Application of the CACM and MPMPO modules using the CMAQ model for the eastern United States

[1] The Caltech Atmospheric Chemistry Mechanism (CACM) and the Model to Predict the Multiphase Partitioning of Organics (MPMPO) have been updated with a detailed treatment of the oxidation mechanisms and secondary organic aerosol (SOA) formation potentials of α-pinene, β-pinene, and d-limonene. The updated CACM and MPMPO modules have been incorporated into the Community Multiscale Air Quality (CMAQ) model. The revised CMAQ model was used to simulate air quality over the eastern United States, with a particular focus on New England (NE) for the period 3–4 August 2004, which was part of the International Consortium for Atmospheric Research on Transport and Transformation (ICARTT) campaign. On 3 August, 24-hour-average organic aerosol (OA) and PM2.5 concentrations were approximately 7.0 μg m−3 and 13.0 μg m−3, respectively, at Thompson Farm (TF), a rural site in southeastern New Hampshire. The model results (e.g., ozone (O3), PM2.5, and individual PM2.5 chemical components) were compared against various observational data sets (e.g., AIRMAP, IMPROVE, SEARCH, and AIRNOW), as well as CMAQ model predictions using the CB-IV gas-phase mechanism and the SORGAM SOA module. Both CMAQ model simulations with CACM/MPMPO and with CB-IV/SORGAM predicted O3, PM2.5, sulfate, and ammonium reasonably well but underestimated elemental and organic carbon aerosol. SOA predictions from CACM/MPMPO and from CB-IV/SORGAM were very close for the sites where OA concentrations were available on 4 August, though sensitivity of SOA predictions at TF to domain-wide NOx emissions and temperature variations differed significantly. Additionally, on the basis of the predicted chemical composition of OA from CMAQ with CACM/MPMPO, 24-hour averages of the ratio of the organic mass to organic carbon were determined to be in the range of 1.1 to 1.9, depending on the relative abundance of SOA and primary organics.

[1]  John H. Seinfeld,et al.  Secondary organic aerosol formation from isoprene photooxidation under high‐NOx conditions , 2005 .

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

[3]  R. Derwent,et al.  Atmospheric Chemistry and Physics Protocol for the Development of the Master Chemical Mechanism, Mcm V3 (part B): Tropospheric Degradation of Aromatic Volatile Organic Compounds , 2022 .

[4]  Donald Dabdub,et al.  Simulation and analysis of secondary organic aerosol dynamics in the South Coast Air Basin of California , 2006 .

[5]  C H E N S O N G,et al.  Impact of the Hydrocarbon to NO x Ratio on Secondary Organic Aerosol Formation , 2022 .

[6]  Adrian Sandu,et al.  Benchmarking stiff ode solvers for atmospheric chemistry problems II: Rosenbrock solvers , 1997 .

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

[8]  John H. Seinfeld,et al.  Organic aerosol formation from the oxidation of biogenic hydrocarbons , 1999 .

[9]  P. Saxena,et al.  Water-soluble organics in atmospheric particles: A critical review of the literature and application of thermodynamics to identify candidate compounds , 1996 .

[10]  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 .

[11]  W. Parkhurst,et al.  Regional composition of PM2.5 aerosols measured at urban, rural and “background” sites in the Tennessee valley , 2004 .

[12]  A. Thompson,et al.  Smart balloon observations over the North Atlantic: O3 data analysis and modeling , 2006 .

[13]  D. Allen,et al.  Sesquiterpene Emissions and Secondary Organic Aerosol Formation Potentials for Southeast Texas Special Issue of Aerosol Science and Technology on Findings from the Fine Particulate Matter Supersites Program , 2004 .

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

[15]  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.

[16]  H. Mao,et al.  Quantification of ozone formation metrics at Thompson Farm during the New England Air Quality Study (NEAQS) 2002 , 2004 .

[17]  Judith C. Chow,et al.  Temporal and spatial variations of PM2.5 and PM10 aerosol in the Southern California air quality study , 1994 .

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

[19]  R. Gunst,et al.  Response of ozone to changes in hydrocarbon and nitrogen oxide concentrations in outdoor smog chambers filled with Los Angeles air , 1990 .

[20]  D. Shallcross,et al.  Development and application of a possible mechanism for the generation of cis-pinic acid from the ozonolysis of α- and β-pinene , 2000 .

[21]  Frank M. Bowman,et al.  Formation of Organic Aerosols from the Oxidation of Biogenic Hydrocarbons , 1997 .

[22]  W. Stockwell,et al.  The second generation regional acid deposition model chemical mechanism for regional air quality modeling , 1990 .

