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ChArMEx

ChArMEx. In collab with. N. Marchand, JL Jaffrezo. Objectives :. Chemical characterization of aerosols (focus on OC). Receptor site (ERSA, Corsica). Sources. Biomass burning ship emissions primary marine aerosol (Dp<1µm) Biogenic VOC. EOP : off line measurements

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ChArMEx

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  1. ChArMEx In collab with N. Marchand, JL Jaffrezo Objectives : Chemical characterization of aerosols (focus on OC) Receptor site (ERSA, Corsica) Sources • Biomass burning • ship emissions • primary marine aerosol (Dp<1µm) • Biogenic VOC EOP : off line measurements SOP : off line and one line measurements Long range transport, influence of biomass burning, ship emissions and others anthropogenic sources, chemical ageing

  2. Chemical characterization of PM Phytane Pristane 2,6,10,14-tétraméthylhexadécane 2,6,10,14-tétraméthylpentadécane R R R = H, CH -C H 3 6 13 R = H, CH -C H 3 6 13 Stéranes a b 17 (H),21 (H)-hopanes O O O H H O O H O H O O O O H C H CO H CO 14 3 3 3 H CO 3 Alpha palmitin C H O 3 H O H O H O OCH 3 Coniferyl aldéhyde Vanillin Syringaldéhyde OC/EC (WSOC) (EUSAAR2/ NIOSH) Major ionic species (SO42-, NO3-, NH4+, Cl-, Na+,…) (IC) HULIS (HPLC-UV and DOC) / functional Groups Elemental speciation for crustal elements and trace metals (~40) Molecular speciation : Organic markers (GC/MS) Primary compounds : PAH (16 EPA), 13C of PAH n-alkanes (C16-C36) branched alkanes (pristane, phytane) Carboxylic acids (C1-C30) (mono and di) (GC+IC) Hopanes/Steranes Steroides (Cholesterol, sitosterol, stigmasterol) Anhydride sugars (Levoglucosan, mannosan, galactosan) Methoxyphenols (Substitued syringyl and guaiacyl compounds,…) Glycerides (Monopalmitin, Monostearin, …) Phtalates Sugars (glucose..) Others (Nicotine..) Secondary biogenic compounds : Pinic acid, pinonic acid, tetrols, methyl glyceric acid(…) ~ 100 compounds (in 2 GC runs –apolar and polar after BSTFA derivatisation step) Secondary anthropogenic compounds : Aromatic acids and diacids (…)

  3. - HR-ToF-AMS • PTR-ToF-MS (planned in 2011) • (possibility to use an HS-PTR-MS before 2011) - BC analyser (MAAP5012) - SMPS - PM1 or PM2.5 HVS sampler - Wind speed and directions (+T, HR)

  4. Influence de la vallée du Rhône… Influence de la vallée du Po et cote ouest italienne…

  5. Episodes Aout 2009…

  6. Evolution of the particle size distributions Episodes de fines particules d’origine industrielle (observés à Marseille) • ~ 100 000 #/cm3 et plus • Dp < 50 nm • Composition H2SO4, HSO4NH4, Org. • Evolution photochimique au cours du transit au dessus de la méditerranéen (épisodes du 5 et 4 Juillet : composition de brises)

  7. Source apportionment (Marseille) Via Chemical Mass Balance (CMB) Emissions véhiculaires : 17% de l’OC et des PM2.5 Sources industrielles : 2.5 % de l’OC et à 7.1 % des PM2.5 Combustion de biomasse : 0.8 % de l’OC et 0.4 % des PM2.5. 78 % du carbone reste non expliqué El Haddad et al. 2010a Principalement de l’AOS

  8. Source apportionment (Marseille) Eléments de contrainte El Haddad et al. 2010a El Haddad et al. 2010a Excellents accords avec approches AMS/PMF et 14C Très bons scores de Modélisation

  9. Combinaison des approches 14C et CMB Eléments sur l’origine de l’AOS POCF (Primary OC Fossil) ~20% POCC (Primary OC Comtemporain) ~3% SOCF (Secondary Organic Fossil) : ~17% SOCC (Secondary Organic Cont.) : ~60% El Haddad et al. 2010b Prévalence du carbone organique secondaire contemporain (~biogénique), même dans un environnement urbain de fond (Marseille)

  10. Sources de l’AOS biogénique ? El Haddad et al. 2010b « Traditionnal biogenic SOA » déterminé à partir des produits de dégradation de l’isoprène (Methyltétrols et acides glycérique), de l’a-pinene (acide pinique et pinonique) et du β-caryophyllene. ~ 5% de la masse du secondaire contemporain Autres précurseurs? Ou….

  11. Sources de l’AOS biogénique ? Autres précurseurs? Ou…. Vieillissement hétérogène des produits d’oxydation de premières générations : polymérisation ? HULIS Organo-sulfates El Haddad et al. 2010b El Haddad et al. 2010b

  12. Mace Head, Atlantique Nord O’Dowd et Leeuw 2007 O’Dowd et Leeuw 2007 Organic fraction : between 50 et 80% of submicon aerosol mass

  13. Objectives of the primary marine emission task Chemical and physical characterisation of primary particulate marine emissions Is there a specificity of the mediterranean sea? Bubble Bursting Experiments (Action planned in 2011 –LCP/LaMP-) SMPS : Size distribution (10-1000nm) HR-ToF AMS (Size resolved chemical composition of non refractory sub-micron particles) PM1 + PM10 filters samples (organic speciation) Chemical fingerprint VHDTMA : Hygroscopic growth 1- Winter and « bloom » seasons 2- Anthropogenic influenced coastal water (Frioul?), « natural » coastal water (Porquerolles?), open sea ? Mediterranean Sea water

  14. Global ship traffic (fraction of total in each grid cell) 2002-2005(from Wang et al., ES&T, 2008) Mediterranean sea is a hot spot for ship trafic (Marseille : 3rd harbour in the world for crude oil and oil products)

  15. Project APICE (under review) (2010-2013) New : Project selected to get into the second and final phase of the selection procedure Objective : Impact of harbours and harbours related activities to urban PM pollution in 5 mediterranean harbours Scientific partnership • Venice(Lead Partner) : ARPAV Veneto • (P. De Lazzer) • Genoa : University of Genoa(P. Prati) • Thessaloniki : • Aristotle University of Thessaloniki(M. Dimitrios) • University of West Macedonia(G. Bartzis) • Barcelona : • CSIC-Institute of Environmental Assessment and Water Research (IDAEA) • (N. Moreno/X Querol) • Marseille : • University of Provence(N. Marchand) Shipping emissions chemical characterization + 1 year observations of PM composition associated with source apportionment studies are scheduled simultaneously in each harbors (2011-2012)

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