Secondary Organic Aerosol Formation from Acetylene (C 2 H 2 ): seed effect on SOA yields due to organic photochemistry in the aerosol aqueous phase

Abstract. The lightest Non Methane HydroCarbon (NMHC), i.e., acetylene (C2H2) is found to form secondary organic aerosol (SOA). Contrary to current belief, the number of carbon atoms, n, for a NMHC to act as SOA precursor is lowered to n=2 here. The OH-radical initiated oxidation of C2H2 forms glyoxal (CHOCHO) as the highest yield product, and >99% of the SOA from C2H2 is attributed to CHOCHO. SOA formation from C2H2 and CHOCHO was studied in a photochemical and a dark simulation chamber. Further, the experimental conditions were varied with respect to the chemical composition of the seed aerosols, mild acidification with sulphuric acid (SA, 3

[1]  S. Pandis,et al.  Water Absorption by Secondary Organic Aerosol and Its Effect on Inorganic Aerosol Behavior , 2000 .

[2]  A. L. Corrigan,et al.  Uptake of glyoxal by organic and Inorganic aerosol. , 2008, Environmental science & technology.

[3]  J. Burrows,et al.  Simultaneous global observations of glyoxal and formaldehyde from space , 2006 .

[4]  C. Chan,et al.  The hygroscopic properties of dicarboxylic and multifunctional acids: measurements and UNIFAC predictions. , 2001, Environmental science & technology.

[5]  Qi Zhang,et al.  Ubiquity and dominance of oxygenated species in organic aerosols in anthropogenically‐influenced Northern Hemisphere midlatitudes , 2007 .

[6]  Robert McLaren,et al.  Heterogeneous reactions of glyoxal on particulate matter: identification of acetals and sulfate esters. , 2005, Environmental science & technology.

[7]  Charles E. Kolb,et al.  Characterization of ambient aerosols in Mexico City during the MCMA-2003 campaign with Aerosol Mass Spectrometry: results from the CENICA Supersite , 2006 .

[8]  John H. Seinfeld,et al.  Secondary Organic Aerosol from the Photooxidation of Aromatic Hydrocarbons: Molecular Composition , 1997 .

[9]  Sönke Szidat,et al.  Contributions of fossil fuel, biomass-burning, and biogenic emissions to carbonaceous aerosols in Zurich as traced by 14C , 2006 .

[10]  John H. Seinfeld,et al.  Chamber studies of secondary organic aerosol growth by reactive uptake of simple carbonyl compounds , 2005 .

[11]  S. Madronich,et al.  Evaluation of new secondary organic aerosol models for a case study in Mexico City , 2008 .

[12]  A. Córdova,et al.  A kinetic and mechanistic study of the amino acid catalyzed aldol condensation of acetaldehyde in aqueous and salt solutions. , 2008, The journal of physical chemistry. A.

[13]  P. Warneck,et al.  Multi-Phase Chemistry of C2 and C3 Organic Compounds in the Marine Atmosphere , 2005 .

[14]  Alexandre Caseiro,et al.  Source apportionment of PM2.5 organic aerosol over Europe: Primary/secondary, natural/anthropogenic, and fossil/biogenic origin , 2007 .

[15]  P. Crutzen,et al.  Human‐activity‐enhanced formation of organic aerosols by biogenic hydrocarbon oxidation , 2000 .

[16]  David R. Cocker,et al.  The effect of water on gas-particle partitioning of secondary organic aerosol: II. m-xylene and 1,3,5-trimethylbenzene photooxidation systems , 2001 .

[17]  Jun Zhao,et al.  Heterogeneous reactions of methylglyoxal in acidic media: implications for secondary organic aerosol formation. , 2006, Environmental science & technology.

[18]  M. Molina,et al.  DOAS measurement of glyoxal as an indicator for fast VOC chemistry in urban air , 2005 .

[19]  Douglas R. Worsnop,et al.  Chemically-resolved aerosol volatility measurements from two megacity field studies , 2009 .

[20]  Michael J. Pilling,et al.  Development of a detailed chemical mechanism (MCMv3.1) for the atmospheric oxidation of aromatic hydrocarbons , 2004 .

[21]  W. Malm,et al.  Relative Contributions of Fossil and Contemporary Carbon sources to PM 2.5 Aerosols at Nine IMPROVE Network Sites , 2006 .

[22]  G. Takacs,et al.  Atmospheric photodissociation lifetimes for nitromethane, methyl nitrite, and methyl nitrate , 1980 .

