Preprints
https://doi.org/10.5194/egusphere-2023-2343
https://doi.org/10.5194/egusphere-2023-2343
03 Nov 2023
 | 03 Nov 2023

Derivation of Atmospheric Reaction Mechanisms for Volatile Organic Compounds by the SAPRC Mechanism Generation System (MechGen)

William P. L. Carter, Jia Jiang, John J. Orlando, and Kelley C. Barsanti

Abstract. This paper describes the methods that are used in the SAPRC mechanism generation system, MechGen, to estimate rate constants and derive mechanisms for gas-phase reactions of volatile organic compounds (VOCs) in the lower atmosphere. Earlier versions of this system have been used for over 20 years in the development of the SAPRC mechanisms for air quality models and ozone (O3) reactivity assessments. This is the first complete documentation of MechGen as it currently exists. MechGen can be used to derive explicit mechanisms for most compounds with C, H, O, or N atoms. Included are reactions of stable compounds with hydroxy (OH) and nitrate (NO3) radicals, O3, O3P, or by photolysis or unimolecular reactions, and the reactions of the radicals they form in the presence of O2 and oxides of nitrogen (NOx) at atmospheric temperatures and pressures. Measured or theoretically calculated rate constants and branching ratios are used when data are available, but in most cases rate constants and branching ratios are estimated using various structure-reactivity or other estimation methods. Types of reactions that are estimated include initial reactions of organics with atmospheric oxidants or by photolysis, and unimolecular and bimolecular reactions of carbon-centered, alkoxy, and peroxy radicals and Criegee and other intermediates that are formed. This manuscript summarizes the capabilities of the MechGen system for deriving chemical mechanisms and the methods, assignments, and estimates used to derive them. Examples of MechGen predictions also are provided. Many of the estimation methods discussed here have not been published previously, and others have not been used previously in developing comprehensive mechanisms. This paper concludes with a discussion of the areas of uncertainty where additional measurements or theoretical estimates are needed and recommendations for future mechanism development and application.

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William P. L. Carter, Jia Jiang, John J. Orlando, and Kelley C. Barsanti

Status: closed

Comment types: AC – author | RC – referee | CC – community | EC – editor | CEC – chief editor | : Report abuse
  • RC1: 'Comment on egusphere-2023-2343', Luc Vereecken, 07 Dec 2023
  • CC1: 'Comment on egusphere-2023-2343', Tim Wallington, 13 Feb 2024
  • RC2: 'Comment on egusphere-2023-2343', Anonymous Referee #2, 11 Apr 2024
  • AC1: 'Comment on egusphere-2023-2343', Kelley Barsanti, 05 Jul 2024

Status: closed

Comment types: AC – author | RC – referee | CC – community | EC – editor | CEC – chief editor | : Report abuse
  • RC1: 'Comment on egusphere-2023-2343', Luc Vereecken, 07 Dec 2023
  • CC1: 'Comment on egusphere-2023-2343', Tim Wallington, 13 Feb 2024
  • RC2: 'Comment on egusphere-2023-2343', Anonymous Referee #2, 11 Apr 2024
  • AC1: 'Comment on egusphere-2023-2343', Kelley Barsanti, 05 Jul 2024
William P. L. Carter, Jia Jiang, John J. Orlando, and Kelley C. Barsanti
William P. L. Carter, Jia Jiang, John J. Orlando, and Kelley C. Barsanti

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Short summary
SAPRC chemical mechanisms have been widely used to represent the atmospheric chemistry of gas-phase compounds for air quality modeling. These mechanisms have been developed using the SAPRC mechanism generation system (MechGen). MechGen uses data  or structure activity relationships to estimate rate constants and product yields. This manuscript represents the first complete description of MechGen and includes discussion of uncertainty where additional measurements or estimates are needed.