Laboratory investigation of photochemical oxidation of organic aerosol from wood fires 1: measurement and simulation of organic aerosol evolution

Abstract. Experiments were conducted to investigate the effects of photo-oxidation on organic aerosol (OA) emissions from flaming and smoldering hard- and soft-wood fires under plume-like conditions. This was done by exposing the dilute emissions from a small wood stove to UV light in a smog chamber and measuring the gas- and particle-phase pollutant concentrations with a suite of instruments including a Proton Transfer Reaction Mass Spectrometer (PTR-MS), an Aerosol Mass Spectrometer (AMS) and a thermodenuder. The measurements highlight how atmospheric processing can lead to considerable evolution of the mass and volatility of biomass-burning OA. Photochemical oxidation produced substantial new OA, increasing concentrations by a factor of 1.5 to 2.8 after several hours of exposure to typical summertime hydroxyl radical (OH) concentrations. Less than 20% of this new OA could be explained using a state-of-the-art secondary organic aerosol model and the measured decay of traditional SOA precursors. The thermodenuder data indicate that the primary OA is semivolatile; at 50°C between 50 and 80% of the fresh primary OA evaporated. Aging reduced the volatility of the OA; at 50°C only 20 to 40% of aged OA evaporated. The predictions of a volatility basis-set model that explicitly tracks the partitioning and aging of low-volatility organics was compared to the chamber data. The OA production can be explained by the oxidation of low-volatility organic vapors; the model can also reproduce observed changes in OA volatility and composition. The model was used to investigate the competition between photochemical processing and dilution on OA concentrations in plumes.

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

[2]  A. Robinson,et al.  Interactive comment on “ Laboratory investigation of photochemical oxidation of organic aerosol from wood fires – Part 2 : Analysis of aerosol mass spectrometer data ” by A , 2009 .

[3]  W. Asher,et al.  SIMPOL.1: a simple group contribution method for predicting vapor pressures and enthalpies of vaporization of multifunctional organic compounds , 2007 .

[4]  D. Blake,et al.  Physical, chemical, and optical properties of regional hazes dominated by smoke in Brazil , 1998 .

[5]  Trainer,et al.  The influence of canadian forest fires on pollutant concentrations in the united states , 2000, Science.

[6]  Barbara J. Turpin,et al.  Species Contributions to PM2.5 Mass Concentrations: Revisiting Common Assumptions for Estimating Organic Mass , 2001 .

[7]  L A Currie,et al.  Sources of urban contemporary carbon aerosol. , 1994, Environmental science & technology.

[8]  Sangi Lee,et al.  Diagnosis of aged prescribed burning plumes impacting an urban area. , 2008, Environmental science & technology.

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

[10]  S. Pandis,et al.  Evaluation of secondary organic aerosol formation in winter , 1999 .

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

[12]  A. Stohl,et al.  Volatile organic compounds composition of merged and aged forest fire plumes from Alaska and western Canada , 2006 .

[13]  M. Andreae,et al.  An analysis of the chemical processes in the smoke plume from a savanna fire , 2005 .

[14]  M. Andreae,et al.  Emission of trace gases and aerosols from biomass burning , 2001 .

[15]  P. Crutzen,et al.  Comprehensive laboratory measurements of biomass‐burning emissions: 2. First intercomparison of open‐path FTIR, PTR‐MS, and GC‐MS/FID/ECD , 2004 .

[16]  A. Presto,et al.  Secondary Organic Aerosol Production from Terpene Ozonolysis. 2. Effect of NO x Concentration , 2005 .

[17]  J. Schauer,et al.  Spatial distribution of carbonaceous aerosol in the southeastern United States using molecular markers and carbon isotope data , 2006 .

[18]  J. Jimenez,et al.  Technical Note: Description and Use of the New Jump Mass Spectrum Mode of Operation for the Aerodyne Quadrupole Aerosol Mass Spectrometers (Q-AMS) , 2007 .

[19]  Spyros N. Pandis,et al.  Ozonolysis of α-pinene: parameterization of secondary organic aerosol mass fraction , 2007 .

[20]  J. Reid,et al.  A review of biomass burning emissions, part I: gaseous emissions of carbon monoxide, methane, volatile organic compounds, and nitrogen containing compounds , 2005 .

[21]  Charles O Stanier,et al.  Measurements of the volatility of aerosols from alpha-pinene ozonolysis. , 2007, Environmental science & technology.

[22]  J. Schauer,et al.  Source Apportionment of Wintertime Gas-Phase and Particle-Phase Air Pollutants Using Organic Compounds as Tracers , 2000 .

[23]  Jim Haywood,et al.  Evolution of biomass burning aerosol properties from an agricultural fire in southern Africa , 2003 .

[24]  G R Cass,et al.  Measurement of emissions from air pollution sources. 3. C1-C29 organic compounds from fireplace combustion of wood. , 2001, Environmental science & technology.

[25]  Allen L Robinson,et al.  Effects of dilution on fine particle mass and partitioning of semivolatile organics in diesel exhaust and wood smoke. , 2006, Environmental science & technology.

[26]  T. Eck,et al.  A review of biomass burning emissions part III: intensive optical properties of biomass burning particles , 2004 .

[27]  Thomas W. Kirchstetter,et al.  Controlled generation of black carbon particles from a diffusion flame and applications in evaluating black carbon measurement methods , 2007 .

