Monoterpene emissions and carbonyl compound air concentrations during the blooming period of rape (Brassica napus).

An increasing percentage of agricultural land in Germany is used for oil seed plants. Hence, rape has become an important agricultural plant (in Saxony 1998: 12% of the farmland) in the recent years. During flowering of rape along with intensive radiation and high temperatures, a higher production and emission of biogenic VOC was observed. The emissions of terpenes were determined and more importantly, high concentrations of organic carbonyl compounds were observed during this field experiment. All measurements of interest have been carried out during two selected days with optimal weather conditions. It is found that the origin or the mechanism of formation of different group of compounds had strong influence on the day to day variation of their concentrations. The emission flux of terpenes from flowering rape plants was determined to be 16-32 microg h(-1) m(-2) (30-60 ng h(-1) per g dry plant-540-11080 ng h(-1) per plant), in total. Limonene, alpha-thujene and sabinene were the most important compounds (about 60% of total terpenes). For limonene and sabinene reference emission rates (Ms) and temperature coefficients were determined: beta(limonene) = 0.108 K(-1) and Ms = 14.57 microg h(-1) m(-2) beta(sabinene) = 0.095 K(-1) and Ms = 5.39 microg h(-1) m(-2). The detected carbonyl compound concentrations were unexpectedly high (maximum formaldehyde concentration was 18.1 ppbv and 3.4 ppbv for butyraldehyde) for an open field. Possible reasons for these concentrations are the combination of primary emission from the plants induced by high temperature and high ozone stress, the secondary formation from biogenically and advected anthropogenically emitted VOC at high radiation intensities and furthered by the low wind speeds at this time.

Enhanced role of transition metal ion catalysis during in-cloud oxidation of SO2.

Global sulfate production plays a key role in aerosol radiative forcing; more than half of this production occurs in clouds. We found that sulfur dioxide oxidation catalyzed by natural transition metal ions is the dominant in-cloud oxidation pathway. The pathway was observed to occur primarily on coarse mineral dust, so the sulfate produced will have a short lifetime and little direct or indirect climatic effect. Taking this into account will lead to large changes in estimates of the magnitude and spatial distribution of aerosol forcing. Therefore, this oxidation pathway-which is currently included in only one of the 12 major global climate models-will have a significant impact on assessments of current and future climate.

Diaterebic acid acetate and diaterpenylic acid acetate: atmospheric tracers for secondary organic aerosol formation from 1,8-cineole oxidation.

Detailed organic speciation of summer time PM10 collected in Melbourne, Australia, indicated the presence of numerous monoterpene oxidation products that have previously been reported in the literature. In addition, two highly oxygenated compounds with molecular formulas C9H14O6 (MW 218) and C10H16O6 (MW 232), previously unreported, were detected during a period associated with high temperatures and bushfire smoke. These two compounds were also present in laboratory-produced secondary organic aerosol (SOA) through the reaction of OH radicals with 1,8-cineole (eucalyptol), which is emitted by Eucalyptus trees. The retention times and mass spectral behavior of the highly oxygenated compounds in high-performance liquid chromatography (LC) coupled to electrospray ionization-time-of-flight mass spectrometry (MS) in parallel to ion trap MS of agree perfectly between the ambient samples and the laboratory-produced SOA samples, suggesting that 1,8-cineole is the precursor of the highly oxygenated compounds. The proposed structure of the compound with molecular formula C10H16O6 was confirmed by synthesis of a reference compound. The two novel compounds were identified as diaterebic acid acetate (2-[1-(acetyloxy)-1-methylethyl]succinic acid, C9H14O6) and diaterpenylic acid acetate (3-[1-(acetyloxy)-1-methylethyl]glutaric acid, C10H16O6) based on the consideration of reaction mechanisms, the structure of a reference compound, and the interpretation of mass spectral data. Depending on the experimental conditions, the SOA yields determined in chamber experiments ranged between 16 and 20% for approximately 25 ppb of hydrocarbon consumed. The concentrations of these compounds were as high as 50 ng m(-3) during the summertime in Melbourne. This study demonstrates the importance and influence of local vegetation patterns on SOA chemical composition.

Laboratory studies on secondary organic aerosol formation from terpenes.

The formation of secondary organic aerosol (SOA) following the ozonolysis of terpene has been investigated intensively in recent years. The enhancement of SOA yields from the acid catalysed reactions of organics on aerosol surfaces or in the bulk particle phase has been receiving great attention. Recent studies show that the presence of acidic seed particles increases the SOA yield significantly (M. S. Jang and R. M. Kamens, Environ. Sci. Technol., 2001, 35, 4758, ref. 1; M. S. Jang, N. M. Czoschke, S. Lee and R. M. Kamens, Science, 2002, 298, 814, ref. 2; N. M. Czoschke, M. Jang and R. M. Kamens, Atmos. Environ., 2003, 37, 4287, ref. 3; M. S. Jang, B. Carroll, B. Chandramouli and R. M. Kamens, Environ. Sci. Technol., 2003, 37, 3828, ref. 4; Y. Iinuma, O. Böge, T. Gnauk and H. Herrmann, Atmos. Environ., 2004, 38, 761, ref. 5; S. Gao, M. Keywood, N. L. Ng, J. Surratt, V. Varutbangkul, R. Bahreini, R. C. Flagan and J. H. Seinfeld, J. Phys. Chem. A, 2004, 108, 10147, ref. 6). More detailed studies report the formation of higher molecular weight products in SOA (refs. 5 and 6; M. P. Tolocka, M. Jang, J. M. Ginter, F. J. Cox, R. M. Kamens and M. V. Johnston, Environ. Sci. Technol., 2004, 38, 1428, ref. 7; S. Gao, N. L. Ng, M. Keywood, V. Varutbangkul, R. Bahreini, A. Nenes, J. He, K. Y. Yoo, J. L. Beauchamp, R. P. Hodyss, R. C. Flagan and J. H. Seinfeld, Environ. Sci. Technol., 2004, 38, 6582, ref. 8) which could result in a non-reversible uptake of organics into the particle phase. Most of the past studies concentrated on the characterisation of the yields of enhanced SOA and its composition from ozonolysis of terpenes in the presence or absence of acidic and neutral seed particles. Recent findings from cyclohexene ozonolysis show that the presence of OH scavengers can also significantly influence the SOA yield. Our new results from the IfT chemistry department aerosol chamber on terpene ozonolysis in the presence of OH scavengers show that the presence of hydroxyl radical scavengers clearly reduces the amount of formed SOA. The OH scavenger strongly depletes the formation of oligomeric compounds in the particle phase in contrast to previous findings (M. D. Keywood, J. H. Kroll, V. Varatbangkul, R. Bahreini, R. C. Flagan and J. H. Seinfeld, Environ. Sci. Technol., 2004, 38, 3343, ref. 9). This result indicates that hydroxyl radicals play an important role in the formation of precursor compounds (e.g., hydroxy pinonaldehyde) for the particle phase heterogeneous acid catalysed reactions leading to the higher molecular weight compounds and thus the enhancement of SOA yields. Better understanding of the role of hydroxyl radicals in the formation of SOA is necessary to distinguish between the contribution of ozonolysis and hydroxyl radicals to the SOA yield. If the recent findings are a ubiquitous phenomenon in the atmosphere, current atmospheric and climate models might underestimate SOA formation yields, particle phase OC contents and its impact on the atmospheric radiation budget.