[23]  J. Arey,et al.  Formation and reaction of hydroxycarbonyls from the reaction of OH radicals with 1,3-butadiene and isoprene. , 2005, Environmental science & technology.

[24]  D. Kaiser,et al.  0-(2,3,4,5,6-pentafluorobenzyl)hydroxylamine hydrochloride as a sensitive derivatizing agent for the electron capture gas liquid chromatographic analysis of keto steroids. , 1975, Journal of chromatographic science.

[25]  Annmarie G Carlton,et al.  Isoprene forms secondary organic aerosol through cloud processing: model simulations. , 2005, Environmental science & technology.

[26]  J. Seinfeld,et al.  Secondary organic aerosol formation and transport , 1992 .

[27]  J. Seinfeld,et al.  Global distribution and climate forcing of carbonaceous aerosols , 2002 .

[28]  D. Salcedo,et al.  A missing sink for gas‐phase glyoxal in Mexico City: Formation of secondary organic aerosol , 2007 .

[29]  H. Hansson,et al.  High Natural Aerosol Loading over Boreal Forests , 2006, Science.

[30]  Qi Zhang,et al.  O/C and OM/OC ratios of primary, secondary, and ambient organic aerosols with high-resolution time-of-flight aerosol mass spectrometry. , 2008, Environmental science & technology.

[31]  J. Pankow.  An absorption model of GAS/Particle partitioning of organic compounds in the atmosphere , 1994 .

[32]  Barbara J. Turpin,et al.  Secondary organic aerosol formation in cloud and fog droplets: a literature evaluation of plausibility , 2000 .

[33]  Daniel A. Lack,et al.  Seasonal variability of secondary organic aerosol: A global modeling study , 2004 .

[34]  Jean-Francois Lamarque,et al.  Predicted change in global secondary organic aerosol concentrations in response to future climate, emissions, and land use change , 2008 .

[35]  John H. Seinfeld,et al.  Global modeling of secondary organic aerosol formation from aromatic hydrocarbons: high- vs. low-yield pathways , 2007 .

[36]  J. H. Seinfeld,et al.  The Atmospheric Aerosol-Forming Potential of Whole Gasoline Vapor , 1997, Science.

[37]  M. Doré,et al.  Mecanisme d'action des radicaux OH sur les acides glycolique, glyoxylique, acetique et oxalique en solution aqueuse: Incidence sur la consammation de peroxyde d'hydrogene dans les systemes H2O2UV et O3H2O2 , 1997 .

[38]  A. Wexler,et al.  Atmospheric aerosol models for systems including the ions H+, NH4+, Na+, SO42−, NO3−, Cl−, Br−, and H2O , 2002 .

[39]  John P. Burrows,et al.  Global budgets of atmospheric glyoxal and methylglyoxal, and implications for formation of secondary organic aerosols , 2007 .

[40]  Annmarie G. Carlton,et al.  Atmospheric oxalic acid and SOA production from glyoxal: Results of aqueous photooxidation experiments , 2007 .

[41]  James F. Pankow,et al.  Prediction of activity coefficients in liquid aerosol particles containing organic compounds, dissolved inorganic salts, and water—Part 2: Consideration of phase separation effects by an X-UNIFAC model , 2006 .

[42]  Judith C. Chow,et al.  Fossil and contemporary fine particulate carbon fractions at 12 rural and urban sites in the United States , 2008 .

[43]  Christian George,et al.  Uptake Rate Measurements of Methanesulfonic Acid and Glyoxal by Aqueous Droplets , 1998 .

[44]  C. Chan,et al.  Hygroscopicity of water-soluble organic compounds in atmospheric aerosols: amino acids and biomass burning derived organic species. , 2005, Environmental science & technology.

[45]  M. Kleeman,et al.  A 3D Eulerian source-oriented model for an externally mixed aerosol. , 2001, Environmental science & technology.

[46]  M. Hannigan,et al.  Size-resolved source apportionment of airborne particle mass in a roadside environment. , 2008, Environmental science & technology.

[47]  Tami C. Bond,et al.  Critical assessment of the current state of scientific knowledge, terminology, and research needs concerning the role of organic aerosols in the atmosphere, climate, and global change , 2005 .

[48]  M. Andreae,et al.  Formation of Secondary Organic Aerosols Through Photooxidation of Isoprene , 2004, Science.

[49]  Donald Dabdub,et al.  Development and initial evaluation of a dynamic species-resolved model for gas phase chemistry and size-resolved gas/particle partitioning associated with secondary organic aerosol formation , 2005 .

