Oxidation of Atmospheric Humic Like Substances by Ozone: A Kinetic and Structural Analysis Approach

Baduel, Christine; Monge, Marı́a Eugenia; Voisin, Didier; Jaffrezo, Jean-Luc; George, Christian; Haddad, Imad El; Marchand, Nicolas; D’Anna, Barbara

doi:10.1021/es200587z

Cited by 55 publications

(53 citation statements)

References 42 publications

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“…These are potential ozone sinks and sources of oxygenated VOC in ozone-rich environments, as has been shown previously (see e.g. Wisthaler et al, 2005;Weschler et al, 2007;D'Anna et al, 2009;Wisthaler and Weschler, 2010;Baduel et al, 2011). We speculate that some of the ozonolysis-derived products may play important roles in atmospheric processes, influencing the budgets of OH radicals and ozone.…”

Section: Discussionsupporting

confidence: 76%

“…Semi-volatile, unsaturated organic species are common on various surfaces including soil with plant litter (Weiss, 2000;Isidorov et al, 2003;Ormeño et al, 2009), aerosols (Rogge et al, 1993;D'Anna et al, 2009;Baduel et al, 2011), man-made structures (Wisthaler et al, 2005;Weschler et al, 2007;Shi and Zhao, 2015), and even human skin (Wisthaler and Weschler, 2010). These are potential ozone sinks and sources of oxygenated VOC in ozone-rich environments, as has been shown previously (see e.g.…”

Section: Discussionsupporting

confidence: 53%

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

et al. 2016

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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 varietydependent 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 of cis-abienol (C 20 H 34 O) -a diterpenoid with two exocyclic double bonds -caused emissions of formaldehyde (HCHO) and methyl vinyl ketone (C 4 H 6 O). The ring-structured cembratrien-diols (C 20 H 34 O 2 ) with three endocyclic double bonds need at least two ozonolysis steps to form volatile carbonyls such as 4-oxopentanal (C 5 H 8 O 2 ), 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.

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Section: Discussionsupporting

confidence: 76%

Section: Discussionsupporting

confidence: 53%

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

et al. 2016

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“…The seed particles' composition is assumed to model the main features of (mainly organic) ambient aerosol, containing both complex and simple organics as well as inorganic components, possibly representing aged particles during longrange transport. HAs are considered to be proxy for atmospheric humic-like substances generated from biomass and wood burning because they have similar reactivity under irradiation (21)(22)(23). Dicarboxylic acids represent 4-15% of the total aerosol mass of atmospheric aerosol particles from continental and marine samples (24) and are formed from biomass burning, fossil fuel combustion, cooking, automobile exhaust, and atmospheric reactions of biogenic and anthropogenic VOCs (25).…”

Section: Atmospheric Chemistry | Photoinduced Processesmentioning

confidence: 99%

Alternative pathway for atmospheric particles growth

Monge

Rosenørn

Favez

et al. 2012

Proc. Natl. Acad. Sci. U.S.A.

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143

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Credible climate change predictions require reliable fundamental scientific knowledge of the underlying processes. Despite extensive observational data accumulated to date, atmospheric aerosols still pose key uncertainties in the understanding of Earth’s radiative balance due to direct interaction with radiation and because they modify clouds’ properties. Specifically, major gaps exist in the understanding of the physicochemical pathways that lead to aerosol growth in the atmosphere and to changes in their properties while in the atmosphere. Traditionally, the driving forces for particle growth are attributed to condensation of low vapor pressure species following atmospheric oxidation of volatile compounds by gaseous oxidants. The current study presents experimental evidence of an unaccounted-for new photoinduced pathway for particle growth. We show that heterogeneous reactions activated by light can lead to fast uptake of noncondensable Volatile Organic Compounds (VOCs) at the surface of particles when only traces of a photosensitizer are present in the seed aerosol. Under such conditions, size and mass increase; changes in the chemical composition of the aerosol are also observed upon exposure to volatile organic compounds such as terpenes and near-UV irradiation. Experimentally determined growth rate values match field observations, suggesting that this photochemical process can provide a new, unaccounted-for pathway for atmospheric particle growth and should be considered by models.

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“…Previous studies have observed that γ can have a linear dependence on VIS and UV photon flux, but some measurements were limited in the VIS photon flux intensity compared to the sun's total VIS irradiance (Stemmler et al, 2006;Jammoul et al, 2008;Brigante et al, 2008;D'Anna et al, 2009;Baduel et al, 2011;Sosedova et al, 2011;Zelenay et al, 2011). Previous studies have also shown that the uptake of gas phase oxidants may follow a Langmuir-Hinshelwood (LH) type reaction mechanism, where the oxidant first adsorbs on the organic substrate and subsequently reacts, yielding γ values that are reduced at high oxidant concentrations (Stemmler et al, 2007;Jammoul et al, 2008;Brigante et al, 2008;D'Anna et al, 2009;Net et al, 2010;Baduel et al, 2011;Sosedova et al, 2011;Zelenay et al, 2011).…”

