[Warneke2005a] "Development of proton-transfer ion trap-mass spectrometry: On-line detection and identification of volatile organic compounds in air",
Journal of the American Society for Mass Spectrometry
, vol. 16, no. 8: Elsevier, pp. 1316–1324, 2005.
We present a newly developed instrument that uses proton-transfer ion trap-mass spectrometry (PIT-MS) for on-line trace gas analysis of volatile organic compounds (VOCs). The instrument is based on the principle of proton-transfer reaction-mass spectrometry (PTR-MS): VOCs are ionized using PTRs and detected with a mass spectrometer. As opposed to a quadrupole mass filter in a PTR-MS, the PIT-MS instrument uses an IT-MS, which has the following advantages: (1) the ability to acquire a full mass spectrum in the same time as one mass with a quadrupole and (2) extended analytical capabilities of identifying VOCs by performing collision-induced dissociation (CID) and ion molecule reactions in the IT. The instrument described has, at its current status, limits of detection between 0.05 and 0.5 pbbv for 1-min measurements for all tested VOCs. The PIT-MS was tested in an ambient air measurement in the urban area of Boulder, Colorado, and intercompared with PTR-MS. For all measured compounds the degree of correlation between the two measurements was high (r2 > 0.85), except for acetonitrile (CH3CN), which was close to the limit of detection of the PIT-MS instrument. The two measurements agreed within less than 25%, which was within the combined measurement uncertainties. Automated CID measurements on m/z 59 during the intercomparison were used to determine the contributions of acetone and propanal to the measured signal; both are detected at m/z 59 and thus are indistinguishable in PTR-MS. It was determined that m/z 59 was mainly composed of acetone. An influence of propanal was detected only during a high pollution event. The advantages and future developments of PIT-MS are discussed.
[Karl2005] "Senescing grass crops as regional sources of reactive volatile organic compounds",
Journal of geophysical research
, vol. 110, no. D15: American Geophysical Union, pp. D15302, 2005.
Grass crop species, rice and sorghum, that are widely grown in the southeastern Texas region were analyzed for release of biogenic volatile organic compounds (VOCs) in simulated leaf-drying/senescence experiments. VOC release was measured by both online proton transfer reaction mass spectrometry (PTR-MS) and proton transfer ion trap mass spectrometry (PIT-MS) methods, and it was demonstrated that these two grass crops release a large variety of oxygenated VOCs upon drying under laboratory conditions primarily from leaves and not from stems. VOC release from paddy rice varieties was much greater than from sorghum, and major VOCs identified by gas chromatography PTR-MS included methanol, acetaldehyde, acetone, n-pentanal, methyl propanal, hexenol, hexanal, cis-3-hexenal, and trans-2-hexenal. The latter four VOCs, all C6 compounds known to be formed in wounded leaves, were the major volatiles released from drying rice leaves; smaller but substantial amounts of acetaldehyde were observed in all drying experiments. Online detection of VOCs using PIT-MS gave results comparable to those obtained with PTR-MS, and use of PIT-MS with collision-induced dissociation of trapped ions allowed unambiguous determination of the ratios of cis- and trans-hexenals during different phases of drying. As rice is one of the largest harvested crops on a global scale, it is conceivable that during rice senescence releases of biogenic VOCs, especially the reactive C6 wound VOCs, may contribute to an imbalance in regional atmospheric oxidant formation during peak summer/fall ozone formation periods. A county-by-county estimate of the integrated emissions of reactive biogenic VOCs from sorghum and rice production in Texas suggests that these releases are orders of magnitude lower than anthropogenic VOCs in urban areas but also that VOC emissions from rice in southeastern coastal Texas may need to be included in regional air quality assessments during periods of extensive harvesting.