Automobile Emissions of Acetonitrile: Assessment of its Contribution to the Global Source

Based on an estimated global fuel consumption of 2.57 × 10¹⁵g(C) y^–1 and the assumption thatthe fossil fuel burned in Austria is globallyrepresentative, an upper limit of 0.021 (+150%, –50%)Tg y^–1 for global CH₃CN emission dueto fossil fuel burning was obtained from the relativeenhancement of the concentrations of toluene, benzene,and acetonitrile (methyl cyanide) during strong,short-term traffic pollution. This is less than 6% ofthe total global budget of CH₃CN, which is dominatedby an emission rate of 0.8 Tg y^–1 from biomassburning.     

An Atmospheric Chemistry Interpretation of Mass Scans Obtained from a Proton Transfer Mass Spectrometer Flown over the Tropical Rainforest of Surinam

Data on a variety of organic gases are presented, obtained with a protontransfer mass spectrometer (PTR-MS) operated during the March 1998 LBA/CLAIREairborne measurement campaign, between 60 and 12500 m over the rainforest inSurinam (2° N–5° N, 54° W–57° W). The instrumentcan detect molecules with a proton affinity greater than water, includingalkenes, dialkenes, carbonyls, alcohols, and nitriles. Many such molecules areemitted from the rainforest (e.g., isoprene) or formed from the oxidation ofprimary emissions (e.g., methylvinylketone (MVK) and methacrolein (MACR)).From a comparison with modelled data; the variation with altitude; previouslyreported biogenic emissions and the time and location of the measurement,possible and probable identities for the significant masses encountered in therange 33–140 amu have been deduced.The main observed protonated masses, postulated identities and observedaverage boundary layer mixing ratios over the rainforest were: 33 methanol(1.1 nmol/mol); 42 acetonitrile (190 pmol/mol); 43 multiple possibilities (5.9nmol/mol), 45 acetaldehyde (1.7 nmol/mol), 47 formic acid (not quantified);59 acetone (2.9 nmol/mol), 61 acetic acid (not quantified), 63 dimethylsulphide (DMS) (289 pmol/mol), 69 isoprene (1.7 nmol/mol), 71 MVK + MACR (1.3nmol/mol), 73 methyl ethyl ketone (1.8 nmol/mol), 75 hydroxyacetone (606pmol/mol), 83 C₅ isoprene hydroxy carbonylsC₅H₈O₂, methyl furan, and cis 3-hexen-1-ol(732 pmol/mol), 87 C₅ carbonyls and methacrylic acid, 95 possibly2-vinyl furan (656 pmol/mol), 97 unknown (305 pmol/mol), 99 cis hexenal (512pmol/mol) and 101 isoprene C₅ hydroperoxides (575 pmol/mol). Somespecies agreed well with those derived from an isoprene only photochemicalmodel (e.g., mass 71 MVK + MACR) while others did not and were observed athigher than previously reported mixing ratios (e.g., mass 59 acetone, mass 63DMS). Monoterpenes were not detected above the detection limit of 300pmol/mol. Several species postulated are potentially important sources ofHO_x in the free troposphere, e.g., methanol, acetone, methyl ethylketone, methyl vinyl ketone and methacrolein.     

Variation of dimethylsulfide mixing ratio over the Southern Ocean from 36°S to 70°S

Atmospheric dimethylsulfide (DMS) was measured to investigate the variation in its concentration over sea ice free oceans and sea ice regions of the Southern Ocean, using a proton transfer reaction-mass spectrometer (PTR-MS) on board the icebreaker Shirase from 1 December 2009 to 16 March 2010. In general, DMS concentrations over sea ice regions were very low compared with those over the sea ice free ocean. However, abrupt increases in DMS concentrations occurred over sea ice regions while the ship was moving and crushing the sea ice. Undoubtedly, the elevated DMS concentrations were caused by large DMS emissions from gaps in the ice made by the ship. During the period when Shirase had anchored off Syowa Station (69°00.4′S, 39°35.3′E), Antarctica, DMS concentrations were not detected. At this time, the surrounding sea of East Ongul island, on which Syowa Station is located, was completely covered with multi-year fast ice. Sea ice probably inhibits DMS emission from the ocean to the atmosphere. In addition, there was no evidence that chlorophyll a concentration in the sea water or wind speed above the sea surface affect atmospheric DMS concentrations over the sea ice free ocean regions.