Characterization of a real-time tracer for isoprene epoxydiols-derived secondary organic aerosol (IEPOX-SOA) from aerosol mass spectrometer measurements

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.; St. Clair, J. M.; Isaacman-Van Wertz, G.; Yee, L. D.; Goldstein, A. H.; Carbone, S.; Brito, J.; Artaxo, P.; de Gouw, J. A.; Koss, A.; Wisthaler, A.; Mikoviny, T.; Karl, T.; Kaser, L.; Jud, W.; Hansel, A.; Docherty, K. S.; Alexander, M. L.; Robinson, N. H.; Coe, H.; Allan, J. D.; Canagaratna, M. R.; Paulot, F.; Jimenez, J. L.

doi:10.5194/acp-15-11807-2015

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Characterization of a real-time tracer for isoprene epoxydiols-derived secondary organic aerosol (IEPOX-SOA) from aerosol mass spectrometer measurements

2015
By Hu, W. W. ; Campuzano-Jost, P. ; Palm, B. B. ; ...
Source: Atmospheric Chemistry and Physics, 15(20), 11807-11833.

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Journal Title:

Atmospheric Chemistry and Physics
Personal Author:

Hu, W. W. ; Campuzano-Jost, P. ; Palm, B. B. ; Day, D. A. ; Ortega, A. M. ; ... More +

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. ; St. Clair, J. M. ; Isaacman-Van Wertz, G. ; Yee, L. D. ; Goldstein, A. H. ; Carbone, S. ; Brito, J. ; Artaxo, P. ; de Gouw, J. A. ; Koss, A. ; Wisthaler, A. ; Mikoviny, T. ; Karl, T. ; Kaser, L. ; Jud, W. ; Hansel, A. ; Docherty, K. S. ; Alexander, M. L. ; Robinson, N. H. ; Coe, H. ; Allan, J. D. ; Canagaratna, M. R. ; Paulot, F. ; Jimenez, J. L. Less -
NOAA Program & Office:

OAR (Oceanic and Atmospheric Research) ; ESRL (Earth System Research Laboratory) ; GFDL (Geophysical Fluid Dynamics Laboratory) ; CSD (Chemical Sciences Division)

OAR (Oceanic and Atmospheric Research) ; ESRL (Earth System Research Laboratory) ; GFDL (Geophysical Fluid Dynamics Laboratory) ; CSD (Chemical Sciences Division) Less -
Description:

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 C5H6O+ (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 fC(5)H(6)O (fC(5)H(6)O = C5H6O+ / OA) across multiple field, chamber, and source data sets. A background of similar to 1.7 +/- 0.1 parts per thousand (parts per thousand = parts 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 parts per thousand are found in studies strongly influenced by monoterpene emissions. The average laboratory monoterpene SOA value (5.5 +/- 2.0 parts per thousand) is 4 times lower than the average for IEPOX-SOA (22 +/- 7 parts per thousand), which leaves some room to separate both contributions to OA. Locations strongly influenced by isoprene emissions under low-NO levels had higher fC(5)H(6)O (similar to 6.5 +/- 2.2 parts per thousand on average) than other sites, consistent with the expected IEPOX- SOA formation in those studies. fC(5)H(6)O in IEPOX- SOA is always elevated (12-40 parts per thousand) but varies substantially between locations, which is shown to reflect large variations in its detailed molecular composition. The low fC(5)H(6)O (< 3 parts per thousand) 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 f(CO2) vs. fC(5)H(6)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 similar to 2, if the fC(5)H(6)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 IEPOX- SOA and will enable improved characterization of this OA component.
Source:

Atmospheric Chemistry and Physics, 15(20), 11807-11833.
DOI:

https://doi.org/10.5194/acp-15-11807-2015
Document Type:

Journal Article
Funding:

Grant no. NA13OAR4310063
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CC BY
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Submitted
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urn:sha256:d017e83f376ca8fb9fc1bf18b8634c30c90e69811210b1dbfb7c4a21d8dd32d8
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Characterization of a real-time tracer for isoprene epoxydiols-derived secondary organic aerosol (IEPOX-SOA) from aerosol mass spectrometer measurements

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