Photochemical production of aerosols from real plant emissions

ATMOSPHERIC CHEMISTRY AND PHYSICS (Impact Factor: 5.51). 01/2009; DOI: 10.5194/acpd-9-3041-2009
Source: DOAJ

ABSTRACT 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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    ABSTRACT: Atmospheric aerosols impact climate by scattering and absorbing solar radiation and by acting as ice and cloud condensation nuclei. Secondary organic aerosols (SOA) comprise an important component of atmospheric aerosols. Biogenic volatile organic compounds (BVOC) emitted by vegetation are a major source of SOA. Pathogens and insect attacks, heat waves and droughts can induce stress to plants that may impact their BVOC emissions, and hence the yield and type of formed SOA, and possibly their climatic effects. This raises questions whether stress-induced changes in SOA formation may attenuate or amplify effects of climate change. In this study we assess the potential impact of stress-induced BVOC emissions on SOA formation for tree species typical for mixed deciduous and Boreal Eurasian forests. We studied the photochemical SOA formation for infested plants in a laboratory setup under well-controlled conditions and applied in addition heat and drought stress. The results indicate that stress conditions substantially modify SOA formation. While sesquiterpenes, methyl salicylate, and C17-BVOC increase SOA yield, green leaf volatiles suppress SOA formation. By classifying emission types, stressors and SOA formation potential, we propose possible climatic feedbacks regarding aerosol effects. We conclude that stress situations for plants due to climate change should be considered in climate-vegetation feedback mechanisms.
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    ABSTRACT: High molecular weight (300-650 Da) naturally charged negative ions have previously been observed at a boreal forest site in Hyytiälä, Finland. The long-term measurements conducted in this work showed that these ions are observed practically every night between spring and autumn in Hyytiälä. The ambient mass spectral patterns could be reproduced in striking detail during additional measurements of α-pinene (C10H16) oxidation at low-OH conditions in the Jülich Plant Atmosphere Chamber (JPAC). The ions were identified as clusters of the nitrate ion (NO3-) and α-pinene oxidation products reaching oxygen to carbon ratios of 0.7-1.3, while retaining most of the initial ten carbon atoms. Attributing the ions to clusters instead of single molecules was based on additional observations of the same extremely oxidized organics in clusters with HSO4- (Hyytiälä) and C3F5O2- (JPAC). The most abundant products in the ion spectra were identified as C10H14O7, C10H14O9, C10H16O9, and C10H14O11. The mechanism responsible for forming these molecules is still not clear, but the initial reaction is most likely ozone attack at the double bond, as the ions are mainly observed under dark conditions. β-pinene also formed highly oxidized products under the same conditions, but less efficiently, and mainly C9 compounds which were not observed in Hyytiälä, where β-pinene on average is 4-5 times less abundant than α-pinene. Further, to explain the high O/C together with the relatively high H/C, we propose that geminal diols and/or hydroperoxide groups may be important. We estimate that the night-time concentration of the sum of the neutral extremely oxidized products is on the order of 0.1-1 ppt (~106-107 molec cm-3). This is in a similar range as the amount of gaseous H2SO4 in Hyytiälä during day-time. As these highly oxidized organics are roughly 3 times heavier, likely with extremely low vapor pressures, their role in the initial steps of new aerosol particle formation and growth may be important and needs to be explored in more detail in the future.
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    ABSTRACT: The impact of nitrogen oxides (NOx = NO + NO2) on new particle formation (NPF) and on photochemical ozone production from real plant volatile organic compound (BVOC) emissions was studied in a laboratory set up. At high NOx conditions (BVOC/NOx < 7, NOx > 23 ppb) no new particles were formed. Instead photochemical ozone formation was observed resulting in higher hydroxyl radical (OH) and lower nitrogen monoxide (NO) concentrations. As soon as [NO] was reduced to below 1 ppb by OH reactions, NPF was observed. Adding high amounts of NOx caused NPF orders of magnitude slower than in analogous experiments at low NOx conditions (NOx ~ 300 ppt), although OH concentrations were higher. Varying NO2 photolysis enabled showing that NO was responsible for suppression of NPF suggesting that peroxy radicals are involved in NPF. The rates of NPF and photochemical ozone production were related by power law dependence with an exponent of approximately -2. This exponent indicated that the overall peroxy radical concentration must have been the same whenever NPF appeared. Thus permutation reactions of first generation peroxy radicals cannot be the rate limiting step in NPF from monoterpene oxidation. It was concluded that permutation reactions of higher generation peroxy radical like molecules limit the rate of new particle formation. In contrast to the strong effects on the particle numbers, the formation of particle mass was less sensitive to NOx concentrations, if at all. Only at very high NOx concentrations yields were reduced by about an order of magnitude.
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