Ion trap mass spectrometry affords advances in the analytical and atmospheric chemistry of 2-hydroxy-2-methylpropanal, a proposed photooxidation product of 2-methyl-3-buten-2-Ol. Spaulding, R.; Charles, M., J.; Tuazon, E., C.; and Lashley, M. Journal of the American Society for Mass Spectrometry, 13(5):530-542, 2002.
abstract   bibtex   
In the western United States, in areas where emissions of the biogenic hydrocarbon, 2-methyl-3-buten-2-ol (MBO) are high, MBO contributes significantly to the oxidative capacity of the atmosphere. Hydroxyl radical oxidation of MBO can play an important role in forming tropospheric ozone, and MBO reaction products may contribute to the formation of secondary organic aerosols [1-3]. Although 2-hdyroxy-2-methylpropanal was tentatively identified as a product from the reaction of MBO with .OH in indoor chamber studies, the identity of the compound was not confirmed due to the lack of an authentic standard. Further, no data exists on the atmospheric generation and fate of 2-hydroxy-2-methylpropanal in the ambient environment. Herein, we provide further evidence that 2-hydroxy-2-methylpropanol is generated by .OH reaction with MBO by identifying 2-hydroxy-2-methylpropanol in an indoor chamber experiment and in ambient air sampled in the Blodgett Forest, where MBO emissions are high. We analyzed 2-hydroxy-2-methylpropanal by using a method that relies on O-(2,3,4,5,6-pentafluorobenzyl)hydroxylamine (PFBHA) and bis-(trimethylsilyl) trifluoroacetamide (BSTFA) derivatization along with ion-trap mass spectrometry. Tentative identification of 2-hydroxy-2-methylpropanal was possible by using knowledge gained in this study regarding the mass spectrometry of PFBHA-BSTFA derivatives of carbonyls with primary, secondary, and tertiary -OH groups, and ado- and keto-acids. The identification was confirmed by comparing the methane Cl mass spectra and relative gas chromatographic retention time obtained by analyzing 2-hydroxy-2-methylpropanol in a sample extract and a synthesized authentic standard. Since the standard became available at the end of this study (after all samples were analyzed), we also developed a method for semi-quantification of 2-hydroxy-2-methylpropanal, with a detection limit of 27 pptv in air. We used the method to provide the first ambient air measurements of 2-hydroxy-2-methylpropanal. The analyte is not commercially available, and hence other researchers who have not synthesized an authentic standard can employ, the method. (J Am Soc Mass Spectrom 2002, 13, 530-542) (C) 2002 American Society for Mass Spectrometry. [References: 34] 34
@article{
 title = {Ion trap mass spectrometry affords advances in the analytical and atmospheric chemistry of 2-hydroxy-2-methylpropanal, a proposed photooxidation product of 2-methyl-3-buten-2-Ol},
 type = {article},
 year = {2002},
 keywords = {Gas-phase reactions. Chemical-ionization reagent.,Spectroscopy/Instrumentation/Analytical Sciences i},
 pages = {530-542},
 volume = {13},
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 created = {2015-02-12T14:35:21.000Z},
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 last_modified = {2015-02-12T20:21:16.000Z},
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 notes = {<m:note>English Article<m:linebreak/>Current Contents(R)/Physical, Chemical &amp; Earth Sciences.<m:linebreak/>Reprint available from: Charles MJ Univ Calif Davis, Dept Environm Toxicol 1 Shields Ave Davis, CA 95616 USA Univ Calif Davis, Dept Environm Toxicol Davis, CA 95616 USA Univ Calif Riverside, Air Pollut Res Ctr Riverside, CA 92521 USA 0012 J. Am. Soc. Mass Spectrom</m:note>},
 abstract = {In the western United States, in areas where emissions of the biogenic hydrocarbon, 2-methyl-3-buten-2-ol (MBO) are high, MBO contributes significantly to the oxidative capacity of the atmosphere. Hydroxyl radical oxidation of MBO can play an important role in forming tropospheric ozone, and MBO reaction products may contribute to the formation of secondary organic aerosols [1-3]. Although 2-hdyroxy-2-methylpropanal was tentatively identified as a product from the reaction of MBO with .OH in indoor chamber studies, the identity of the compound was not confirmed due to the lack of an authentic standard. Further, no data exists on the atmospheric generation and fate of 2-hydroxy-2-methylpropanal in the ambient environment. Herein, we provide further evidence that 2-hydroxy-2-methylpropanol is generated by .OH reaction with MBO by identifying 2-hydroxy-2-methylpropanol in an indoor chamber experiment and in ambient air sampled in the Blodgett Forest, where MBO emissions are high. We analyzed 2-hydroxy-2-methylpropanal by using a method that relies on O-(2,3,4,5,6-pentafluorobenzyl)hydroxylamine (PFBHA) and bis-(trimethylsilyl) trifluoroacetamide (BSTFA) derivatization along with ion-trap mass spectrometry. Tentative identification of 2-hydroxy-2-methylpropanal was possible by using knowledge gained in this study regarding the mass spectrometry of PFBHA-BSTFA derivatives of carbonyls with primary, secondary, and tertiary -OH groups, and ado- and keto-acids. The identification was confirmed by comparing the methane Cl mass spectra and relative gas chromatographic retention time obtained by analyzing 2-hydroxy-2-methylpropanol in a sample extract and a synthesized authentic standard. Since the standard became available at the end of this study (after all samples were analyzed), we also developed a method for semi-quantification of 2-hydroxy-2-methylpropanal, with a detection limit of 27 pptv in air. We used the method to provide the first ambient air measurements of 2-hydroxy-2-methylpropanal. The analyte is not commercially available, and hence other researchers who have not synthesized an authentic standard can employ, the method. (J Am Soc Mass Spectrom 2002, 13, 530-542) (C) 2002 American Society for Mass Spectrometry. [References: 34] 34},
 bibtype = {article},
 author = {Spaulding, R and Charles, M J and Tuazon, E C and Lashley, M},
 journal = {Journal of the American Society for Mass Spectrometry},
 number = {5}
}
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