scholarly journals Plant surface reactions: an opportunistic ozone defence mechanism impacting atmospheric chemistry

2016 ◽  
Vol 16 (1) ◽  
pp. 277-292 ◽  
Author(s):  
W. Jud ◽  
L. Fischer ◽  
E. Canaval ◽  
G. Wohlfahrt ◽  
A. Tissier ◽  
...  

Abstract. Elevated tropospheric ozone concentrations are considered a toxic threat to plants, responsible for global crop losses with associated economic costs of several billion dollars per year. Plant injuries have been linked to the uptake of ozone through stomatal pores and oxidative damage of the internal leaf tissue. But a striking question remains: can surface reactions limit the stomatal uptake of ozone and therefore reduce its detrimental effects to plants?In this laboratory study we could show that semi-volatile organic compounds exuded by the glandular trichomes of different Nicotiana tabacum varieties are an efficient ozone sink at the plant surface. In our experiments, different diterpenoid compounds were responsible for a strongly variety-dependent ozone uptake of plants under dark conditions, when stomatal pores are almost closed. Surface reactions of ozone were accompanied by a prompt release of oxygenated volatile organic compounds, which could be linked to the corresponding precursor compounds: ozonolysis cis-abienol (C20H34O) – a diterpenoid with two exocyclic double bonds – caused emissions of formaldehyde (HCHO) and methyl vinyl ketone (C4H6O). The ring-structured cembratrien-diols (C20H34O2) with three endocyclic double bonds need at least two ozonolysis steps to form volatile carbonyls such as 4-oxopentanal (C5H8O2), which we could observe in the gas phase, too.Fluid dynamic calculations were used to model ozone distribution in the diffusion-limited leaf boundary layer under daylight conditions. In the case of an ozone-reactive leaf surface, ozone gradients in the vicinity of stomatal pores are changed in such a way that the ozone flux through the open stomata is strongly reduced.Our results show that unsaturated semi-volatile compounds at the plant surface should be considered as a source of oxygenated volatile organic compounds, impacting gas phase chemistry, as well as efficient ozone sink improving the ozone tolerance of plants.

2015 ◽  
Vol 15 (14) ◽  
pp. 19873-19902
Author(s):  
W. Jud ◽  
L. Fischer ◽  
E. Canaval ◽  
G. Wohlfahrt ◽  
A. Tissier ◽  
...  

Abstract. Elevated tropospheric ozone concentrations are considered a toxic threat to plants, responsible for global crop losses with associated economic costs of several billion dollars per year. Plant injuries have been linked to the uptake of ozone through stomatal pores and oxidative damage of the internal leaf tissue. But a striking question remains: how much ozone effectively enters the plant through open stomata and how much is lost by chemical reactions at the plant surface? In this laboratory study we could show that semi-volatile organic compounds exuded by the glandular trichomes of different Nicotiana tabacum varieties are an efficient ozone sink at the plant surface. In our experiments, different diterpenoid compounds were responsible for a strongly variety dependent ozone uptake of plants under dark conditions, when stomatal pores are almost closed. Surface reactions of ozone were accompanied by prompt release of oxygenated volatile organic compounds, which could be linked to the corresponding precursor compounds: ozonolysis of cis-abienol (C20H34O) – a diterpenoid with two exocyclic double bonds – caused emissions of formaldehyde (HCHO) and methyl vinyl ketone (C4H6O). The ring-structured cembratrien-diols (C20H34O2) with three endocyclic double bonds need at least two ozonolysis steps to form volatile carbonyls such as 4-oxopentanal (C5H8O2), which we could observe in the gas phase, too. Fluid dynamic calculations were used to model ozone distribution in the diffusion limited leaf boundary layer under daylight conditions. In the case of an ozone-reactive leaf surface, ozone gradients in the vicinity of stomatal pores are changed in such a way, that ozone flux through the open stomata is strongly reduced. Our results show that unsaturated semi-volatile compounds at the plant surface should be considered as a source of oxygenated volatile organic compounds, impacting gas phase chemistry, as well as efficient ozone sink improving the ozone tolerance of plants.