Section: S M Forrester and D A Knopf: Photosensitised Kinetics Ofmentioning

confidence: 99%

“…Previous studies have also shown that the uptake of gas phase oxidants may follow a Langmuir-Hinshelwood (LH) type reaction mechanism, where the oxidant first adsorbs on the organic substrate and subsequently reacts, yielding γ values that are reduced at high oxidant concentrations (Stemmler et al, 2007;Jammoul et al, 2008;Brigante et al, 2008;D'Anna et al, 2009;Net et al, 2010;Baduel et al, 2011;Sosedova et al, 2011;Zelenay et al, 2011). A recent modelling study by Konovalov et al (2012) indicated that there may be a positive feedback between the O 3 loss rate and O 3 mixing ratio because of this inverse dependence of γ on O 3 concentration (Konovalov et al, 2012).…”

Section: S M Forrester and D A Knopf: Photosensitised Kinetics Ofmentioning

confidence: 99%

Photosensitised heterogeneous oxidation kinetics of biomass burning aerosol surrogates by ozone using an irradiated rectangular channel flow reactor

Forrester

Knopf

2013

Atmos. Chem. Phys.

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Abstract. Heterogeneous reaction kinetics involving organic aerosol and atmospheric oxidants such as ozone can be enhanced under visible or UV irradiation in the presence of a photosensitiser, with subsequent implications for the climate, cloud radiative properties, air quality, and source appointment. In this study we report the steady-state reactive uptake coefficient, γ, of O3 by levoglucosan and 5-nitroguaiacol acting as surrogates for biomass burning aerosol particles, with and without the presence of Pahokee peat acting as a photosensitiser. The reactive uptake has been determined in the dark and as a function of visible and UV-A irradiation and ozone concentration. In addition, γ was determined for 1 : 1, 1 : 10, and 1 : 100 by mass mixtures of Pahokee peat and 5-nitroguaiacol, and for a 10 : 1 : 3 mixture of levoglucosan, Pahokee peat, and 5-nitroguaiacol. We developed a novel irradiated rectangular channel flow reactor (I-RCFR) that was operated under low pressures of about 2–4 hPa, and allowed for uniform irradiation of the organic substrates. The I-RCFR was coupled to a chemical ionisation mass spectrometer and has been successfully validated by measuring the kinetics between various organic species and oxidants. γ of O3 and levoglucosan in the dark and under visible and UV-A irradiation was determined to be in the range of (2–11) × 10−6 and did not change in the presence of Pahokee peat. The determined γ of O3 and 5-nitroguaiacol in the dark was 5.7 × 10−6 and was only enhanced under UV-A irradiation, yielding a value of 3.6 × 10−5. γ of the 1 : 1 Pahokee peat/5-nitroguaiacol substrate was enhanced under visible and UV-A irradiation to 2.4 × 10−5 and 2.8 × 10−5, respectively. Decreasing the amount of Pahokee peat in the 5-nitroguaiacol/Pahokee peat substrate resulted in lower values of γ under visible irradiation, however, γ was consistent under UV-A irradiation regardless of the amount of Pahokee peat. The 10 : 1 : 3 mixture by mass of levoglucosan, Pahokee peat, and 5-nitroguaiacol, under both visible and UV-A irradiation yielded γ values of 2.8 × 10−5 and 1.4 × 10−5, respectively. γ was determined as a function of photon flux for O3 with the 1 : 1 Pahokee peat/5-nitroguaiacol substrate, yielding a linear relationship under both visible and UV-A irradiation. γ of O3 with the 1 : 1 Pahokee peat/5-nitroguaiacol substrate was determined as a function of ozone concentration and exhibited an inverse dependence of γ on ozone concentration, commonly interpreted as a Langmuir–Hinshelwood mechanism. The reactive uptake data have been represented by a Langmuir-type isotherm. From the O3 uptake data under visible irradiation, the following fit parameters have been derived: ks = (5.5 ± 2.7) × 10−19 cm2 s−1 molecule−1 and KO3 = (2.3 ± 2.0) × 10−12 cm3 molecule−1; and under UV-A irradiation: ks = (8.1 ± 2.0) × 10−19 cm2 s−1 molecule−1 and KO3 = (1.7 ± 0.7) × 10−12 cm3 molecule−1. The oxidative power, or the product of γ and [O3], was determined for O3 with the 1 : 1 Pahokee peat/5-nitroguaiacol substrate and was in the range of (1.2–26) × 106 molecule cm−3. Atmospheric particle lifetimes were estimated for a 0.4 μm 5-nitroguaiacol particle as a function of visible and UV-A irradiation and ozone concentration.

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Oxidation of Atmospheric Humic Like Substances by Ozone: A Kinetic and Structural Analysis Approach

Cited by 55 publications

References 42 publications

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

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

Alternative pathway for atmospheric particles growth

Photosensitised heterogeneous oxidation kinetics of biomass burning aerosol surrogates by ozone using an irradiated rectangular channel flow reactor

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