[Gouw2004] "Inter-comparison between airborne measurements of methanol, acetonitrile and acetone using two differently configured PTR-MS instruments",
International Journal of Mass Spectrometry
, vol. 239, no. 2: Elsevier, pp. 129–137, 2004.
Proton-transfer-reaction mass spectrometry (PTR-MS) has emerged as a useful tool to study the atmospheric chemistry of volatile organic compounds (VOCs). The technique combines a fast response time with a low detection limit, and allows atmospheric measurements of many important VOCs and their oxidation products. Here, we inter-compare the results obtained with two differently configured PTR-MS instruments operated onboard a Falcon aircraft during the Mediterranean Intensive Oxidants Study (MINOS) campaign in the Mediterranean region. One PTR-MS was operated at a drift tube pressure of 2.3 mbar and an electric field divided by gas number density value (E/N) of 120 Td for the detection of VOCs and aromatic hydrocarbons. The other PTR-MS was operated at an increased pressure of 2.8 mbar and a reduced E/N of 97 Td for the detection of peroxyacetyl nitrate (PAN). As a consequence, more H3O+(H2O)n cluster ions were present in the drift tube, which undergo proton-transfer reactions with VOCs similar to H3O+ ions. The results for methanol (CH3OH), acetonitrile (CH3CN) and acetone (CH3COCH3) obtained with the instruments compared very well. The agreement between the two results was relatively independent of the ambient mixing ratio of water, which influences the H3O+(H2O)n cluster ion distribution, and of ozone, which has been implicated in the artificial formation of aldehydes and ketones.
[Roberts2011] "Isocyanic acid in the atmosphere and its possible link to smoke-related health effects.",
Proc Natl Acad Sci U S A
, vol. 108, no. 22: National Oceanic and Atmospheric Administration, Earth System Research Laboratories, Chemical Sciences Division, R/CSD7, 325 Broadway, Boulder, CO 80305, USA. firstname.lastname@example.org, pp. 8966–8971, May, 2011.
<p>We measured isocyanic acid (HNCO) in laboratory biomass fires at levels up to 600 parts per billion by volume (ppbv), demonstrating that it has a significant source from pyrolysis/combustion of biomass. We also measured HNCO at mixing ratios up to 200 pptv (parts-per-trillion by volume) in ambient air in urban Los Angeles, CA, and in Boulder, CO, during the recent 2010 Fourmile Canyon fire. Further, our measurements of aqueous solubility show that HNCO is highly soluble, as it dissociates at physiological pH. Exposure levels > 1 ppbv provide a direct source of isocyanic acid and cyanate ion (NCO(-)) to humans at levels that have recognized health effects: atherosclerosis, cataracts, and rheumatoid arthritis, through the mechanism of protein carbamylation. In addition to the wildland fire and urban sources, we observed HNCO in tobacco smoke, HNCO has been reported from the low-temperature combustion of coal, and as a by-product of urea-selective catalytic reduction (SCR) systems that are being phased-in to control on-road diesel NO(x) emissions in the United States and the European Union. Given the current levels of exposure in populations that burn biomass or use tobacco, the expected growth in biomass burning emissions with warmer, drier regional climates, and planned increase in diesel SCR controls, it is imperative that we understand the extent and effects of this HNCO exposure.</p>