scholarly journals The oxidation regime and SOA composition in limonene ozonolysis: roles of different double bonds, radicals, and water

2018 ◽  
Vol 18 (20) ◽  
pp. 15105-15123 ◽  
Author(s):  
Yiwei Gong ◽  
Zhongming Chen ◽  
Huan Li
Keyword(s):  
Mass Fraction ◽  
Reaction Pathway ◽  
Performic Acid ◽  
Oh Radicals ◽  
Double Bonds ◽  
Criegee Intermediates ◽  
Volatile Organic ◽  
Partitioning Coefficients ◽  
Reaction With Water ◽  
Partitioning Behavior

Abstract. Volatile organic compounds play an important role in air quality and climate change, largely because they contribute to the formation of oxidizing compounds and secondary organic aerosol (SOA). In this study, a series of products, including peroxides and carbonyl compounds in both gaseous and particulate phases, were simultaneously detected to investigate the oxidation regime and SOA composition in limonene ozonolysis. The roles of different double bonds (DBs), radicals, and water were also examined. In our first investigation, we focused on representative oxidizing compounds produced in limonene ozonolysis, including stabilized Criegee intermediates (SCIs), OH radicals, and peroxides. The dependence of H2O2 and hydroxymethyl hydroperoxide (HMHP) formation on RH demonstrates that the reaction with water is an important reaction pathway for limonene SCIs, and the lower limit SCI yields of endocyclic and exocyclic DBs were estimated to be ∼0.24 and ∼0.43, respectively. The OH yield was determined by adding sufficient amounts of an OH scavenger, and the OH yields of endocyclic and exocyclic DBs were ∼0.65 and ∼0.24, respectively. These results indicate that in limonene ozonolysis the endocyclic DB is inclined to generate OH radicals through the hydroperoxide channel, while the exocyclic DB has a higher fraction of forming SCIs. Additionally, other gas-phase and particle-phase peroxides were also studied in this work. The formation of performic acid (PFA) and peracetic acid (PAA) was promoted significantly by increasing RH and the degree of oxidation, and the discrepancy between the experimental and model results suggested some missing formation pathways. Considerable generation of H2O2 from SOA in the aqueous phase was observed, especially at a high [O3] ∕ [limonene] ratio, which was mainly attributed to the hydration and decomposition of unstable peroxides in SOA such as peroxycarboxylic acids and peroxyhemiacetals. Different DBs and OH scavengers had a large impact on the particulate peroxides, and their stability indicated that the types of peroxides in SOA changed under different conditions. As for the contribution of peroxides to SOA, the results demonstrated that the mass fraction of particulate peroxides in limonene SOA was less than 0.2 at a low [O3] ∕ [limonene] ratio, while the mass fraction was 0.4–0.6 at a high [O3] ∕ [limonene] ratio. The partitioning behavior of peroxides showed that multi-generation oxidation helped produce more low-volatility peroxides, which partially explained the higher SOA yield. The partitioning behavior of carbonyls was also examined and the experimental partitioning coefficients (Kp) were found to be typically several orders of magnitude higher than the theoretical values. This study provided new insights into the oxidation regime and SOA composition in limonene ozonolysis, and limonene showed its specificity in many aspects when both endocyclic and exocyclic DBs were ozonated. We suggest that the atmospheric implications of terpenes containing more than one DB and the SOA composition, especially particulate peroxides, need further study.

scholarly journals Understanding the oxidants transition and SOA property in limonene ozonolysis: Role of different double bonds, radical chemistry, and water

2018 ◽  
Author(s):  
Yiwei Gong ◽  
Zhongming Chen ◽  
Huan Li
Keyword(s):  
Radical Scavenger ◽  
Oh Radical ◽  
Aerosol Formation ◽  
Double Bonds ◽  
Radical Chemistry ◽  
Criegee Intermediates ◽  
Partitioning Coefficients ◽  
Reaction With Water ◽  
Relationship Of ◽  
Partitioning Behavior

