Document Detail


Investigation of Aqueous-Phase Photooxidation of Glyoxal and Methylglyoxal by Aerosol Chemical Ionization Mass Spectrometry: Observation of Hydroxyhydroperoxide Formation.
MedLine Citation:
PMID:  22296207     Owner:  NLM     Status:  Publisher    
Abstract/OtherAbstract:
Aqueous-phase processing of glyoxal (GLY) and methylglyoxal (MG) produces highly oxygenated, less volatile organic acids that can contribute to SOA formation and aging. In this study, Aerosol Chemical Ionization Mass Spectrometry (Aerosol CIMS) is employed to monitor aqueous-phase photooxidation of GLY and MG. Using iodide (I<sup>-</sup>) as the reagent ion, Aerosol CIMS can simultaneously detect important species involved in the reactions: organic acids, peroxides, and aldehydes, so that the reconstructed total organic carbon (TOC) concentrations from Aerosol CIMS data agree well with offline TOC analysis. This study also reports the first direct detection of hydroxyhydroperoxide (HHP) formation from the reaction of H<sub>2</sub>O<sub>2</sub> with GLY or MG. The formation of HHPs is observed to be reversible and an estimate of their equilibrium constants is made to be between 40 and 200 M<sup>-1</sup>. Results of this study suggest that HHPs can form additional formic acid and acetic acid via photooxidation and regenerate GLY or MG during photooxidation, compensating their loss. HHP formation needs to be further studied for inclusion in aqueous phase chemical models given that it may affect the aqueous partitioning of carbonyls in the atmosphere.
Authors:
Ran Zhao; Alex K Y Lee; Jonathan P D Abbatt
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Publication Detail:
Type:  JOURNAL ARTICLE     Date:  2012-2-1
Journal Detail:
Title:  The journal of physical chemistry. A     Volume:  -     ISSN:  1520-5215     ISO Abbreviation:  -     Publication Date:  2012 Feb 
Date Detail:
Created Date:  2012-2-2     Completed Date:  -     Revised Date:  -    
Medline Journal Info:
Nlm Unique ID:  9890903     Medline TA:  J Phys Chem A     Country:  -    
Other Details:
Languages:  ENG     Pagination:  -     Citation Subset:  -    
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