Isoprene Epoxydiols as Precursors to Secondary Organic Aerosol Formation: Acid-Catalyzed Reactive Uptake Studies with Authentic Compounds
- 21 November 2011
- journal article
- research article
- Published by American Chemical Society (ACS) in Environmental Science & Technology
- Vol. 46 (1), 250-258
- https://doi.org/10.1021/es202554c
Abstract
Isoprene epoxydiols (IEPOX), formed from the photooxidation of isoprene under low-NOx conditions, have recently been proposed as precursors of secondary organic aerosol (SOA) on the basis of mass spectrometric evidence. In the present study, IEPOX isomers were synthesized in high purity (>99%) to investigate their potential to form SOA via reactive uptake in a series of controlled dark chamber studies followed by reaction product analyses. IEPOX-derived SOA was substantially observed only in the presence of acidic aerosols, with conservative lower-bound yields of 4.7–6.4% for β-IEPOX and 3.4–5.5% for δ-IEPOX, providing direct evidence for IEPOX isomers as precursors to isoprene SOA. These chamber studies demonstrate that IEPOX uptake explains the formation of known isoprene SOA tracers found in ambient aerosols, including 2-methyltetrols, C5-alkene triols, dimers, and IEPOX-derived organosulfates. Additionally, we show reactive uptake on the acidified sulfate aerosols supports a previously unreported acid-catalyzed intramolecular rearrangement of IEPOX to cis- and trans-3-methyltetrahydrofuran-3,4-diols (3-MeTHF-3,4-diols) in the particle phase. Analysis of these novel tracer compounds by aerosol mass spectrometry (AMS) suggests that they contribute to a unique factor resolved from positive matrix factorization (PMF) of AMS organic aerosol spectra collected from low-NOx, isoprene-dominated regions influenced by the presence of acidic aerosols.This publication has 26 references indexed in Scilit:
- Kinetics and Products of the Acid-Catalyzed Ring-Opening of Atmospherically Relevant Butyl Epoxy AlcoholsThe Journal of Physical Chemistry A, 2010
- Reactive intermediates revealed in secondary organic aerosol formation from isopreneProceedings of the National Academy of Sciences of the United States of America, 2009
- Unexpected Epoxide Formation in the Gas-Phase Photooxidation of IsopreneScience, 2009
- The formation, properties and impact of secondary organic aerosol: current and emerging issuesAtmospheric Chemistry and Physics, 2009
- A review of Secondary Organic Aerosol (SOA) formation from isopreneAtmospheric Chemistry and Physics, 2009
- Evidence for Organosulfates in Secondary Organic AerosolEnvironmental Science & Technology, 2006
- Estimates of global terrestrial isoprene emissions using MEGAN (Model of Emissions of Gases and Aerosols from Nature)Atmospheric Chemistry and Physics, 2006
- Chemical Composition of Secondary Organic Aerosol Formed from the Photooxidation of IsopreneThe Journal of Physical Chemistry A, 2006
- Characterization of oxygenated derivatives of isoprene related to 2‐methyltetrols in Amazonian aerosols using trimethylsilylation and gas chromatography/ion trap mass spectrometryRapid Communications in Mass Spectrometry, 2005
- Formation of Secondary Organic Aerosols Through Photooxidation of IsopreneScience, 2004