Evaluation of detailed aromatic mechanisms (MCMv3 and MCMv3.1) against environmental chamber data

Abstract. A high quality dataset on the photo-oxidation of benzene, toluene, p-xylene and 1,3,5-trimethylbenzene has been obtained from experiments in the European Photoreactor (EUPHORE), a large outdoor environmental reaction chamber. The experiments were designed to test sensitive features of detailed aromatic mechanisms, and the dataset has been used to evaluate the performance of the Master Chemical Mechanism Version 3 (MCMv3). An updated version (MCMv3.1) was constructed based on recent experimental data, and details of its development are described in a companion paper. The MCMv3.1 aromatic mechanisms have also been evaluated using the EUPHORE dataset. Significant deficiencies have been identified in the mechanisms, in particular: 1) an over-estimation of the ozone concentration, 2) an under-estimation of the NO oxidation rate, 3) an under-estimation of OH. The use of MCMv3.1 improves the model-measurement agreement in some areas but significant discrepancies remain.

[1]  Michael J. Pilling,et al.  Quantitative assessment of uncertainties for a model of tropospheric ethene oxidation using the European Photoreactor (EUPHORE) , 2005 .

[2]  M. Jenkin,et al.  Simulating the Formation of Secondary Organic Aerosol from the Photooxidation of Aromatic Hydrocarbons , 2005 .

[3]  Michael E. Jenkin,et al.  Simulating the Formation of Secondary Organic Aerosol from the Photooxidation of Toluene , 2004 .

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

[5]  Alfons Bora,et al.  Final Report to the European Commission , 2004 .

[6]  Michael J. Pilling,et al.  Validation of the calibration of a laser-induced fluorescence instrument for the measurement of OH radicals in the atmosphere , 2003 .

[7]  A. Lewis,et al.  Measurements of photo-oxidation products from the reaction of a series of alkyl-benzenes with hydroxyl radicals during EXACT using comprehensive gas chromatography , 2003 .

[8]  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 .

[9]  M. Jenkin,et al.  Modelling of the photooxidation of toluene: conceptual ideas for validating detailed mechanisms , 2002 .

[10]  I. Barnes,et al.  FT–IR study of the ring-retaining products from the reaction of OH radicals with phenol, o-, m-, and p-cresol , 2002 .

[11]  Jack G. Calvert,et al.  The mechanisms of atmospheric oxidation of aromatic hydrocarbons , 2002 .

[12]  Takashi Imamura,et al.  OH-initiated oxidation of benzene Part I . Phenol formation under atmospheric conditions , 2002 .

[13]  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.

[14]  Ulrich Platt,et al.  Primary and Secondary Glyoxal Formation from Aromatics: Experimental Evidence for the Bicycloalkyl−Radical Pathway from Benzene, Toluene, and p-Xylene , 2001 .

[15]  M. C. Dodge,et al.  Chemical oxidant mechanisms for air quality modeling: critical review , 2000 .

[16]  Paul A. Solomon,et al.  Comparison of scientific findings from major ozone field studies in North America and Europe , 2000 .

[17]  M. Jacobson,et al.  Comparison of a 4000-reaction chemical mechanism with the carbon bond IV and an adjusted carbon bond IV-EX mechanism using SMVGEAR II , 2000 .

[18]  James N. Pitts,et al.  Chemistry of the Upper and Lower Atmosphere: Theory, Experiments, and Applications , 1999 .

[19]  T. Kleindienst,et al.  Primary Product Distributions from the Reaction of OH with m-, p-Xylene, 1,2,4- and 1,3,5-Trimethylbenzene , 1999 .

[20]  Ian Barnes,et al.  Atmospheric Oxidation of Toluene in a Large-Volume Outdoor Photoreactor: In Situ Determination of Ring-Retaining Product Yields , 1998 .

[21]  T. Kleindienst,et al.  Primary Product Distribution from the Reaction of Hydroxyl Radicals with Toluene at ppb NOX Mixing Ratios , 1998 .

[22]  R. Derwent,et al.  Photochemical ozone creation potentials for organic compounds in northwest Europe calculated with a master chemical mechanism , 1998 .

[23]  Sander Houweling,et al.  The impact of nonmethane hydrocarbon compounds on tropospheric photochemistry , 1998 .

[24]  B. Finlayson‐Pitts,et al.  Tropospheric air pollution: ozone, airborne toxics, polycyclic aromatic hydrocarbons, and particles. , 1997, Science.

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

[26]  R. Derwent,et al.  Photochemical ozone creation potentials for a large number of reactive hydrocarbons under European conditions , 1996 .

[27]  W. Carter.  Computer modeling of environmental chamber measurements of maximum incremental reactivities of volatile organic compounds , 1995 .

[28]  Environmental chamber studies of atmospheric reactivities of volatile organic compounds. Effects of varying chamber and light source. Final report , 1995 .

[29]  William P. L. Carter,et al.  Evaluation of a detailed gas-phase atmospheric reaction mechanism using environmental chamber data , 1991 .

[30]  G. Whitten,et al.  Background reactivity in smog chambers , 1990 .

[31]  Roger Atkinson,et al.  Formation of ring-retaining products from the OH radical-initiated reactions of benzene and toluene , 1989 .

[32]  A. Winer,et al.  The reaction of gas phase N2O5 with water vapor , 1983 .