Reactive uptake of glyoxal by particulate matter

from 1.05 � 10 � 11 to 23.1 � 10 � 11 mg particle � 1 min � 1 in the presence of � 5 ppb glyoxal. Uptake coefficients (g) of glyoxal varied from 8.0 � 10 � 4 to 7.3 � 10 � 3 with a median g =2 .9� 10 � 3 , observed for (NH4)2SO4 seed aerosols at 55% relative humidity. Increased g values were related to increased particle acidity, indicating that acid catalysis played a role in the heterogeneous mechanism. Experiments conducted at very low relative humidity, with the potential to be highly acidic, resulted in very low reactive uptake. These uptake coefficients indicated that the heterogeneous loss of glyoxal in the atmosphere is at least as important as gas phase loss mechanisms, including photolysis and reaction with hydroxyl radicals. Glyoxal lifetime due to heterogeneous reactions under typical ambient conditions was estimated to be thet = 5–287 min. In rural and remote areas the glyoxal uptake can lead to 5–257 ng m � 3 of secondary organic aerosols in 8 hours, consistent with recent ambient measurements.

[1]  A. Wexler,et al.  Thermodynamic Model of the System H+−NH4+−Na+−SO42-−NO3-−Cl-−H2O at 298.15 K , 1998 .

[2]  L. Kleinman,et al.  Ozone formation at a rural site in the southeastern United States , 1994 .

[3]  B. Vogel,et al.  Hydrogen peroxide, organic peroxides, carbonyl compounds, and organic acids measured at Pabstthum during BERLIOZ , 2003 .

[4]  J. Seinfeld,et al.  Atmospheric Chemistry and Physics: From Air Pollution to Climate Change , 1997 .

[5]  M. Molina,et al.  GAS-PHASE AND HETEROGENEOUS CHEMICAL KINETICS OF THE TROPOSPHERE AND STRATOSPHERE , 1996 .

[6]  K. Mopper,et al.  Measurement of sub-parts-per-billion levels of carbonyl compounds in marine air by a simple cartridge trapping procedure followed by liquid chromatography , 1990 .

[7]  John H. Seinfeld,et al.  Sensitivity of direct climate forcing by atmospheric aerosols to aerosol size and composition , 1995 .

[8]  P. Ziemann,et al.  Thermal desorption mass spectrometric analysis of organic aerosol formed from reactions of 1-tetradecene and O3 in the presence of alcohols and carboxylic acids , 2000 .

[9]  G. Carmichael,et al.  Heterogeneous reactions of volatile organic compounds on oxide particles of the most abundant crustal elements: Surface reactions of acetaldehyde, acetone, and propionaldehyde on SiO2, Al2O3, Fe2O3, TiO2, and CaO , 2001 .

[10]  K. Kawamura Identification of C2-C10 .omega.-oxocarboxylic acids, pyruvic acid, and C2-C3 .alpha.-dicarbonyls in wet precipitation and aerosol samples by capillary GC and GC/MS , 1993 .

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

[12]  W. H. Hatcher,et al.  The Kinetics of the Decomposition of Gaseous Glyoxal , 1935 .

[13]  J. Seinfeld,et al.  Mathematical model for gas-particle partitioning of secondary organic aerosols , 1997 .

[14]  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 .

[15]  D. Dockery,et al.  Particulate air pollution and daily mortality in Steubenville, Ohio. , 1992, American journal of epidemiology.

[16]  R. Talbot,et al.  Optimization of a mist chamber (Cofer scrubber) for sampling water-soluble organics in air. , 2002, Environmental science & technology.

[17]  M. Hoffmann,et al.  Hydroxyalkylsulfonate formation: Its role as a S(IV) reservoir in atmospheric water droplets , 1989 .

[18]  D. Worsnop,et al.  Uptake of Gas-Phase Formaldehyde by Aqueous Acid Surfaces , 1996 .

[19]  M. Holdren,et al.  Atmospheric chemistry and distribution of formaldehyde and several multioxygenated carbonyl compounds during the 1995 Nashville/Middle Tennessee Ozone Study , 1998 .

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

[21]  P. Brimblecombe,et al.  A Thermodynamic Model of the System HCl-HNO 3H 2 S 04-H 20 , Including Solubilities of HBr , from < 200 to 328 K , 2001 .

[22]  R. A. Cox,et al.  Evaluated kinetic and photochemical data for atmospheric chemistry: Volume III - gas phase reactions of inorganic halogens , 2006 .

[23]  Kenneth A. Smith,et al.  Aerosol mass spectrometer for size and composition analysis of submicron particles , 1998 .

[24]  Hugh Coe,et al.  Quantitative sampling using an Aerodyne aerosol mass spectrometer 1. Techniques of data interpretation and error analysis , 2003 .

