Browsing by Subject "Monoterpenes"

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  • Thomas, Steven Job (Helsingin yliopisto, 2020)
    Biogenic Volatile Organic Compounds play a major role in the atmosphere by acting as precursors in the formation of secondary organic aerosols and by also affecting the concentration of ozone. The chemical diversity of BVOCs is vast but global emissions are dominated by isoprene and monoterpenes. The emissions of BVOCs from plants are affected by environmental parameters with temperature and light having significant impacts on the emissions. The Downy birch and Norway spruce trees consist of heavy and low volatile compounds but published results are limited up to observing sesquiterpenoid emissions from these two trees. In this study, the Vocus proton-transfer-reaction time-of-flight mass spectrometer is deployed in the field to examine BVOC emissions from Downy birch and Norway spruce trees. With higher mass resolution, shorter time response and lower limits of detection than conventional PTR instruments, the Vocus can effectively measure a broader range of VOCs. For the first time, real-time emissions of diterpenes and 12 different oxygenated compounds were observed from birch and spruce trees. The emission spectrum of birch was dominated by C10H17+, while for spruce C5H9+ contributed the most. The sum emissions of oxygenated compounds contributed significantly to the observed total emissions from both the trees. The emission rates of all compounds varied dramatically throughout the period due to fluctuations in temperature and light. Due to lack of data from spruce, conclusive results for temperature and light response on terpene emissions could not be drawn. For birch, the emission rates were well explained by the temperature and temperature-light algorithms. The terpene emissions modelled using both algorithms correlated similarly with experimental data making it difficult to decisively conclude if the emissions originated from synthesis or pools.
  • Draper, Danielle C.; Myllys, Nanna; Hyttinen, Noora; Moller, Kristian H.; Kjaergaard, Henrik G.; Fry, Juliane L.; Smith, James N.; Kurten, Theo (2019)
    NO3 radical oxidation of most monoterpenes is a significant source of secondary organic aerosol (SOA) in many regions influenced by both biogenic and anthropogenic emissions, but there are very few published mechanistic studies of NO3 chemistry beyond simple first generation products. Here, we present a computationally derived mechanism detailing the unimolecular pathways available to the second generation of peroxy radicals following NO3 oxidation of Delta-3-carene, defining generations based on the sequence of peroxy radicals formed rather than number of oxidant attacks. We assess five different types of unimolecular reactions, including peroxy and alkoxy radical (RO2 and RO) hydrogen shifts, RO2 and RO ring closing (e.g., endoperoxide formation), and RO decomposition. Rate constants calculated using quantum chemical methods indicate that this chemical system has significant contribution from both bimolecular and unimolecular pathways. The dominant unimolecular reactions are endoperoxide formation, RO H-shifts, and RO decomposition. However, the complexity of the overall reaction is tempered as only 1 or 2 radical propagation pathways dominate the fate of each radical intermediate. Chemical ionization mass spectrometry (CIMS) measurements using the NO3- reagent ion during Delta-3-carene + NO3 chamber experiments show products consistent with each of the three types of unimolecular reactions predicted to be important from the computational mechanism. Moreover, the SIMPOL group contribution method for predicting vapor pressures suggests that a majority of the closed-shell products inferred from these unimolecular reactions are likely to have low enough vapor pressure to be able to contribute to SOA formation.
  • Rissanen, Kaisa; Hölttä, Teemu; Barreira, Luis F. M.; Hyttinen, Noora; Kurtén, Theo; Bäck, Jaana (2019)
    Resin is a first-line defense in pine trees, but important questions regarding its temporal and spatial variation remain unsolved. Resin pressure varies according to water potential in dry conditions, but in moist conditions, it follows temperature dynamics for a yet unknown reason. Relations between resin composition, resin pressure, and shoot monoterpene emissions are also unquantified. To gain mechanistic understanding on the resin dynamics in a boreal forest, we measured temperature and water potential dependency of Scots pine resin pressure. We attempted to quantify the temperature dependency of resin pressure in terms of three contributions: 1) saturation vapor pressure, 2) thermal expansion, and 3) N2, O2, and CO2 solubility. We also analyzed monoterpene composition in the resin and the shoot emissions of 16 pines with gas chromatography mass spectrometry to study their interrelations. We show that in moist conditions, resin pressure is driven by temperature at a diurnal scale, but also affected by soil water potential at a day-to-day scale. Diurnal temperature dependency was explained by thermal expansion of resin and changes in bubble volume due to changes in gas solubility in resin with temperature. Resin pressures correlated also with total monoterpene and α-pinene content in resin and with total monoterpene and ∆3-carene and terpinolene emissions from shoots.