[50]  John H. Seinfeld,et al.  Oxalic acid in clear and cloudy atmospheres: Analysis of data from International Consortium for Atmospheric Research on Transport and Transformation 2004 , 2006 .

[51]  C. Brühl,et al.  The influence of natural and anthropogenic secondary sources on the glyoxal global distribution , 2008 .

[52]  Robert McLaren,et al.  Reactive uptake of glyoxal by particulate matter , 2005 .

[53]  F. Bowman,et al.  Effect of activity coefficient models on predictions of secondary organic aerosol partitioning , 2004 .

[54]  Allen L Robinson,et al.  Rethinking Organic Aerosols: Semivolatile Emissions and Photochemical Aging , 2007, Science.

[55]  Xianliang Zhou,et al.  Apparent partition coefficients of 15 carbonyl compounds between air and seawater and between air and freshwater ; implications for air-sea exchange , 1990 .

[56]  Qi Zhang,et al.  Free and combined amino compounds in atmospheric fine particles (PM2.5) and fog waters from Northern California , 2003 .

[57]  Mark Bydder,et al.  CAPRAM 2.4 (MODAC mechanism): An extended and condensed tropospheric aqueous phase mechanism and its application , 2003 .

[58]  B. Lamb,et al.  © Author(s) 2006. This work is licensed under a Creative Commons License. Atmospheric Chemistry and Physics Atmospheric oxidation in the Mexico City Metropolitan Area , 2003 .

[59]  H. Jeffries,et al.  Identifying Airborne Carbonyl Compounds in Isoprene Atmospheric Photooxidation Products by Their PFBHA Oximes Using Gas Chromatography/Ion Trap Mass Spectrometry. , 1995, Environmental science & technology.

[60]  John H. Seinfeld,et al.  Secondary organic aerosol formation from m-xylene, toluene, and benzene , 2007 .

[61]  Peter Spietz,et al.  High-resolution absorption cross-section of glyoxal in the UV–vis and IR spectral ranges , 2005 .

[62]  D. R. Worsnop,et al.  Hydrocarbon-like and oxygenated organic aerosols in Pittsburgh: insights into sources and processes of organic aerosols , 2005 .

[63]  James F. Pankow,et al.  Thermodynamics of the formation of atmospheric organic particulate matter by accretion reactions—2. Dialdehydes, methylglyoxal, and diketones , 2005 .

[64]  James M. Roberts,et al.  Budget of organic carbon in a polluted atmosphere: Results from the New England Air Quality Study in 2002 , 2005 .

[65]  Hiroaki Minoura,et al.  Temperature dependence of secondary organic aerosol formation by photo-oxidation of hydrocarbons , 2003 .

[66]  J. Burrows,et al.  Volatile organic compounds in the polluted atmosphere: The 3rd ACCENT Barnsdale Expert Meeting , 2007 .

[67]  J. Seinfeld,et al.  Incremental Aerosol Reactivity: Application to Aromatic and Biogenic Hydrocarbons , 1999 .

[68]  Christian Seigneur,et al.  Uncertainties in modeling secondary organic aerosols: three-dimensional modeling studies in Nashville/western Tennessee. , 2003, Environmental science & technology.

[69]  Alla Zelenyuk,et al.  Effect of hydrophobic primary organic aerosols on secondary organic aerosol formation from ozonolysis of α‐pinene , 2007 .

[70]  Christoph Hueglin,et al.  Source apportionment of submicron organic aerosols at an urban site by factor analytical modelling of aerosol mass spectra , 2007 .

[71]  Earl L. Bailey,et al.  Secondary organic aerosol formation by glyoxal hydration and oligomer formation: humidity effects and equilibrium shifts during analysis. , 2005, Environmental science & technology.

[72]  R. Volkamer.  A DOAS Study on the Oxidation Mechanism of Aromatic Hydrocarbons under Simulated Atmospheric Conditions , 2001 .

[73]  Barry J. Huebert,et al.  A large organic aerosol source in the free troposphere missing from current models , 2005 .

[74]  Kostas Tsigaridis,et al.  Secondary organic aerosol importance in the future atmosphere , 2007 .

[75]  R. Derwent,et al.  Simulating regional scale secondary organic aerosol formation during the TORCH 2003 campaign in the southern UK , 2005 .

[76]  Edward O. Edney,et al.  Thermal properties of secondary organic aerosols , 2006 .

[77]  M. Uematsu,et al.  Free amino acids in marine aerosols over the western North Pacific Ocean , 2005 .

[78]  C. Zetzsch,et al.  Addition of OH to Acetylene and Consecutive Reactions of the Adduct with O2 , 1995 .