[25]  A. Goldstein,et al.  Secondary Atmospheric Photooxidation Products: Evidence for Biogenic and Anthropogenic Sources , 2001 .

[26]  Jeffrey T. Roberts,et al.  Chemistry at and near the Surface of Liquid Sulfuric Acid: A Kinetic, Thermodynamic, and Mechanistic Analysis of Heterogeneous Reactions of Acetone , 1999 .

[27]  L. Barrie,et al.  Source and reaction pathways of dicarboxylic acids, ketoacids and dicarbonyls in arctic aerosols: One year of observations , 1996 .

[28]  D. Riemer,et al.  The chemical processing of gas-phase carbonyl compounds by sulfuric acid aerosols: 2,4-pentanedione , 2003 .

[29]  D. Dockery,et al.  An association between air pollution and mortality in six U.S. cities. , 1993, The New England journal of medicine.

[30]  P. Reilly,et al.  Thermodynamic and kinetic analysis of the dimerization of aqueous glyoxal , 1986 .

[31]  S. Twomey,et al.  Aerosols, clouds and radiation , 1991 .

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

[33]  Shao-Meng Li,et al.  Chemical and physical characterizations of atmospheric aerosols over southern California , 1997 .

[34]  J. Fick,et al.  Effect of OH radicals, relative humidity, and time on the composition of the products formed in the ozonolysis of α-pinene , 2003 .

[35]  T. Nunes,et al.  Volatile organic compounds in rural atmospheres of central Portugal. , 2003, The Science of the total environment.

[36]  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.

[37]  R. Kamens,et al.  Characterization of secondary aerosol from the photooxidation of toluene in the presence of NOx and 1-propene. , 2001, Environmental science & technology.

[38]  J. Seinfeld,et al.  Atmospheric Chemistry of 1-Octene, 1-Decene, and Cyclohexene: Gas-Phase Carbonyl and Peroxyacyl Nitrate Products , 1996 .

[39]  Yin‐Nan Lee,et al.  Atmospheric carbonyl compounds at a rural southeastern United States site , 1995 .

[40]  H. Destaillats,et al.  Ambient air measurement of acrolein and other carbonyls at the Oakland-San Francisco Bay Bridge toll plaza. , 2002, Environmental science & technology.

[41]  R. Kamens,et al.  Atmospheric secondary aerosol formation by heterogeneous reactions of aldehydes in the presence of a sulfuric acid aerosol catalyst. , 2001, Environmental science & technology.

[42]  R. McLaren,et al.  An optimized method for the determination of volatile and semi-volatile aldehydes and ketones in ambient particulate matter , 2003 .

[43]  Charles E. Kolb,et al.  Ambient aerosol sampling using the Aerodyne Aerosol Mass Spectrometer , 2003 .

[44]  Roger Atkinson,et al.  Evaluated kinetic and photochemical data for atmospheric chemistry: Volume III - gas phase reactions of inorganic halogens , 2006 .

[45]  M. Jenkin,et al.  The tropospheric degradation of volatile organic compounds: a protocol for mechanism development , 1997 .

[46]  E. Grosjean,et al.  Speciated ambient carbonyls in Rio de Janeiro, Brazil. , 2002, Environmental science & technology.

[47]  J. Yu,et al.  Atmospheric photooxidation of alkylbenzenes-I. Carbonyl product analyses , 1997 .

[48]  Roger Atkinson,et al.  Development and evaluation of a detailed mechanism for the atmospheric reactions of isoprene and NOx , 1996 .

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

[50]  Martin Gallagher,et al.  Quantitative sampling using an Aerodyne aerosol mass spectrometer 2. Measurements of fine particulate chemical composition in two U.K. cities: QUANTITATIVE AEROSOL MASS SPECTROMETER ANALYSIS, 2 , 2003 .

[51]  M. Prather,et al.  Uptake of formaldehyde by sulfuric acid solutions: Impact on stratospheric ozone , 1993 .

[52]  Kevin J. Hussey,et al.  Development of an Improved Image Processing Based Visibility Model , 1993 .

[53]  U. Baltensperger,et al.  Identification of Polymers as Major Components of Atmospheric Organic Aerosols , 2004, Science.

[54]  L. Iraci,et al.  Heterogeneous interaction of formaldehyde with cold sulfuric acid: Implications for the upper troposphere and lower stratosphere , 1997 .

[55]  G. Cass,et al.  Source-oriented model for air pollutant effects on visibility , 1996 .

[56]  R. Kamens,et al.  Particle growth by acid-catalyzed heterogeneous reactions of organic carbonyls on preexisting aerosols. , 2003, Environmental science & technology.

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

[58]  Kenneth A. Smith,et al.  Development of an Aerosol Mass Spectrometer for Size and Composition Analysis of Submicron Particles , 2000 .