[28]  A. Goldstein,et al.  Atmospheric volatile organic compound measurements during the Pittsburgh Air Quality Study: Results, interpretation, and quantification of primary and secondary contributions , 2005 .

[29]  Yong Bin Lim,et al.  Products and mechanism of secondary organic aerosol formation from reactions of n-alkanes with OH radicals in the presence of NOx. , 2005, Environmental science & technology.

[30]  A. Robinson,et al.  Source apportionment of molecular markers and organic aerosol. 2. Biomass smoke. , 2006, Environmental science & technology.

[31]  W. Parkhurst,et al.  Fossil Sources of Ambient Aerosol Carbon Based on 14C Measurements Special Issue of Aerosol Science and Technology on Findings from the Fine Particulate Matter Supersites Program , 2004 .

[32]  M. Andreae,et al.  Smoking Rain Clouds over the Amazon , 2004, Science.

[33]  J. Watson.  Visibility: Science and Regulation , 2002, Journal of the Air & Waste Management Association.

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

[35]  M. Andreae,et al.  Chemical processes in a young biomass-burning plume , 2003 .

[36]  Albert A Presto,et al.  Secondary organic aerosol production from terpene ozonolysis. 2. Effect of NOx concentration. , 2005, Environmental science & technology.

[37]  Spyros N. Pandis,et al.  Measurements of the volatility of aerosols from α-pinene ozonolysis , 2007 .

[38]  Bonyoung Koo,et al.  Integrated approaches to modeling the organic and inorganic atmospheric aerosol components , 2003 .

[39]  A. Robinson,et al.  Modeling semivolatile organic aerosol mass emissions from combustion systems. , 2006, Environmental science & technology.

[40]  A. Sullivan,et al.  Fine Aerosol Bulk Composition Measured on WP-3D Research Aircraft in Vicinity of the Northeastern United States - Results from NEAQS , 2007 .

[41]  Allen L Robinson,et al.  Organic aerosol formation from photochemical oxidation of diesel exhaust in a smog chamber. , 2007, Environmental science & technology.

[42]  D. Streets,et al.  A technology‐based global inventory of black and organic carbon emissions from combustion , 2004 .

[43]  John T. Pisano,et al.  A new environmental chamber for evaluation of gas-phase chemical mechanisms and secondary aerosol formation , 2005 .

[44]  Allen L. Robinson,et al.  Is the gas‐particle partitioning in alpha‐pinene secondary organic aerosol reversible? , 2007 .

[45]  S. Pandis,et al.  Aerosol volatility measurement using an improved thermodenuder: Application to secondary organic aerosol , 2007 .

[46]  Allen L. Robinson,et al.  Effects of gas particle partitioning and aging of primary emissions on urban and regional organic aerosol concentrations , 2008 .

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

[48]  Barbara J. Turpin,et al.  Measuring and simulating particulate organics in the atmosphere: problems and prospects , 2000 .

[49]  D. Allen,et al.  Estimates of heterogeneous formation of secondary organic aerosol during a wood smoke episode in Houston, Texas , 2007 .

[50]  P. Pilewskie,et al.  Evolution of gases and particles from a savanna fire in South Africa , 2003 .

[51]  Allen L. Robinson,et al.  Positive and Negative Artifacts in Particulate Organic Carbon Measurements with Denuded and Undenuded Sampler Configurations Special Issue of Aerosol Science and Technology on Findings from the Fine Particulate Matter Supersites Program , 2004 .

[52]  Allen L. Robinson,et al.  Evolving mass spectra of the oxidized component of organic aerosol: results from aerosol mass spectrometer analyses of aged diesel emissions , 2008 .

[53]  P. S. Praveen,et al.  Atmospheric brown clouds: Hemispherical and regional variations in long‐range transport, absorption, and radiative forcing , 2007 .

[54]  J. Lelieveld,et al.  The Indian Ocean Experiment: Widespread Air Pollution from South and Southeast Asia , 2001, Science.

[55]  W. Hao,et al.  The Tropical Forest and Fire Emissions Experiment: method evaluation of volatile organic compound emissions measured by PTR-MS, FTIR, and GC from tropical biomass burning , 2007 .

[56]  A. Grieshop.  Laboratory studies of the atmospheric aging of wood smoke , 2008 .

[57]  P. Ziemann,et al.  Chemically-resolved volatility measurements of organic aerosol fom different sources. , 2009, Environmental science & technology.

[58]  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.

[59]  C E Kolb,et al.  Guest Editor: Albert Viggiano CHEMICAL AND MICROPHYSICAL CHARACTERIZATION OF AMBIENT AEROSOLS WITH THE AERODYNE AEROSOL MASS SPECTROMETER , 2022 .

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

[61]  Albert A Presto,et al.  Secondary organic aerosol production from terpene ozonolysis. 1. Effect of UV radiation. , 2005, Environmental science & technology.

[62]  Michael J. Kleeman,et al.  Size and Composition Distribution of Fine Particulate Matter Emitted from Wood Burning, Meat Charbroiling, and Cigarettes , 1999 .

[63]  J. Pierce,et al.  Constraining Particle Evolution from Wall Losses, Coagulation, and Condensation-Evaporation in Smog-Chamber Experiments: Optimal Estimation Based on Size Distribution Measurements , 2008 .

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