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Organic Aerosol Sources and Chemistry: Insights from Development and Application of In-Situ Thermal Desorption Gas Chromatograph for Semi-Volatile Organic Compounds (SV-TAG)

  • Author(s): Zhao, Yunliang
  • Advisor(s): Goldstein, Allen H
  • et al.

Understanding organic aerosol (OA) sources and secondary OA (SOA) formation is crucial to elucidate their human health and climate change effects, but has been limited by lack of instrumentation capable of in-situ measurements of organic speciation in the atmosphere across the vapor pressure range of semi-volatile organic compounds (SVOCs) and OA. This dissertation describes 1) the development of a novel instrument based on a thermal desorption aerosol gas chromatograph (TAG), called semi-volatile TAG (SV-TAG) which enables quantitative measurements of specific chemical tracers in SVOCs and OA and 2) application of this new instrument to investigate the various source contributions to OA and SOA formation.

The development of the SV-TAG was initiated by employing a denuder difference method to improve the capability of the TAG for quantitative gas/particle separation. Using this technique, hourly time resolution in-situ measurements of organic species were made and then used to investigate the pathways of gas-to-particle partitioning for oxygenated compounds and particle-phase organics were used for source apportionment calculations. The measurements of gas/particle partitioning of phthalic acid, pinonaldehyde and 6, 10, 14-trimethyl-2-pentadecanone were explored to elucidate the pathways of gas-to-particle partitioning whereby SOA was formed. The observations show that multiple pathways of gas-to-particle partitioning contribute to formation of SOA in the atmosphere and the dominance of different pathways are compound-dependent. Absorption into particles is shown to be the dominant pathway for 6, 10, 14-trimethyl-2-pentadecanone to contribute to SOA in Bakersfield, CA. The major pathway to form particle-phase phthalic acid is likely attributed to formation of condensable salts through reactions between phthalic acid and gas-phase ammonia. The observations of pinonaldehyde in particles while inorganic acids in particles were fully neutralized suggest that the occurrence of reactive uptake of pinonaldehyde onto particles does not require the presence of inorganic acids. The relationship between particle-phase pinonaldehyde and RH suggests that aerosol water content plays a significant role in the formation of particle-phase pinonaldehyde. To investigate the contributions of various sources to OA in Bakersfield, CA, positive matrix factorization (PMF) analysis was performed on a subset of the measured particle-phase organic compounds. Six OA source factors were identified, including one representing primary organic aerosol (POA), four different types of secondary organic aerosol (SOA) representing local, regional, and nighttime production, and one representing a complex mixture of additional OA sources that were not further resolvable. POA accounted for 15% of OA on average with a significant contribution from local vehicles. SOA was the dominant contributor to OA, accounting for on average 72% of OA. The rest of OA was unresolved as a mixture of OA sources. Both local and regional SOA had a significant contribution to OA during the day but regional SOA was the largest contributor to OA during the afternoon. SOA formed from the oxidation of biogenic SOA precursors substantially contributed to OA at night. The absorption of organic compounds into particles is suggested to be the major pathway to form SOA, although other pathways also played significant roles.

To achieve quantitative collection of SVOCs following improved gas/particle separation, a new collection and thermal desorption system was developed with the key component being a passivated metal fiber filter collector. This final configuration of the SV-TAG enabled in-situ quantitative measurements of speciated SVOCs with vapor pressures lower than n-tetradecane (C14). The capability for measurements of gas/particle partitioning was demonstrated by measurements of n-alkanes in both gas and particle phases. Organic tracers in both gas and particle phases can be quantified. Percentages of speciated organic compounds in total measured organics can be estimated. For example, ~7% and less than 1% of total measured organics in the same retention range of n-alkanes (C14-C20) in the atmosphere in Berkeley, CA were accounted for by the sum of measured n-alkanes (C14-C20) and the sum of n alkylcyclohexanes (C14-C20).

The SV-TAG has been demonstrated to enable investigation of the pathways of gas-to-particle partitioning and source apportionment of OA with hourly time resolution. The SV-TAG is also capable of quantitative measurements of speciated SVOCs, defining their gas/particle partitioning in-situ for the first time, and providing observational constraints on the abundance of SVOCs with which to investigate their primary emissions, chemical transformation, and fate.

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