Chemical composition of secondary organic aerosol formed from the photooxidation of isoprene. Surratt, J., D., Murphy, S., M., Kroll, J., H., Ng, N., L., Hildebrandt, L., Sorooshian, A., Szmigielski, R., Vermeylen, R., Maenhaut, W., Claeys, M., Flagan, R., C., & Seinfeld, J., H. The journal of physical chemistry. A, 110(31):9665-90, 8, 2006.
Chemical composition of secondary organic aerosol formed from the photooxidation of isoprene. [link]Website  abstract   bibtex   
Recent work in our laboratory has shown that the photooxidation of isoprene (2-methyl-1,3-butadiene, C(5)H(8)) leads to the formation of secondary organic aerosol (SOA). In the current study, the chemical composition of SOA from the photooxidation of isoprene over the full range of NO(x) conditions is investigated through a series of controlled laboratory chamber experiments. SOA composition is studied using a wide range of experimental techniques: electrospray ionization-mass spectrometry, matrix-assisted laser desorption ionization-mass spectrometry, high-resolution mass spectrometry, online aerosol mass spectrometry, gas chromatography/mass spectrometry, and an iodometric-spectroscopic method. Oligomerization was observed to be an important SOA formation pathway in all cases; however, the nature of the oligomers depends strongly on the NO(x) level, with acidic products formed under high-NO(x) conditions only. We present, to our knowledge, the first evidence of particle-phase esterification reactions in SOA, where the further oxidation of the isoprene oxidation product methacrolein under high-NO(x) conditions produces polyesters involving 2-methylglyceric acid as a key monomeric unit. These oligomers comprise approximately 22-34% of the high-NO(x) SOA mass. Under low-NO(x) conditions, organic peroxides contribute significantly to the low-NO(x) SOA mass (approximately 61% when SOA forms by nucleation and approximately 25-30% in the presence of seed particles). The contribution of organic peroxides in the SOA decreases with time, indicating photochemical aging. Hemiacetal dimers are found to form from C(5) alkene triols and 2-methyltetrols under low-NO(x) conditions; these compounds are also found in aerosol collected from the Amazonian rainforest, demonstrating the atmospheric relevance of these low-NO(x) chamber experiments.
@article{
 title = {Chemical composition of secondary organic aerosol formed from the photooxidation of isoprene.},
 type = {article},
 year = {2006},
 identifiers = {[object Object]},
 keywords = {Aerosols,Aerosols: chemistry,Butadienes,Butadienes: chemistry,Hemiterpenes,Hemiterpenes: chemistry,Mass Spectrometry,Molecular Structure,Nitric Oxide,Nitric Oxide: chemistry,Oxidation-Reduction,Pentanes,Pentanes: chemistry,Photochemistry},
 pages = {9665-90},
 volume = {110},
 websites = {http://www.ncbi.nlm.nih.gov/pubmed/20108685},
 month = {8},
 day = {10},
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 notes = {<b>From Duplicate 1 (<i>Chemical composition of secondary organic aerosol formed from the photooxidation of isoprene.</i> - Surratt, Jason D; Murphy, Shane M; Kroll, Jesse H; Ng, Nga L; Hildebrandt, Lea; Sorooshian, Armin; Szmigielski, Rafal; Vermeylen, Reinhilde; Maenhaut, Willy; Claeys, Magda; Flagan, Richard C; Seinfeld, John H)<br/></b><br/><b>From Duplicate 1 (<i>Chemical composition of secondary organic aerosol formed from the photooxidation of isoprene.</i> - Surratt, Jason D; Murphy, Shane M; Kroll, Jesse H; Ng, Nga L; Hildebrandt, Lea; Sorooshian, Armin; Szmigielski, Rafal; Vermeylen, Reinhilde; Maenhaut, Willy; Claeys, Magda; Flagan, Richard C; Seinfeld, John H)<br/></b><br/>Gives chemical composition of isoprene SOA products under a range of NOx conditions. <br/><br/><br/><br/><br/><br/><br/><br/><br/><br/><br/><br/><br/><br/><br/><br/><br/>Gas phase chemistry section on p. 9675: <br/>Gas phase oxidation is dominateed by OH.},
 abstract = {Recent work in our laboratory has shown that the photooxidation of isoprene (2-methyl-1,3-butadiene, C(5)H(8)) leads to the formation of secondary organic aerosol (SOA). In the current study, the chemical composition of SOA from the photooxidation of isoprene over the full range of NO(x) conditions is investigated through a series of controlled laboratory chamber experiments. SOA composition is studied using a wide range of experimental techniques: electrospray ionization-mass spectrometry, matrix-assisted laser desorption ionization-mass spectrometry, high-resolution mass spectrometry, online aerosol mass spectrometry, gas chromatography/mass spectrometry, and an iodometric-spectroscopic method. Oligomerization was observed to be an important SOA formation pathway in all cases; however, the nature of the oligomers depends strongly on the NO(x) level, with acidic products formed under high-NO(x) conditions only. We present, to our knowledge, the first evidence of particle-phase esterification reactions in SOA, where the further oxidation of the isoprene oxidation product methacrolein under high-NO(x) conditions produces polyesters involving 2-methylglyceric acid as a key monomeric unit. These oligomers comprise approximately 22-34% of the high-NO(x) SOA mass. Under low-NO(x) conditions, organic peroxides contribute significantly to the low-NO(x) SOA mass (approximately 61% when SOA forms by nucleation and approximately 25-30% in the presence of seed particles). The contribution of organic peroxides in the SOA decreases with time, indicating photochemical aging. Hemiacetal dimers are found to form from C(5) alkene triols and 2-methyltetrols under low-NO(x) conditions; these compounds are also found in aerosol collected from the Amazonian rainforest, demonstrating the atmospheric relevance of these low-NO(x) chamber experiments.},
 bibtype = {article},
 author = {Surratt, Jason D and Murphy, Shane M and Kroll, Jesse H and Ng, Nga L and Hildebrandt, Lea and Sorooshian, Armin and Szmigielski, Rafal and Vermeylen, Reinhilde and Maenhaut, Willy and Claeys, Magda and Flagan, Richard C and Seinfeld, John H},
 journal = {The journal of physical chemistry. A},
 number = {31}
}

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