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Characterization of organosulfates from the photooxidation of isoprene and unsaturated fatty acids in ambient aerosol using liquid chromatography/( − ) electrospray ionization mass spectrometry
Author(s) -
GómezGonzález Yadian,
Surratt Jason D.,
Cuyckens Filip,
Szmigielski Rafal,
Vermeylen Reinhilde,
Jaoui Mohammed,
Lewandowski Michael,
Offenberg John H.,
Kleindienst Tadeusz E.,
Edney Edward O.,
Blockhuys Frank,
Van Alsenoy Christian,
Maenhaut Willy,
Claeys Magda
Publication year - 2008
Publication title -
journal of mass spectrometry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.475
H-Index - 121
eISSN - 1096-9888
pISSN - 1076-5174
DOI - 10.1002/jms.1329
Subject(s) - chemistry , glyoxal , electrospray ionization , mass spectrometry , isoprene , formic acid , chemical ionization , methylglyoxal , sulfate , deprotonation , organic chemistry , chromatography , ion , ionization , enzyme , copolymer , polymer
In the present study, we have characterized in detail the MS 2 and MS 3 fragmentation behaviors, using electrospray ionization (ESI) in the negative ion mode, of previously identified sulfated isoprene secondary organic aerosol compounds, including 2‐methyltetrols, 2‐methylglyceric acid, 2‐methyltetrol mononitrate derivatives, glyoxal and methylglyoxal. A major fragmentation pathway for the deprotonated molecules of the sulfate esters of 2‐methyltetrols and 2‐methylglyceric acid and of the sulfate derivatives of glyoxal and methylglyoxal is the formation of the bisulfate [HSO 4 ] − anion, while the deprotonated sulfate esters of 2‐methyltetrol mononitrate derivatives preferentially fragment through loss of nitric acid. Rational interpretation of MS 2 , MS 3 and accurate mass data led to the structural characterization of unknown polar compounds in K‐puszta fine aerosol as organosulfate derivatives of photooxidation products of unsaturated fatty acids, i.e. 2‐hydroxy‐1,4‐butanedialdehyde, 4,5‐ and 2,3‐dihydroxypentanoic acids, and 2‐hydroxyglutaric acid, and of α‐pinene, i.e. 3‐hydroxyglutaric acid. The deprotonated molecules of the sulfated hydroxyacids, 2‐methylglyceric acid, 4,5‐ and 2,3‐dihydroxypentanoic acid, and 2‐ and 3‐hydroxyglutaric acids, showed in addition to the [HSO 4 ] − ion ( m / z 97) neutral losses of water, CO 2 and/or SO 3 , features that are characteristic of humic‐like substances. The polar organosulfates characterized in the present work are of climatic relevance because they may contribute to the hydrophilic properties of fine ambient aerosol. In addition, these compounds probably serve as ambient tracer compounds for the occurrence of secondary organic aerosol formation under acidic conditions. Copyright © 2007 John Wiley & Sons, Ltd.