical trial.

AIMS: To investigate the effects of spironolactone on fibrosis and cardiac function in people at increased risk of developing heart failure. METHODS AND RESULTS: Randomized, open-label, blinded-endpoint trial comparing spironolactone (50 mg/day) or control for up to 9 months in people with, or at high risk of, coronary disease and raised plasma B-type natriuretic peptides. The primary endpoint was the interaction between baseline serum galectin-3 and changes in serum procollagen type-III N-terminal pro-peptide (PIIINP) in participants assigned to spironolactone or control. Procollagen type-I C-terminal pro-peptide (PICP) and collagen type-1 C-terminal telopeptide (CITP), reflecting synthesis and degradation of type-I collagen, were also measured. In 527 participants (median age 73 years, 26% women), changes in PIIINP were similar for spironolactone and control [mean difference (mdiff): -0.15; 95% confidence interval (CI) -0.44 to 0.15 μg/L; P = 0.32] but those receiving spironolactone had greater reductions in PICP (mdiff: -8.1; 95% CI -11.9 to -4.3 μg/L; P < 0.0001) and PICP/CITP ratio (mdiff: -2.9; 95% CI -4.3 to -1.5; <0.0001). No interactions with serum galectin were observed. Systolic blood pressure (mdiff: -10; 95% CI -13 to -7 mmHg; P < 0.0001), left atrial volume (mdiff: -1; 95% CI -2 to 0 mL/m2; P = 0.010), and NT-proBNP (mdiff: -57; 95% CI -81 to -33 ng/L; P < 0.0001) were reduced in those assigned spironolactone. CONCLUSIONS: Galectin-3 did not identify greater reductions in serum concentrations of collagen biomarkers in response to spironolactone. However, spironolactone may influence type-I collagen metabolism. Whether spironolactone can delay or prevent progression to symptomatic heart failure should be investigated

Développement d'une méthode de prélèvement simultané et d'analyse chimique des phases gazeuse et particulaire atmosphériques pour une approche multiphasique de l'aérosol organique secondaire

Parmi les particules en suspension dans l'atmosphère, influençant le climat et impactant la santé des populations, l'Aérosol Organique Secondaire (AOS) est issu de processus réactifs complexes difficilement appréhendables. Les connaissances grandissantes dans ce domaine ont en particulier mis en lumière le rôle de la chimie multiphasique sur ses processus de formation et d'évolution. L'objectif de ce travail a ainsi été d'établir une méthodologie analytique permettant une approche globale de la matière organique secondaire atmosphérique au travers d'une part de la caractérisation poussée de sa composition chimique à l'échelle moléculaire et d'autre part de la quantification du partage des espèces semi-volatiles entre les phases gazeuse et particulaire. Ainsi, sur la base de la thermo-désorption couplée à la chromatographie 'en phase gazeuse et à la spectrométrie de masse, une méthode permettant le prélèvement simultané et la dérivatisation d'échantillons gazeux sur tubes d'adsorbant, et particulaires sur filtres, à été développée pour la détection et la quantification spécifiques des composés organiques oxygénés et fonctionnalisés composant la matière organique secondaire. La mise en application de la méthodologie ainsi développée à l'étude de l'ozonolyse du limonène a permis de confirmer sa simplicité d'utilisation et de mettre en avant ses capacités d'exploration, de quantification et d'évaluation du partage gaz/particules de la matière organique secondaire et/ou fonctionnalisée dans différents environnements : atmosphère simulée, atmosphère réelle extérieure et air intérieur.Among the suspended particles in the atmosphere, influencing climate and impacting people's health, the Secondary Organic Aerosol (SOA) is the result of complex reactive processes. The growing knowledge in this area has particularly highlighted the role of multiphase chemistry on its formation and evolution processes. SOA has nevertheless so far been most often experimentally studied from a particulate phase point of view, while the gas phase influence was neglected. In this context, this study aimed at establishing a new analytical methodology for a comprehensive approach of the atmospheric secondary organic matter through an extensive characterization of its chemical composition at the molecular scale and the quantification of semi-volatile compounds partitioning between the gas and the particulate phases. Based on the easy to use thermal desorption - gas chromatography - mass spectrometry analytical coupling, the developed method involved simultaneous sampling of both phases and on sampling support derivatisation processes of gas and particulate samples - on sorbent tubes and on-filters respectively - for the detection and the quantification of oxygenated and functionalized secondary organic matter. The implementation of the developed methodology to the limonene ozonolysis study in different environments - simulated atmosphere, real outdoor atmosphere and indoor air - has highlighted its capabilities to explore the secondary organic matter chemical composition, and to quantify gas/particulate partitioning of oxygenated semi-volatile species.PARIS7-Bibliothèque centrale (751132105) / SudocSudocFranceF

Simultaneous study of gas phase and secondary organic aerosols chemical composition

International audienceSecondary Organic Aerosols (SOAs) are formed in the atmosphere by gas-to-particle conversion of organic gase

Cycle de vie des composés organiques dans l'atmosphère : quantifier la partition phase gazeuse - phase particulaire

Comprendre le devenir des composés organiques dans l'atmosphère est un enjeu majeur dans l'évaluation des impacts climatiques et sanitaires des émissions d'origines biotiques comme anthropiques. Ce travail propose une nouvelle approche analytique de la problématique en permettant d'accéder à la spéciation chimique à l'échelle moléculaire de la matière organique atmosphérique, notamment d'origine secondaire, simultanément en phases gazeuse et particulaire. L'objectif est de décrire la chimie multiphasique impliquée dans la formation et l'évolution des aérosols organiques secondaires (AOS) et d'améliorer la prise en compte des phénomènes de partition gaz/particules des composés organiques secondaires. Les phases gazeuse et particulaire sont simultanément prélevées, respectivement sur tubes d'adsorbant et sur filtres. La méthode adapte les techniques de dérivatisation des fonctions carbonylées et hydroxylées afin de les réaliser directement sur ces supports de prélèvement avant analyse des échantillons par thermo-désorption - chromatographie en phase gazeuse - spectrométrie de masse. La technique réduit l'utilisation de solvant, limite les pertes et contaminations et simplifie le traitement des échantillons. Potentiellement applicable à une large gamme de systèmes chimiques (précurseur/oxydant) et de type de sites (rural, urbain, trafic...), seront présentés ici les résultats de l'application de la méthode à l'étude de l'ozonolyse du limonène, l'un des terpènes les plus émis par la végétation à l'échelle globale et à fort rendement d'AOS