2008 ◽  
Vol 42 (34) ◽  
pp. 7844-7850 ◽  
Author(s):  
Aikaterini K. Boulamanti ◽  
Christos A. Korologos ◽  
Constantine J. Philippopoulos

2013 ◽  
Vol 13 (12) ◽  
pp. 32649-32701 ◽  
Author(s):  
M. Li ◽  
Q. Zhang ◽  
D. G. Streets ◽  
K. B. He ◽  
Y. F. Cheng ◽  
...  

Abstract. An accurate speciation mapping of non-methane volatile organic compounds (NMVOC) emissions has an important impact on the performance of chemical transport models (CTMs) in simulating ozone mixing ratios and secondary organic aerosols. In this work, we developed an improved speciation framework to generate model-ready anthropogenic Asian NMVOC emissions for various gas-phase chemical mechanisms commonly used in CTMs by using an explicit assignment approach and updated NMVOC profiles, based on the total NMVOC emissions in the INTEX-B Asian inventory for the year 2006. NMVOC profiles were selected and aggregated from a wide range of new measurements and the SPECIATE database. To reduce potential uncertainty from individual measurements, composite profiles were developed by grouping and averaging source profiles from the same category. The fractions of oxygenated volatile organic compounds (OVOC) were corrected during the compositing process for those profiles which used improper sampling and analyzing methods. Emissions of individual species were then lumped into species in different chemical mechanisms used in CTMs by applying mechanism-dependent species mapping tables, which overcomes the weakness of inaccurate mapping in previous studies. Gridded emissions for eight chemical mechanisms are developed at 30 min × 30 min resolution using various spatial proxies and are provided through the website: http://mic.greenresource.cn/intex-b2006. Emission estimates for individual NMVOC species differ between one and three orders of magnitude for some species when different sets of profiles are used, indicating that source profile is the most important source of uncertainties of individual species emissions. However, those differences are diminished in lumped species as a result of the lumping in the chemical mechanisms.


The Analyst ◽  
2010 ◽  
Vol 135 (2) ◽  
pp. 306 ◽  
Author(s):  
Leonard A. Dillon ◽  
Victoria N. Stone ◽  
Laura A. Croasdell ◽  
Peter R. Fielden ◽  
Nicholas J. Goddard ◽  
...  

2019 ◽  
Vol 19 (22) ◽  
pp. 13741-13758
Author(s):  
Carlton Xavier ◽  
Anton Rusanen ◽  
Putian Zhou ◽  
Chen Dean ◽  
Lukas Pichelstorfer ◽  
...  

Abstract. In this study we modeled secondary organic aerosol (SOA) mass loadings from the oxidation (by O3, OH and NO3) of five representative biogenic volatile organic compounds (BVOCs): isoprene, endocyclic bond-containing monoterpenes (α-pinene and limonene), exocyclic double-bond compound (β-pinene) and a sesquiterpene (β-caryophyllene). The simulations were designed to replicate an idealized smog chamber and oxidative flow reactors (OFRs). The Master Chemical Mechanism (MCM) together with the peroxy radical autoxidation mechanism (PRAM) were used to simulate the gas-phase chemistry. The aim of this study was to compare the potency of MCM and MCM + PRAM in predicting SOA formation. SOA yields were in good agreement with experimental values for chamber simulations when MCM + PRAM was applied, while a stand-alone MCM underpredicted the SOA yields. Compared to experimental yields, the OFR simulations using MCM + PRAM yields were in good agreement for BVOCs oxidized by both O3 and OH. On the other hand, a stand-alone MCM underpredicted the SOA mass yields. SOA yields increased with decreasing temperatures and NO concentrations and vice versa. This highlights the limitations posed when using fixed SOA yields in a majority of global and regional models. Few compounds that play a crucial role (>95 % of mass load) in contributing to SOA mass increase (using MCM + PRAM) are identified. The results further emphasized that incorporating PRAM in conjunction with MCM does improve SOA mass yield estimation.


2019 ◽  
Vol 12 (3) ◽  
pp. 1861-1870 ◽  
Author(s):  
Alexander Zaytsev ◽  
Martin Breitenlechner ◽  
Abigail R. Koss ◽  
Christopher Y. Lim ◽  
James C. Rowe ◽  
...  