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

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

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

[26]  H. Mao,et al.  Diurnal characteristics of surface level O3 and other important trace gases in New England , 2005 .

[27]  Sonia M. Kreidenweis,et al.  A modeling study of aqueous production of dicarboxylic acids: 1. Chemical pathways and speciated organic mass production , 2004 .

[28]  A. Nenes,et al.  ISORROPIA: A New Thermodynamic Equilibrium Model for Multiphase Multicomponent Inorganic Aerosols , 1998 .

[29]  J. Seinfeld,et al.  Secondary organic aerosol 1. Atmospheric chemical mechanism for production of molecular constituents , 2002 .

[30]  Donald Dabdub,et al.  Secondary organic aerosol 3. Urban/regional scale model of size- and composition-resolved aerosols , 2002 .

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

[32]  Judith C. Chow,et al.  Fine Particle and Gaseous Emission Rates from Residential Wood Combustion , 2000 .

[33]  M. C. Dodge,et al.  A photochemical kinetics mechanism for urban and regional scale computer modeling , 1989 .

[34]  Christian Seigneur,et al.  Application and Evaluation of Two Air Quality Models for Particulate Matter for a Southeastern U.S. Episode , 2004, Journal of the Air & Waste Management Association.

[35]  G. Hidy,et al.  The Southeastern Aerosol Research and Characterization Study: Part 1—Overview , 2003, Journal of the Air & Waste Management Association.

[36]  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 .

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

[38]  M. Pilling,et al.  European Geosciences Union 2002 Atmospheric Chemistry and Physics Discussions Protocol for the development of the Master Chemical Mechanism , MCM v 3 ( Part B ) : tropospheric degradation of aromatic volatile organic compounds , 2002 .

[39]  I. J. Ackermann,et al.  Modeling the formation of secondary organic aerosol within a comprehensive air quality model system , 2001 .

[40]  Michael E. Jenkin,et al.  Modelling the formation and composition of secondary organic aerosol from α- and β-pinene ozonolysis using MCM v3 , 2004 .

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

[42]  J. Blom,et al.  Benchmarking Stiff ODE Solvers for Atmospheric Chemistry Problems II: Rosenbrock Methods , 1996 .

[43]  Michael E. Jenkin,et al.  Simulating the detailed chemical composition of secondary organic aerosol formed on a regional scale during the TORCH 2003 campaign in the southern UK , 2005 .

[44]  David R Cocker,et al.  Impact of the hydrocarbon to NOx ratio on secondary organic aerosol formation. , 2005, Environmental science & technology.

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

[46]  Samuel H. Yalkowsky,et al.  Estimating Pure Component Vapor Pressures of Complex Organic Molecules , 1997 .

[47]  W. Carter A detailed mechanism for the gas-phase atmospheric reactions of organic compounds , 1990 .

[48]  Hal Westberg,et al.  A biogenic hydrocarbon emission inventory for the U.S.A. using a simple forest canopy model , 1993 .

[49]  R. Griffin,et al.  Modeling secondary organic aerosol formation from oxidation of α-pinene, β-pinene, and d-limonene , 2005 .

[50]  B. Lamb,et al.  Natural emissions of non-methane volatile organic compounds, carbon monoxide, and oxides of nitrogen from North America , 2000 .

[51]  J Wayne Miller,et al.  Emission rates of particulate matter and elemental and organic carbon from in-use diesel engines. , 2004, Environmental science & technology.

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

[53]  Christian Seigneur,et al.  Secondary organic aerosol 2. Thermodynamic model for gas/particle partitioning of molecular constituents , 2002 .

[54]  D. Byun Science algorithms of the EPA Models-3 community multi-scale air quality (CMAQ) modeling system , 1999 .

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

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

[57]  Jay R. Turner,et al.  A method for on‐line measurement of water‐soluble organic carbon in ambient aerosol particles: Results from an urban site , 2004 .

[58]  S. Madronich,et al.  Contribution of Secondary VOC to the Composition of Aqueous Atmospheric Particles: A Modeling Approach , 2000 .

[59]  W. Malm,et al.  Spatial and seasonal trends in particle concentration and optical extinction in the United States , 1994 .

[60]  J. Seinfeld,et al.  Development and application of the Model of Aerosol Dynamics, Reaction, Ionization, and Dissolution (MADRID) , 2004 .

[61]  Donald Dabdub,et al.  A Coupled Hydrophobic-Hydrophilic Model for Predicting Secondary Organic Aerosol Formation , 2003 .

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

[63]  Christian Seigneur,et al.  Current Status of Air Quality Models for Particulate Matter , 2001, Journal of the Air & Waste Management Association.