Multi-generation chemical aging of α -pinene ozonolysis products by reactions with OH

Abstract. Secondary organic aerosol (SOA) formation from volatile organic compounds (VOCs) in the atmosphere can be thought of as a succession of oxidation steps. The production of later-generation SOA via continued oxidation of the first-generation products is defined as chemical aging. This study investigates aging in the α -pinene ozonolysis system with hydroxyl radicals (OH) through smog chamber experiments. The first-generation α -pinene ozonolysis products were allowed to react further with OH formed via HONO photolysis. After an equivalent of 2–4 days of typical atmospheric oxidation conditions, homogeneous OH oxidation of the α -pinene ozonolysis products resulted in a 20–40 % net increase in the SOA for the experimental conditions used in this work. A more oxygenated product distribution was observed after aging based on the increase in aerosol atomic oxygen-to-carbon ratio (O : C) by up to 0.04. Experiments performed at intermediate relative humidity (RH) of 50 % showed no significant difference in additional SOA formation during aging compared to those performed at a low RH of less than 20 %.

[1]  J. Pierce,et al.  Particle wall-loss correction methods in smog chamber experiments , 2018, Atmospheric Measurement Techniques.

[2]  J. Seinfeld,et al.  Influence of seed aerosol surface area and oxidation rate on vapor walldeposition and SOA mass yields: a case study with α -pineneozonolysis , 2016 .

[3]  E. Robinson,et al.  Vapor wall loss of semi-volatile organic compounds in a Teflon chamber , 2016 .

[4]  P. Ziemann,et al.  Quantification of Gas-Wall Partitioning in Teflon Environmental Chambers Using Rapid Bursts of Low-Volatility Oxidized Species Generated in Situ. , 2016, Environmental science & technology.

[5]  E. Robinson,et al.  Uptake of Semivolatile Secondary Organic Aerosol Formed from α-Pinene into Nonvolatile Polyethylene Glycol Probe Particles. , 2016, The journal of physical chemistry. A.

[6]  J. Jimenez,et al.  In situ secondary organic aerosol formation from ambient pine forest air using an oxidation flow reactor , 2015 .

[7]  I. Riipinen,et al.  Near-Unity Mass Accommodation Coefficient of Organic Molecules of Varying Structure , 2014, Environmental science & technology.

[8]  Edward Charles Fortner,et al.  Elemental ratio measurements of organic compounds using aerosol mass spectrometry: characterization, improved calibration, and implications , 2014 .

[9]  Xuan Zhang,et al.  Influence of vapor wall loss in laboratory chambers on yields of secondary organic aerosol , 2014, Proceedings of the National Academy of Sciences.

[10]  I. Riipinen,et al.  Interactions between atmospheric ultrafine particles and secondary organic aerosol mass: a model study , 2014 .

[11]  S. Nakao,et al.  Aging of secondary organic aerosol from α-pinene ozonolysis: Roles of hydroxyl and nitrate radicals , 2012, Journal of the Air & Waste Management Association.

[12]  T. Lohaus,et al.  Organic aerosol yields from α-pinene oxidation: bridging the gap between first-generation yields and aging chemistry. , 2012, Environmental science & technology.

[13]  T. Leisner,et al.  Aging of biogenic secondary organic aerosol via gas-phase OH radical reactions , 2012, Proceedings of the National Academy of Sciences.

[14]  N. Donahue,et al.  Photochemical aging of α-pinene secondary organic aerosol: effects of OH radical sources and photolysis. , 2012, The journal of physical chemistry. A.

[15]  N. Donahue,et al.  Photo-oxidation of pinonaldehyde at low NO x : from chemistry to organic aerosol formation , 2012 .

[16]  S. Martin,et al.  Using elemental ratios to predict the density of organic material composed of carbon, hydrogen, and oxygen. , 2012, Environmental science & technology.

[17]  P. DeCarlo,et al.  OH clock determination by proton transfer reaction mass spectrometry at an environmental chamber , 2011 .

[18]  I. Riipinen,et al.  Volatility and hygroscopicity of aging secondary organic aerosol in a smog chamber , 2011 .

[19]  Hendrik Fuchs,et al.  Volatility of secondary organic aerosol during OH radical induced ageing , 2011 .

[20]  J. Seinfeld,et al.  Chemical aging of m -xylene secondary organic aerosol: laboratory chamber study , 2011 .

[21]  T. Hoffmann,et al.  Supporting material , 2019, Manual for Developing Intercultural Competencies.

[22]  L. Molina,et al.  Sources and production of organic aerosol in Mexico City: insights from the combination of a chemical transport model (PMCAMx-2008) and measurements during MILAGRO , 2010 .

[23]  A. Matsunaga,et al.  Gas-Wall Partitioning of Organic Compounds in a Teflon Film Chamber and Potential Effects on Reaction Product and Aerosol Yield Measurements , 2010 .

[24]  J. Stockman,et al.  Fine-Particulate Air Pollution and Life Expectancy in the United States , 2010 .

[25]  Majid Ezzati,et al.  Fine-particulate air pollution and life expectancy in the United States. , 2009, The New England journal of medicine.

[26]  A. Robinson,et al.  Effective rate constants and uptake coefficients for the reactions of organic molecular markers (n-alkanes, hopanes, and steranes) in motor oil and diesel primary organic aerosols with hydroxyl radicals. , 2009, Environmental science & technology.

[27]  Spyros N. Pandis,et al.  Simulating secondary organic aerosol formation using the volatility basis-set approach in a chemical transport model , 2008 .

[28]  Jay Slowik,et al.  Chemical aging of ambient organic aerosol from heterogeneous reaction with hydroxyl radicals , 2008 .

[29]  Spyros N. Pandis,et al.  An Algorithm for the Calculation of Secondary Organic Aerosol Density Combining AMS and SMPS Data , 2007 .

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

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

[32]  J. Burkholder,et al.  Rate coefficients for the OH + pinonaldehyde (C10H16O2) reaction between 297 and 374 K. , 2007, Environmental science & technology.

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

[34]  Markus Kalberer,et al.  Molecular size evolution of oligomers in organic aerosols collected in urban atmospheres and generated in a smog chamber. , 2006, Environmental science & technology.

[35]  A L Robinson,et al.  Coupled partitioning, dilution, and chemical aging of semivolatile organics. , 2006, Environmental science & technology.

[36]  P. Solomon,et al.  Airborne Particulate Matter and Human Health: A Review , 2005 .

[37]  J. Seinfeld,et al.  Secondary organic aerosol formation from the ozonolysis of cycloalkenes and related compounds. , 2004, Environmental science & technology.

[38]  Donald Dabdub,et al.  Estimate of global atmospheric organic aerosol from oxidation of biogenic hydrocarbons , 1999 .

[39]  S. Paulson,et al.  Measurement of OH radical formation from the reaction of ozone with several biogenic alkenes , 1998 .

[40]  J. Seinfeld,et al.  Gas/Particle Partitioning and Secondary Organic Aerosol Yields , 1996 .

[41]  K. Izumi,et al.  Photochemical aerosol formation from aromatic hydrocarbons in the presence of NOx , 1990 .

[42]  John H. Seinfeld,et al.  Parameterization of the formation potential of secondary organic aerosols , 1989 .

[43]  Daniel J. Rader,et al.  Aerosol Wall Losses in Electrically Charged Chambers , 1985 .

[44]  John H. Seinfeld,et al.  Turbulent deposition and gravitational sedimentation of an aerosol in a vessel of arbitrary shape , 1981 .