Abstract. Chemical ionization mass spectrometry (CIMS) instruments routinely detect hundreds of oxidized organic compounds in the atmosphere. A major limitation of these instruments is the uncertainty in their sensitivity to many of the detected ions. We describe the development of a new high-resolution time-of-flight chemical ionization mass spectrometer that operates in one of two ionization modes: using either ammonium ion ligand-switching reactions such as for NH4+ CIMS or proton transfer reactions such as for proton-transfer-reaction mass spectrometer (PTR-MS). Switching between the modes can be done within 2 min. The NH4+ CIMS mode of the new instrument has sensitivities of up to 67 000 dcps ppbv−1 (duty-cycle-corrected ion counts per second per part per billion by volume) and detection limits between 1 and 60 pptv at 2σ for a 1 s integration time for numerous oxygenated volatile organic compounds. We present a mass spectrometric voltage scanning procedure based on collision-induced dissociation that allows us to determine the stability of ammonium-organic ions detected by the NH4+ CIMS instrument. Using this procedure, we can effectively constrain the sensitivity of the ammonia chemical ionization mass spectrometer to a wide range of detected oxidized volatile organic compounds for which no calibration standards exist. We demonstrate the application of this procedure by quantifying the composition of secondary organic aerosols in a series of laboratory experiments.


Atmosphere ◽  
2019 ◽  
Vol 10 (12) ◽  
pp. 760 ◽  
Author(s):  
Wanyi Qiu ◽  
Shule Li ◽  
Yuhan Liu ◽  
Keding Lu

Due to the development of industrialization and urbanization, secondary pollution is becoming increasingly serious in the Yangtze River Delta. Volatile organic compounds (VOCs) are key precursors of the near-surface ozone, secondary organic aerosol (SOA), and other secondary pollutants. In this study, we chose a serious ozone pollution period (01 May–31 July 2017) in Jinshan, which is a petrochemical and industrial area in Shanghai. We explored the VOCs distribution characteristics and contribution to secondary pollutants via constructing a regional network based on wind patterns. We determined that dense pollutants were accumulated at adjacent sites under local circulation (LC), and pollution from petrochemical discharge was more serious than industry for all sites under southeast (SE) wind. We also found that cyclopentane, o-xylene, m/p-xylene, 1-3-butadiene, and 1-hexene were priority-controlled species as they were most vital to form secondary pollutants. This study proves that regional network analysis can be successfully applied to explore pollution characteristics and regional secondary pollutants formation.


2019 ◽  
Vol 19 (3) ◽  
pp. 1867-1880 ◽  
Author(s):  
Shino Toma ◽  
Steve Bertman ◽  
Christopher Groff ◽  
Fulizi Xiong ◽  
Paul B. Shepson ◽  
...  

Abstract. Gas-phase atmospheric concentrations of peroxyacetyl nitrate (PAN), peroxypropionyl nitrate (PPN), and peroxymethacryloyl nitrate (MPAN) were measured on the ground using a gas chromatograph electron capture detector (GC-ECD) during the Southern Oxidants and Aerosols Study (SOAS) 2013 campaign (1 June to 15 July 2013) in Centreville, Alabama, in order to study biosphere–atmosphere interactions. Average levels of PAN, PPN, and MPAN were 169, 5, and 9 pptv, respectively, and the sum accounts for an average of 16 % of NOy during the daytime (10:00 to 16:00 local time). Higher concentrations were seen on average in air that came to the site from the urban NOx sources to the north. PAN levels were the lowest observed in ground measurements over the past two decades in the southeastern US. A multiple regression analysis indicates that biogenic volatile organic compounds (VOCs) account for 66 % of PAN formation during this study. Comparison of this value with a 0-D model simulation of peroxyacetyl radical production indicates that at least 50 % of PAN formation is due to isoprene oxidation. MPAN has a statistical correlation with isoprene hydroxynitrates (IN). Organic aerosol mass increases with gas-phase MPAN and IN concentrations, but the mass of organic nitrates in particles is largely unrelated to MPAN.


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