Comparison of photochemical mechanisms for air quality modeling

Abstract Photochemical mechanisms are a critical module of air quality models. In the past 20 years, several mechanisms have been developed to study the chemistry of the troposphere. This work compares several state-of-the-science photochemical mechanisms (including LCC, CBM-IV, RADM2, EMEP, RACM, SAPRC99, and CACM which have never been compared before in other studies). Concise descriptions of the chemical schemes are included. The main difference among existing mechanisms is the lumping technique used to classify organic compounds into surrogate groups. First, box model calculations are conducted to highlight the features that lead to differences in the modeled behaviors of photochemical pollutants and their precursors. Results indicate that most chemical schemes yield similar ozone concentrations. Nevertheless, there are significant discrepancies, mainly in predicted concentration of HNO 3 , HO 2 and total PAN among model simulations. Finally, the sources of the discrepancy are identified.

[1]  G. D. Byrne,et al.  VODE: a variable-coefficient ODE solver , 1989 .

[2]  William R. Stockwell,et al.  First-order sensitivity analysis of models with time-dependent parameters: an application to PAN and ozone , 1999 .

[3]  Paulette Middleton,et al.  Aggregation and analysis of volatile organic compound emissions for regional modeling , 1990 .

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

[5]  J. Milford,et al.  The effect of acetyl peroxy-peroxy radical reactions on peroxyacetyl nitrate and ozone concentrations , 1995 .

[6]  Lori M. Perliski,et al.  Results from the Intergovernmental Panel on Climatic Change Photochemical Model Intercomparison (PhotoComp) , 1997 .

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

[8]  D. Simpson,et al.  Biogenic emissions in Europe: 2. Implications for ozone control strategies , 1995 .

[9]  Robin L. Dennis,et al.  NARSTO critical review of photochemical models and modeling , 2000 .

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

[11]  Differences in NOy speciation predicted by three photochemical mechanisms , 1999 .

[12]  Daewon W. Byun,et al.  The next generation of integrated air quality modeling: EPA's models-3 , 1996 .

[13]  W. Stockwell On the HO2 + HO2 reaction: Its misapplication in atmospheric chemistry models , 1995 .

[14]  Meehye Lee,et al.  Hydrogen peroxide and organic hydroperoxide in the troposphere: a review , 2000 .

[15]  J. Seinfeld,et al.  Development and evaluation of a photooxidation mechanism for isoprene , 1992 .

[16]  H. Gäggeler,et al.  Gas-phase Chemistry , 2003 .

[17]  D. Simpson,et al.  Comparison of the chemical schemes of the EMEP MSC-W and IVL photochemical trajectory models , 1999 .

[18]  Jana B. Milford,et al.  Global uncertainty analysis of a regional-scale gas-phase chemical mechanism , 1996 .

[19]  F. Kirchner,et al.  A new mechanism for regional atmospheric chemistry modeling , 1997 .

[20]  Harvey E. Jeffries,et al.  A comparison of two photochemical reaction mechanisms using mass balance and process analysis , 1994 .

[21]  Intercomparison of Photochemical Mechanisms using Response Surfaces and Process Analysis , 2004 .

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

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

[24]  E. Grosjean,et al.  Peroxyacetyl nitrate and peroxypropionyl nitrate during SCOS 97-NARSTO. , 2001, Environmental science & technology.

[25]  D. Simpson,et al.  Long-period modelling of photochemical oxidants in Europe. Model calculations for July 1985 , 1992 .

[26]  B. Vogel,et al.  Intercomparison of the gas-phase chemistry in several chemistry and transport models , 1998 .

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

[28]  R. Atkinson Atmospheric chemistry of VOCs and NOx , 2000 .

[29]  F. Lurmann A Surrogate Species chemical Reaction Mechanism for Urban-Scale Air Quality Simulation Models , 1987 .

[30]  R. A. Cox,et al.  Evaluated Kinetic and Photochemical Data for Atmospheric Chemistry, Organic Species: Supplement VII , 1999 .

[31]  M. Molina,et al.  Chemical kinetics and photochemical data for use in stratospheric modeling , 1985 .

[32]  S. Krupa,et al.  Photochemical oxidants: state of the science. , 1999, Environmental pollution.

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

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

[35]  Scenarios for Modeling Multiphase Tropospheric Chemistry , 2001 .

[36]  W. Stockwell A homogeneous gas phase mechanism for use in a regional acid deposition model , 1986 .