Evidence for Organosulfates in Secondary Organic Aerosol

University of Antwerp, Antwerpen, Flemish, Belgium
Environmental Science and Technology (Impact Factor: 5.33). 02/2007; 41(2):517-27. DOI: 10.1021/es062081q
Source: PubMed


Recent work has shown that particle-phase reactions contribute to the formation of secondary organic aerosol (SOA), with enhancements of SOA yields in the presence of acidic seed aerosol. In this study, the chemical composition of SOA from the photooxidations of alpha-pinene and isoprene, in the presence or absence of sulfate seed aerosol, is investigated through a series of controlled chamber experiments in two separate laboratories. By using electrospray ionization-mass spectrometry, sulfate esters in SOA produced in laboratory photooxidation experiments are identified for the first time. Sulfate esters are found to account for a larger fraction of the SOA mass when the acidity of seed aerosol is increased, a result consistent with aerosol acidity increasing SOA formation. Many of the isoprene and alpha-pinene sulfate esters identified in these chamber experiments are also found in ambient aerosol collected at several locations in the southeastern U.S. It is likely that this pathway is important for other biogenic terpenes, and may be important in the formation of humic-like substances (HULIS) in ambient aerosol.

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Available from: Edward O. Edney
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    • "Analysis of filter extracts is commonly performed by liquid chromatography (LC) and gas chromatography (GC), coupled to mass spectrometry with the use of electron ionization (EI), chemical ionization (CI), electrospray ionization (ESI), and atmospheric pressure chemical ionization (APCI) (Dye and Yttri, 2005; Simpson et al., 2005; Surratt et al., 2006 and 2007a, b; Lavrich and Hays, 2007; Szmigielski et al., 2007; Lin et al., 2012). Major organic classes in SOA that have been identified from filter-based analysis include (nitrooxy)organosulfates (Surratt et al., 2007a, b and 2008; Iinuma et al., 2007; Chan et al., 2011), dimers, trimers, and oligomers (Jang et al., 2002; Limbeck et al., 2003; Gao et al., 2004; Kalberer et al., 2004; Fahnestock et al., 2014), and humic-like substances (Gelencser et al., 2002; Graham et al., 2002). A limitation of filterbased analysis is low time resolution and, consequently, the inability to track particle-phase kinetics. "
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    ABSTRACT: Real-time and quantitative measurement of particulate matter chemical composition represents one of the most challenging problems in the field of atmospheric chemistry. In the present study, we integrate the Particle-into-Liquid Sampler (PILS) with Ultra Performance Liquid Chromatography/Electrospray ionization Quadrupole Time-of-Flight High-Resolution/Mass Spectrometry (UPLC/ESI-Q-TOFMS) for the time-resolved molecular speciation of chamber-derived secondary organic aerosol (SOA). The unique aspect of the combination of these two well-proven techniques is to provide quantifiable molecular-level information of particle-phase organic compounds on timescales of minutes. We demonstrate that the application of the PILS+UPLC/ESI-Q-TOFMS method is not limited to water-soluble inorganic ions and organic carbon, but is extended to slightly water-soluble species through collection efficiency calibration together with sensitivity and linearity tests. By correlating the water solubility of individual species with their O:C ratio, a parameter that is available for aerosol ensembles as well, we define an average aerosol O:C ratio threshold of 0.3, above which the PILS overall particulate mass collection efficiency approaches ~0.7. The PILS+UPLC/ESI-Q-TOFMS method can be potentially applied to probe the formation and evolution mechanism of a variety of biogenic and anthropogenic SOA systems in laboratory chamber experiments. We illustrate the application of this method to the reactive uptake of isoprene epoxydiols (IEPOX) on hydrated and acidic ammonium sulfate aerosols.
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    • "The effects of acid enhancement on BSOA formation were examined by comparing paired samples collected under high and low SO 2 or NH 3 scenarios. Even though some of these BSOA tracers have been previously characterized from PM 2.5 samples collected from the SEARCH network in a time-integrated manner (Chan et al., 2010b; Gao et al., 2006; Surratt et al., 2007a, 2008), using conditional sampling approaches to collect PM 2.5 in this study is to our knowledge one of the first attempts to systematically examine if BSOA formation is enhanced or suppressed due to anthropogenic emissions in this region. "
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    • "Radical reactions involve a variety of atmospheric oxidants, including OH radicals, NO 3 radicals, O 3 , H 2 O 2 , and can be initiated by photolysis (Lim et al., 2010). Non-radical reactions include hemiacetal formation (Liggio et al., 2005b; Loeffler et al., 2006), esterification via condensation reactions (Gao et al., 2004; Surratt et al., 2006; Surratt et al., 2007; Altieri et al., 2008), imine formation (De Haan et al., 2009a; De Haan et al., 2009c), anhydride formation (Gao et al., 2004), aldol condensation (Jang et al., 2002; Kalberer et al., 2004; Noziere and Cordova, 2008; Shapiro et al., 2009), and organosulfate formation (Liggio et al., 2005a; Surratt et al., 2007). Presently only a few studies have attempted to quantitatively explore the factors that contribute to the formation of cloud SOA. "
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