Hydroxyaldehyde products from hydroxyl radical reactions of Z-3-hexen-1-ol and 2-methyl-3-buten-2-ol quantified by SPME and API-MS.
Hydroxyaldehyde products of the OH radical-initiated reactions (in the presence of NO) of two volatile vegetative emissions, Z-3-hexen-1-ol and 2-methyl-3-buten-2-ol, were examined to assess the qualitative and quantitative potential of two analysis techniques (1) sampling by Solid-Phase MicroExtraction (SPME) with on-fiber derivatization followed by gas chromatographic analyses and (2) in situ analysis by negative ion mode atmospheric pressure ionization mass spectrometry (API-MS). The compounds were chosen because reaction mechanisms predict hydroxyaldehyde products, and reliable coproduct yield data are available. The API-MS analyses showed product ion peaks attributed to the NO2- adducts of 3-hydroxypropanal and dihydroxynitrates from Z-3-hexen-1-ol, and a formation yield of 3-hydroxypropanal of 44% was derived. Product ion peaks attributed to NO2- adducts of glycolaldehyde [HOCH2CHO], 2-hydroxy-2-methylpropanal [(CH3)2C(OH)CHO], and dihydroxynitrates were observed by API-MS from 2-methyl-3-buten-2-ol, and a formation yield of 2-hydroxy-2-methylpropanal of 16% was obtained. In experiments with SPME sampling, the formation yields of hydroxycarbonyls measured as their oxime derivatives were as follows: from Z-3-hexen-1-ol, propanal, 56 +/- 8%; 3-hydroxypropanal, 101 +/- 24%; and from 2-methyl-3-buten-2-ol, 2-hydroxy-2-methylpropanal, 31 +/- 4%. Both the API-MS and SPME analyses provided product information, and hydroxycarbonyl yields from the SPME data are in reasonable agreement with previously measured formation yields of coproducts.
Reisen
Fabienne
F
Air Pollution Research Center, University of California, Riverside, California 92521, USA.
Aschmann
Sara M
SM
Atkinson
Roger
R
Arey
Janet
J
D002623:Chemistry Techniques, Analytical / Q000379:methods; D000441:Hexanols / Q000737:chemistry*; D017665:Hydroxyl Radical / Q000737:chemistry*; D013058:Mass Spectrometry; D016877:Oxidants / Q000737:chemistry*; D000439:Pentanols / Q000737:chemistry*; D014835:Volatilization
D000441:Hexanols; D016877:Oxidants; D000439:Pentanols; C051918:3-hexen-1-ol; D017665:Hydroxyl Radical; C027250:3-hydroxy-3-methylbutene