[79]  Annmarie G. Carlton,et al.  Oligomers formed through in-cloud methylglyoxal reactions: Chemical composition, properties, and mechanisms investigated by ultra-high resolution FT-ICR mass spectrometry , 2008 .

[80]  P. Ziemann,et al.  Yields of beta-hydroxynitrates and dihydroxynitrates in aerosol formed from OH radical-initiated reactions of linear alkenes in the presence of NO(x). , 2009, The journal of physical chemistry. A.

[81]  Klaus Wirtz,et al.  Is benzene a precursor for secondary organic aerosol? , 2005, Environmental science & technology.

[82]  E. Kassianov,et al.  Estimation of the mass absorption cross section of the organic carbon component of aerosols in the Mexico City Metropolitan Area , 2008 .

[83]  R. Kamens,et al.  Heterogeneous Atmospheric Aerosol Production by Acid-Catalyzed Particle-Phase Reactions , 2002, Science.

[84]  Armistead G. Russell,et al.  Gas/particle partitioning of water-soluble organic aerosol in Atlanta , 2009 .

[85]  J. Seinfeld,et al.  Organic atmospheric particulate material. , 2003, Annual review of physical chemistry.

[86]  David R. Cocker,et al.  The effect of water on gas–particle partitioning of secondary organic aerosol. Part I: α-pinene/ozone system , 2001 .

[87]  James F. Pankow,et al.  An absorption model of the gas/aerosol partitioning involved in the formation of secondary organic aerosol , 1994 .

[88]  T J Wallington,et al.  Organic aerosol formation during the atmospheric degradation of toluene. , 2001, Environmental science & technology.

[89]  H. Akimoto,et al.  Rate constants and mechanisms for the reaction of OH (OD) radicals with acetylene, propyne, and 2-butyne in air at 297 ± 2 K , 1986 .

[90]  R C Flagan,et al.  Measurements of secondary organic aerosol from oxidation of cycloalkenes, terpenes, and m-xylene using an Aerodyne aerosol mass spectrometer. , 2005, Environmental science & technology.

[91]  J. A. de Gouw,et al.  Airborne measurements of carbonaceous aerosol soluble in water over northeastern United States: Method development and an investigation into water-soluble organic carbon sources , 2006 .

[92]  John H. Seinfeld,et al.  the Creative Commons Attribution 3.0 License. Atmospheric Chemistry , 2008 .

[93]  John H Seinfeld,et al.  Reactions of semivolatile organics and their effects on secondary organic aerosol formation. , 2007, Environmental science & technology.

[94]  M. Molina,et al.  Secondary organic aerosol formation from anthropogenic air pollution: Rapid and higher than expected , 2006 .

[95]  L. Yeung,et al.  Kinetics and mechanistic studies of the atmospheric oxidation of alkynes. , 2005, The journal of physical chemistry. A.

[96]  Tami C. Bond,et al.  Color of brown carbon: A model for ultraviolet and visible light absorption by organic carbon aerosol , 2007 .

[97]  Erik Swietlicki,et al.  Organic aerosol and global climate modelling: a review , 2004 .

[98]  D. M. Cunnold,et al.  Evidence for Substantial Variations of Atmospheric Hydroxyl Radicals in the Past Two Decades , 2001, Science.

[99]  D. Hauglustaine,et al.  Change in global aerosol composition since preindustrial times , 2006 .

[100]  Kirsten W Loeffler,et al.  Oligomer formation in evaporating aqueous glyoxal and methyl glyoxal solutions. , 2006, Environmental science & technology.

[101]  Thomas W. Kirchstetter,et al.  Evidence that the spectral dependence of light absorption by aerosols is affected by organic carbon , 2004 .

[102]  Barbara J. Turpin,et al.  Oligomers, organosulfates, and nitrooxy organosulfates in rainwater identified by ultra-high resolution electrospray ionization FT-ICR mass spectrometry , 2008 .

[103]  L. A. Currie,et al.  Direct Quantification of PM2.5 Fossil and Biomass Carbon within the Northern Front Range Air Quality Study's Domain , 1999 .

[104]  Joost A. de Gouw,et al.  A study of secondary organic aerosol formation in the anthropogenic-influenced southeastern United States , 2007 .

[105]  M. Pilling,et al.  Measurement of OH and HO2 in the troposphere. , 2003, Chemical reviews.

[106]  Annmarie G. Carlton,et al.  Secondary organic aerosol yields from cloud‐processing of isoprene oxidation products , 2008 .