Abstract. Volatile organic compounds (VOCs) play an important role in air quality and climate change, largely because of their contribution to atmospheric oxidation capacity and secondary organic aerosol (SOA) formation through their oxidation. In this study, a series of products including peroxides and carbonyl compounds in both gaseous and particulate phases were simultaneously detected to help us investigate the oxidants transition and SOA property in limonene ozonolysis. Reactants ratio, OH radical scavenger and relative humidity (RH) were controlled to discuss the effect of endocyclic and exocyclic double bonds (DBs), radial chemistry and water. Alkene ozonolysis not only consumed but also regenerated oxidants, which made a great impact on atmospheric chemical processes. For this issue, we first paid attention to the generation of stabilized Criegee intermediates (SCIs) and OH radical. The variation of H2O2 and hydroxymethyl hydroperoxide (HMHP) formation with RH showed the importance of the reaction with water for limonene SCIs, and the estimated SCIs yields of endocyclic and exocyclic DBs were ~ 0.24 and ~ 0.43, respectively. OH yield was determined by adding sufficient OH scavenger, and the OH yields of endocyclic and exocyclic DBs were ~ 0.65 and ~ 0.24, respectively. The results indicated that in limonene ozonolysis the endocyclic DB was inclined to generate OH radical through hydroperoxide channel, while the exocyclic DB had higher fraction of forming SCIs. Besides, other gas-phase and particle-phase peroxides were also studied. The formation of peroxyformic acid (PFA) and peroxyacetic acid (PAA) were promoted significantly by the increasing RH and the oxidation degree, and the discrepancy between the experimental and model results suggested some missing formation pathways. Considerable H2O2 generation from SOA in aqueous phase was observed especially at high [O3]/[limonene], which was mainly attributed to the hydration and decomposition of particulate unstable peroxides such as peroxycarboxylic acids and peroxyhemiacetals. Different DBs and radical chemistry revealed their influence on aerosol property through affecting the behavior of SOA on generating H2O2. As a species owning high SOA formation potential, another key issue we investigated in limonene ozonolysis was SOA property, for which peroxides and carbonyls were chosen as representatives. The results showed that in limonene SOA, peroxides could account for 0.07–0.19 at low [O3]/[limonene] and 0.40–0.58 at high [O3]/[limonene], which confirmed the important contribution of peroxides to aerosol formation. The partitioning behavior of peroxides showed that multigeneration oxidation helped produce more low-volatility peroxides, which provided some explanation for higher SOA yield. The partitioning behavior of carbonyls was also discussed and the experimental partitioning coefficients (Kp) were usually several orders of magnitude higher than theoretical values, yet the relationship of Kp observed in laboratory with vapor pressure offered some reference for predicting the contribution of carbonyls to SOA formation. This study provided new insights into the oxidants transition and SOA property in limonene ozonolysis, and limonene showed its specificity in many aspects when both endocyclic and exocyclic DBs were ozonated. We suggested that the atmospheric implications of terpenes containing more than one DB and the properties of particulate products especially peroxides still needed further study.

scholarly journals Role of Criegee intermediates in the formation of sulfuric acid at a Mediterranean (Cape Corsica) site under influence of biogenic emissions

2021 ◽  
Vol 21 (17) ◽  
pp. 13333-13351
Author(s):  
Alexandre Kukui ◽  
Michel Chartier ◽  
Jinhe Wang ◽  
Hui Chen ◽  
Sébastien Dusanter ◽  
...  
Keyword(s):  
Steady State ◽  
Sulfuric Acid ◽  
Organic Compounds ◽  
Rate Coefficients ◽  
Oh Radicals ◽  
Additional Source ◽  
So2 Oxidation ◽  
Criegee Intermediates ◽  
Volatile Organic

Abstract. Reaction of stabilized Criegee intermediates (SCIs) with SO2 was proposed as an additional pathway of gaseous sulfuric acid (H2SO4) formation in the atmosphere, supplementary to the conventional mechanism of H2SO4 production by oxidation of SO2 in reaction with OH radicals. However, because of a large uncertainty in mechanism and rate coefficients for the atmospheric formation and loss reactions of different SCIs, the importance of this additional source is not well established. In this work, we present an estimation of the role of SCIs in H2SO4 formation at a western Mediterranean (Cape Corsica) remote site, where comprehensive field observations including gas-phase H2SO4, OH radicals, SO2, volatile organic compounds (VOCs) and aerosol size distribution measurements were performed in July–August 2013 as a part of the project ChArMEx (Chemistry-Aerosols Mediterranean Experiment). The measurement site was under strong influence of local emissions of biogenic volatile organic compounds, including monoterpenes and isoprene generating SCIs in reactions with ozone, and, hence, presenting an additional source of H2SO4 via SO2 oxidation by the SCIs. Assuming the validity of a steady state between H2SO4 production and its loss by condensation on existing aerosol particles with a unity accommodation coefficient, about 90 % of the H2SO4 formation during the day could be explained by the reaction of SO2 with OH. During the night the oxidation of SO2 by OH radicals was found to contribute only about 10 % to the H2SO4 formation. The accuracy of the derived values for the contribution of OH + SO2 reaction to the H2SO4 formation is limited mostly by a large, at present factor of 2, uncertainty in the OH + SO2 reaction rate coefficient. The contribution of the SO2 oxidation by SCIs to the H2SO4 formation was evaluated using available measurements of unsaturated VOCs and steady-state SCI concentrations estimated by adopting rate coefficients for SCI reactions based on structure–activity relationships (SARs). The estimated concentration of the sum of SCIs was in the range of (1–3) × 103 molec. cm−3. During the day the reaction of SCIs with SO2 was found to account for about 10 % and during the night for about 40 % of the H2SO4 production, closing the H2SO4 budget during the day but leaving unexplained about 50 % of the H2SO4 formation during the night. Despite large uncertainties in used kinetic parameters, these results indicate that the SO2 oxidation by SCIs may represent an important H2SO4 source in VOC-rich environments, especially during nighttime.

