Formation and reaction of hydroxycarbonyls from the reaction of OH radicals with 1,3-butadiene and isoprene

1,3-Butadiene and isoprene (2-methyl-1,3-butadiene) are emitted into the atmosphere in vehicle exhaust and, in the case of isoprene, from vegetation. We have investigated the formation and further reaction of products of their hydroxyl radical-initiated reactions using atmospheric pressure ionization mass spectrometry (API-MS) and solid-phase microextraction fibers precoated with O-(2,3,4,5,6-pentafluorobenzyl)hydroxylamine for on-fiber derivatization of carbonyl compounds, with subsequent analysis by thermal desorption and gas chromatography with flame ionization detection (SPME/GC-FID) or MS detection. Products attributed as HOCH2CHCHCHO and HOCH2CHCHCH2ONO2 (and isomers) from 1,3-butadiene; HOCD2CD=CDCDO and HOCD2CD=CDCD2ONO2 (and isomers) from 1,3-butadiene-d6; HOCH2C(CH3)CHCHO and/or HOCH2CHC(CH3)CHO, and HOCH2C(CH3)CHCH2ONO2 (and isomers) from isoprene; and HOCD2C(CD3)CDCDO and/or HOCD2CD=C(CD3)CDO, and HOCD2C(CD3)CDCD2ONO2 (and isomers) from isoprene-d8 were observed as their NO2- adducts in the AP...