1. Characterization of a real-time tracer for isoprene epoxydiols-derived secondary organic aerosol (IEPOX-SOA) from aerosol mass spectrometer measurements.
- Author
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Hu, W. W., Campuzano-Jost, P., Palm, B. B., Day, D. A., Ortega, A. M., Hayes, P. L., Krechmer, J. E., Chen, Q., Kuwata, M., Liu, Y. J., de Sá, S. S., McKinney, K., Martin, S. T., Hu, M., Budisulistiorini, S. H., Riva, M., Surratt, J. D., Clair, J. M. St., Isaacman-Van Wertz, G., and Yee, L. D.
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ISOPRENE ,ATMOSPHERIC aerosols ,MASS spectrometers ,CHEMICAL amplification ,BIOMASS burning - Abstract
Substantial amounts of secondary organic aerosol (SOA) can be formed from isoprene epoxydiols (IEPOX), which are oxidation products of isoprene mainly under low- NO conditions. Total IEPOX-SOA, which may include SOA formed from other parallel isoprene oxidation pathways, was quantified by applying positive matrix factorization (PMF) to aerosol mass spectrometer (AMS) measurements. The IEPOX-SOA fractions of organic aerosol (OA) in multiple field studies across several continents are summarized here and show consistent patterns with the concentration of gas-phase IEPOX simulated by the GEOS-Chem chemical transport model. During the Southern Oxidant and Aerosol Study (SOAS), 78% of PMF-resolved IEPOX-SOA is accounted by the measured IEPOX-SOA molecular tracers (2-methyltetrols, C5-Triols, and IEPOX-derived organosulfate and its dimers), making it the highest level of molecular identification of an ambient SOA component to our knowledge. An enhanced signal at C
5 H6 O+ (m=z 82) is found in PMF-resolved IEPOX-SOA spectra. To investigate the suitability of this ion as a tracer for IEPOX-SOA, we examine fC5 H6 O (fC5 H6 O D C5 H6 O+ =OA) across multiple field, chamber, and source data sets. A background of ~1.7±0.1% (%Dparts per thousand) is observed in studies strongly influenced by urban, biomass-burning, and other anthropogenic primary organic aerosol (POA). Higher background values of 3.1±0.6% are found in studies strongly influenced by monoterpene emissions. The average laboratory monoterpene SOA value (5.5±2.0 %) is 4 times lower than the average for IEPOX-SOA (22±7 %), which leaves some room to separate both contributions to OA. Locations strongly influenced by isoprene emissions under low-NO levels had higher fC5 H6 O (~6.5±2.2% on average) than other sites, consistent with the expected IEPOX-SOA formation in those studies. fC5 H6 O in IEPOX-SOA is always elevated (12-40 %) but varies substantially between locations, which is shown to reflect large variations in its detailed molecular composition. The low fC5 H6 O (<3 %) reported in non-IEPOX-derived isoprene-SOA from chamber studies indicates that this tracer ion is specifically enhanced from IEPOX-SOA, and is not a tracer for all SOA from isoprene. We introduce a graphical diagnostic to study the presence and aging of IEPOX-SOA as a triangle plot of fCO2 vs. fC5 H6 O. Finally, we develop a simplified method to estimate ambient IEPOX-SOA mass concentrations, which is shown to perform well compared to the full PMF method. The uncertainty of the tracer method is up to a factor of ~2, if the fC5 H6 O of the local IEPOX-SOA is not available. When only unit mass-resolution data are available, as with the aerosol chemical speciation monitor (ACSM), all methods may perform less well because of increased interferences from other ions at m=z 82. This study clarifies the strengths and limitations of the different AMS methods for detection of IEPOXSOA and will enable improved characterization of this OA component. [ABSTRACT FROM AUTHOR]- Published
- 2015
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