Temperature dependence of the gas-particle partitioning of selected VOCs

2021 ◽  
Author(s):  
Jeonghyeon Ahn ◽  
Guiying Rao ◽  
Eric Vejerano
Keyword(s):  
Volatile Organic Compounds ◽  
Temperature Dependence ◽  
Organic Compounds ◽  
Aerosol Particle ◽  
Mass Fraction ◽  
Small Mass ◽  
Volatile Organic ◽  
Partitioning Coefficients

The gas-particle partitioning coefficients for volatile organic compounds (VOCs) are difficult to acquire because discriminating the small mass fraction of the VOCs in the aerosol particle relative to that in...

scholarly journals Role of Criegee intermediates in the formation of sulfuric acid at a Mediterranean (Cape Corsica) site under influence of biogenic emissions

2021 ◽  
Author(s):  
Alexandre Kukui ◽  
Michel Chartier ◽  
Jinhe Wang ◽  
Hui Chen ◽  
Sébastien Dusanter ◽  
...  
Keyword(s):  
Steady State ◽  
Sulfuric Acid ◽  
Organic Compounds ◽  
Rate Coefficients ◽  
Oh Radicals ◽  
Additional Source ◽  
So2 Oxidation ◽  
Criegee Intermediates ◽  
Volatile Organic

Abstract. Reaction of stabilized Criegee Intermediates (SCIs) with SO2 was proposed as an additional pathway of gaseous sulfuric acid (H2SO4) formation in the atmosphere, supplementary to the conventional mechanism of H2SO4 production by oxidation of SO2 in reaction with OH radicals. However, because of a large uncertainty in mechanism and rate coefficients for the atmospheric formation and loss reactions of different SCIs, the importance of this additional source is not well established. In this work, we present an estimation of the role of SCIs in H2SO4 formation at a western Mediterranean (Cape Corsica) remote site, where a comprehensive field observations including gas phase H2SO4, OH radicals, SO2, volatile organic compounds (VOCs) and aerosol size distribution measurements have been performed in July–August 2013 as a part of the project ChArMEx. The measurement site was under strong influence of local emissions of biogenic volatile organic compounds including monoterpenes and isoprene generating SCIs in reactions with ozone and, hence, presenting an additional source of H2SO4 via SO2 oxidation by the SCIs. Assuming the validity of a steady state between H2SO4 production and its loss by condensation on existing aerosol particles with a unity accommodation coefficient, about 90 % of the H2SO4 formation during the day could be explained by the reaction of SO2 with OH. During the night the oxidation of SO2 by OH radicals was found to contribute only about 10 % to the H2SO4 formation. The accuracy of the derived values for the contribution of OH+SO2 reaction to the H2SO4 formation is limited mostly by a large, presently of a factor of 2, uncertainty in OH+SO2 reaction rate coefficient. The contribution of the SO2 oxidation by SCIs to the H2SO4 formation was evaluated using available measurements of unsaturated VOCs and steady state SCIs concentrations estimated by adopting rate coefficients for SCIs reactions based on structure–activity relationships (SARs). The estimated concentration of the sum of SCIs was in the range of (1–3) × 103 molecule cm−3. During the day the reaction of SCIs with SO2 was found to account for about 10 % and during the night for about 40 % of the H2SO4 production, closing the H2SO4 budget during the day but leaving unexplained about 50 % of the H2SO4 formation during the night. Despite large uncertainties in used kinetic parameters, these results indicate that the SO2 oxidation by SCIs may represent an important H2SO4 source in VOCs-rich environments, especially during night-time.

scholarly journals Measurements of the OH radical yield from the ozonolysis of biogenic alkenes: A potential interference with laser-induced fluorescence measurements of ambient OH

