Atmospheric Chemistry of 2-Amino-2-methyl-1-propanol: A Theoretical and Experimental Study of the OH-Initiated Degradation under Simulated Atmospheric Conditions

Wen Tan, Liang Zhu, Tomáš Mikoviny, Claus J. Nielsen*, Yizhen Tang, Armin Wisthaler, Philipp Eichler, Markus Müller, Barbara D'Anna, Naomi J. Farren, Jacqueline F. Hamilton, Jan B.C. Pettersson, Mattias Hallquist, Simen Antonsen, Yngve Stenstrøm

*Corresponding author for this work

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The OH-initiated degradation of 2-amino-2-methyl-1-propanol [CH3C(NH2)(CH3)CH2OH, AMP] was investigated in a large atmospheric simulation chamber, employing time-resolved online high-resolution proton-transfer reaction-time-of-flight mass spectrometry (PTR-ToF-MS) and chemical analysis of aerosol online PTR-ToF-MS (CHARON-PTR-ToF-MS) instrumentation, and by theoretical calculations based on M06-2X/aug-cc-pVTZ quantum chemistry results and master equation modeling of the pivotal reaction steps. The quantum chemistry calculations reproduce the experimental rate coefficient of the AMP + OH reaction, aligning k(T) = 5.2 × 10-12 × exp (505/T) cm3 molecule-1 s-1 to the experimental value kexp,300K = 2.8 × 10-11 cm3 molecule-1 s-1. The theoretical calculations predict that the AMP + OH reaction proceeds via hydrogen abstraction from the -CH3 groups (5-10%), -CH2- group, (>70%) and -NH2 group (5-20%), whereas hydrogen abstraction from the -OH group can be disregarded under atmospheric conditions. A detailed mechanism for atmospheric AMP degradation was obtained as part of the theoretical study. The photo-oxidation experiments show 2-amino-2-methylpropanal [CH3C(NH2)(CH3)CHO] as the major gas-phase product and propan-2-imine [(CH3)2C=NH], 2-iminopropanol [(CH3)(CH2OH)C=NH], acetamide [CH3C(O)NH2], formaldehyde (CH2O), and nitramine 2-methyl-2-(nitroamino)-1-propanol [AMPNO2, CH3C(CH3)(NHNO2)CH2OH] as minor primary products; there is no experimental evidence of nitrosamine formation. The branching in the initial H abstraction by OH radicals was derived in analyses of the temporal gas-phase product profiles to be BCH3/BCH2/BNH2 = 6:70:24. Secondary photo-oxidation products and products resulting from particle and surface processing of the primary gas-phase products were also observed and quantified. All the photo-oxidation experiments were accompanied by extensive particle formation that was initiated by the reaction of AMP with nitric acid and that mainly consisted of this salt. Minor amounts of the gas-phase photo-oxidation products, including AMPNO2, were detected in the particles by CHARON-PTR-ToF-MS and GC×GC-NCD. Volatility measurements of laboratory-generated AMP nitrate nanoparticles gave ΔvapH = 80 ± 16 kJ mol-1 and an estimated vapor pressure of (1.3 ± 0.3) × 10-5 Pa at 298 K. The atmospheric chemistry of AMP is evaluated and a validated chemistry model for implementation in dispersion models is presented.

Original languageEnglish
JournalJournal of Physical Chemistry A
Publication statusPublished - 23 Aug 2021

Bibliographical note

Funding Information:
This work is part of the Atmospheric Chemistry of Amines project (ACA) supported by the CLIMIT program under contract 244055 and received additional support from the Research Council of Norway through its Centers of Excellence scheme, project number 262695, and from the VISTA-program, project 6157.

Publisher Copyright:
© 2021 The Authors. Published by American Chemical Society.

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