Photochemical production of aerosols from real plant emissions

ATMOSPHERIC CHEMISTRY AND PHYSICS (Impact Factor: 5.05). 07/2009; 9(13). DOI: 10.5194/acpd-9-3041-2009
Source: DOAJ


Emission of biogenic volatile organic compounds (VOC) which on oxidation form secondary organic aerosols (SOA) can couple the vegetation with the atmosphere and climate. Particle formation from tree emissions was investigated in a new setup: a plant chamber coupled to a reaction chamber for oxidizing the plant emissions and for forming SOA. Emissions from the boreal tree species birch, pine, and spruce were studied. In addition, α-pinene was used as reference compound. Under the employed experimental conditions, OH radicals were essential for inducing new particle formation, although O3 (≤80 ppb) was always present and a fraction of the monoterpenes and the sesquiterpenes reacted with ozone before OH was generated. Formation rates of 3 nm particles were linearly related to the VOC carbon mixing ratios, as were the maximum observed volume and the condensational growth rates. For all trees, the threshold of new particle formation was lower than for α-pinene. It was lowest for birch which emitted the largest fraction of oxygenated VOC (OVOC), suggesting that OVOC may play a role in the nucleation process. Incremental mass yields were ≈5% for pine, spruce and α-pinene, and ≈10% for birch. α-Pinene was a good model compound to describe the yield and the growth of SOA particles from coniferous emissions. The mass fractional yields agreed well with observations for boreal forests. Despite the somewhat enhanced VOC and OH concentrations our results may be up-scaled to eco-system level. Using the mass fractional yields observed for the tree emissions and weighting them with the abundance of the respective trees in boreal forests SOA mass concentration calculations agree within 6% with field observations. For a future VOC increase of 50% we predict a particle mass increase due to SOA of 19% assuming today's mass contribution of pre-existing aerosol and oxidant levels.

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    • "The chamber was run in steadystate mode with constant addition of 30 ppb α-pinene and 80 ppb ozone. We began with α-pinene ozonolysis in the dark followed by OH oxidation, where the OH was produced by shielded UV lamps (Mentel et al., 2009). For both conditions, we added seed particles to increase the particle/chamber wall surface ratio in order to better compete with condensation and partitioning of low and semivolatile gases to the chamber walls (Matsunaga and Ziemann, 2010). "
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    ABSTRACT: We measured a large suite of gas and particle phase multi-functional organic compounds with a Filter Inlet for Gases and AEROsols (FIGAERO) coupled to a high-resolution time-of-flight chemical ionization mass spectrometer (HR-ToF-CIMS) developed at the University of Washington. The instrument was deployed on environmental simulation chambers to study monoterpene oxidation as a secondary organic aerosol (SOA) source. We focus here on results from experiments utilizing an ionization method most selective towards acids (acetate negative ion proton transfer), but our conclusions are based on more general physical and chemical properties of the SOA. Hundreds of compounds were observed in both gas and particle phases, the latter being detected upon temperature programmed thermal desorption of collected particles. Particulate organic compounds detected by the FIGAERO HR-ToF-CIMS are highly correlated with, and explain at least 25–50% of, the organic aerosol mass measured by an Aerodyne Aerosol Mass Spectrometer (AMS). Reproducible multi-modal structures in the thermograms for individual compounds of a given elemental composition reveal a significant SOA mass contribution from large molecular weight organics and/or oligomers (i.e. multi-phase accretion reaction products). Approximately 50% of the HR-ToF-CIMS particle phase mass is associated with compounds having effective vapor pressures 4 or more orders of magnitude lower than commonly measured monoterpene oxidation products. The relative importance of these accretion-type and other extremely low volatility products appears to vary with photochemical conditions. We present a desorption temperature based framework for apportionment of thermogram signals into volatility bins. The volatility-based apportionment greatly improves agreement between measured and modeled gas–particle partitioning for select major and minor components of the SOA, consistent with thermal decomposition during desorption causing the conversion of lower volatility components into the detected higher volatility compounds.
    Full-text · Article · Feb 2015 · Atmospheric Chemistry and Physics
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    • "However, climate change is likely to bring about an increase in the importance of boreal forests as a source of volatiles because the activity of evergreen vegetation would be expected to increase when the cooler months become increasingly warmer and extend the growing season (Peñuelas & Staudt 2010). Apart from of inter-specific variation (Mentel et al. 2009) boreal tree species exhibit significant intra-species variation in the composition of emitted VOCs, especially for terpenoid emissions (Muona et al. 1986; Pohjola 1993; Hakola et al. 2001; Vuorinen et al. 2005; Tarvainen et al. 2005; Thoss et al. 2007). The physical or biochemical processes behind this variation remain unclear, but the variation is considered to be genetically determined property (Muona et al. 1986). "

    Preview · Article · Jan 2015
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    • "A major strength of this study is that both the emission factors of SIE/constitutive emissions and SIE-SOA mass yields are determined from the same experimental JPAC data for relevant forest species. As shown for new particle formation and SOA yields the results from the JPAC studies can be transferred to atmospheric situations (Mentel et al., 2009). Uncertainties arise from the estimates of the fraction and spatial distribution of infested trees, as well as limited knowledge of the seasonal variation of some of the infestations. "
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    ABSTRACT: We have investigated the potential impact on organic aerosol formation from biotic stress-induced emissions (SIE) of organic molecules from forests in Europe (north of lat. 45° N). Emission estimates for sesquiterpenes (SQT), methyl salicylate (MeSA) and unsaturated C17 compounds, due to different stressors, are based on experiments in the Jülich Plant Atmosphere Chamber (JPAC), combined with estimates of the fraction of stressed trees in Europe based on reported observed tree damage. SIE were introduced in the EMEP MSC-W chemical transport model and secondary organic aerosol (SOA) yields from the SIE were taken from the JPAC experiments. Based on estimates of current levels of infestation and the JPAC aerosol yields, the model results suggest that the contribution to SOA in large parts of Europe may be substantial. It is possible that SIE contributes as much, or more, to organic aerosol than the constitutive biogenic VOC emissions, at least during some periods. Based on the assumptions in this study, SIE-SOA are estimated to constitute between 50 and 70 % of the total biogenic SOA (BSOA) in a current-situation scenario where the biotic stress in northern and central European forests causes large SIE of MeSA and SQT. An alternative current-situation scenario with lower SIE, consisting solely of SQT, leads to lower SIE-SOA, between 20 and 40 % of the total BSOA. Hypothetical future scenarios with increased SIE, due to higher degrees of biotic stress, show that SOA formation due to SIE can become even larger. Unsaturated C17 BVOC (biogenic volatile organic compounds) emitted by spruce infested by the forest-honey generating bark louse, Cinara pilicornis, have a high SOA-forming potential. A model scenario investigating the effect of a regional, episodic infestation of Cinara pilicornis in Baden-Württemberg, corresponding to a year with high production of forest honey, shows that these types of events could lead to very large organic aerosol formation in the infested region. We have used the best available laboratory data on biotic SIE applicable to northern and central European forests. Using these data and associated assumptions, we have shown that SIE are potentially important for SOA formation but the magnitude of the impact is uncertain and needs to be constrained by further laboratory, field and modelling studies. As an example, the MeSA, which is released as a consequence of various types of biotic stress, is found to have a potentially large impact on SIE-SOA in Europe, but different assumptions regarding the nighttime chemistry of MeSA can change its SOA potential substantially. Thus, further investigations of the atmospheric chemistry of MeSA and observational field studies are needed to clarify the role of this compound in the atmosphere.
    Full-text · Article · Dec 2014 · Atmospheric Chemistry and Physics
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