2017 ◽  
Author(s):  
Pamela Rickly ◽  
Philip S. Stevens
Keyword(s):  
Flow Reactor ◽  
Laser Induced Fluorescence ◽  
Fluorescence Measurements ◽  
Criegee Intermediates ◽  
Volatile Organic ◽  
Forested Areas ◽  
Rigorous Test ◽  
Reactor Operating ◽  
Gas Expansion ◽  
Radical Yield

Abstract. Reactions of the hydroxyl radical (OH) play a central role in the chemistry of the atmosphere, and measurements of its concentration can provide a rigorous test of our understanding of atmospheric oxidation. Several recent studies have shown large discrepancies between measured and modeled OH concentrations in forested areas impacted by emissions of biogenic volatile organic compounds (BVOCs), where modeled concentrations were significantly lower than measurements. A potential reason for some of these discrepancies involves interferences associated with the measurement of OH using the Laser-Induced Fluorescence – Fluorescence Assay with Gas Expansion (LIF-FAGE) technique in these environments. In this study, a turbulent flow reactor operating at atmospheric pressure was coupled to a LIF-FAGE cell and the OH signal produced from the ozonolysis of several BVOCs was measured. To distinguish between OH produced from the ozonolysis reactions and any OH artefact produced inside the LIF-FAGE cell, an external chemical scrubbing technique was used, allowing for the direct measurement of any interference. An interference under high ozone and BVOC concentrations was observed that was not laser generated and was independent of the ozonolysis reaction time. Addition of acetic acid to the reactor eliminated the interference, suggesting that the source of the interference in these experiments involved the decomposition of stabilized Criegee intermediates inside the FAGE detection cell.

scholarly journals Importance of SOA formation of α-pinene, limonene and <i>m</i>-cresol comparing day-and night-time radical chemistry

2020 ◽  
Author(s):  
Anke Mutzel ◽  
Yanli Zhang ◽  
Olaf Böge ◽  
Maria Rodigast ◽  
Agata Kolodziejczyk ◽  
...  
Keyword(s):  
Mass Fraction ◽  
Radical Reaction ◽  
Water Soluble ◽  
Oh Radicals ◽  
Oh Radical ◽  
Night Time ◽  
Formation Potential ◽  
Phase Constituent ◽  
Dry Conditions ◽  
The One

Abstract. The oxidation of biogenic and anthropogenic compounds leads to the formation of secondary organic aerosol mass (SOA). The present study aims to investigate α-pinene, limonene and m-cresol with regards to their SOA formation potential dependent on relative humidity (RH) under night- (NO3 radicals) and day-time conditions (OH radicals) and the resulting chemical composition. It was found that SOA formation potential of limonene with NO3 significantly exceeds the one of the OH radical reaction, with SOA yields of 15–30 % and 10–21 %, respectively. Additionally, the nocturnal SOA yield was found to be very sensitive towards RH, yielding more SOA under dry conditions. On the contrary, the SOA formation potential of α-pinene with NO3 slightly exceeds that of the OH radical reaction, independent from RH. In average, α-pinene yielded SOA with about 6–7 % from NO3 radicals and 3–4 % from OH radical reaction. Surprisingly, unexpected high SOA yields were found for m-cresol oxidation with OH radicals (3–9 %) with the highest yield under elevated RH (9 %) which is most likely attributed to a higher fraction of 3-methyl-6-nitro-catechol (MNC). While α-pinene and m-cresol SOA was found to be mainly composed of water-soluble compounds, 50–68 % of nocturnal SOA and 22–39 % of daytime limonene SOA is water-insoluble. The fraction of SOA-bound peroxides which originated from α-pinene varied between 2–80 % as a function of RH. Furthermore, SOA from α-pinene revealed pinonic acid as the most important particle-phase constituent under day- and night-time conditions with fraction of 1–4 %. Further compounds detected are norpinonic acid (0.05–1.1 % mass fraction), terpenylic acid (0.1–1.1 % mass fraction), pinic acid (0.1–1.8 % mass fraction) and 3-methyl-1,2,3-tricarboxylic acid (0.05–0.5 % mass fraction). All marker compounds showed higher fractions under dry conditions when formed during daytime and almost no RH effect when formed during night.

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 ◽  
...  
Keyword(s):  
Volatile Organic Compounds ◽  
Gas Phase ◽  
Organic Compounds ◽  
Surface Reactions ◽  
Surface Ozone ◽  
Plant Surface ◽  
Double Bonds ◽  
Oxygenated Volatile Organic Compounds ◽  
Volatile Organic ◽  
Ozone Sink

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.

Sign in / Sign up

Export Citation Format

Share Document