Peroxy radical chemistry during ozonolysis experiments of monoterpene mixtures: Field, laboratory and 0-D modelling
Ahmad LahibNina G. ReijrinkHichem BouzidiMarius DuncianuÉmilie PerraudinP.-M. FlaudÉric VillenaveJonathan WilliamsAlexandre TomasSébastien Dusanter
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Monoterpene
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Abstract. The effect of NO2 on secondary organic aerosol (SOA) formation from ozonolysis of α-pinene, β-pinene, Δ3-carene, and limonene was investigated using a dark flow-through reaction chamber. SOA mass yields were calculated for each monoterpene from ozonolysis with varying NO2 concentrations. Kinetics modeling of the first-generation gas-phase chemistry suggests that differences in observed aerosol yields for different NO2 concentrations are consistent with NO3 formation and subsequent competition between O3 and NO3 to oxidize each monoterpene. α-Pinene was the only monoterpene studied that showed a systematic decrease in both aerosol number concentration and mass concentration with increasing [NO2]. β-Pinene and Δ3-carene produced fewer particles at higher [NO2], but both retained moderate mass yields. Limonene exhibited both higher number concentrations and greater mass concentrations at higher [NO2]. SOA from each experiment was collected and analyzed by HPLC-ESI-MS, enabling comparisons between product distributions for each system. In general, the systems influenced by NO3 oxidation contained more high molecular weight products (MW > 400 amu), suggesting the importance of oligomerization mechanisms in NO3-initiated SOA formation. α-Pinene, which showed anomalously low aerosol mass yields in the presence of NO2, showed no increase in these oligomer peaks, suggesting that lack of oligomer formation is a likely cause of α-pinene's near 0 % yields with NO3. Through direct comparisons of mixed-oxidant systems, this work suggests that NO3 is likely to dominate nighttime oxidation pathways in most regions with both biogenic and anthropogenic influences. Therefore, accurately constraining SOA yields from NO3 oxidation, which vary substantially with the volatile organic compound precursor, is essential in predicting nighttime aerosol production.
Monoterpene
Pinene
Oligomer
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Biogenic monoterpenes are major sources of Criegee intermediates (CIs) in the troposphere. Recent studies underscored the importance of their heterogeneous chemistry. The study of monoterpene CI reactions on liquid surfaces, however, is challenging due to the lack of suitable probes. Here, we report the first mass spectrometric detection of the intermediates and products, which include labile hydroperoxides, from reactions of CIs of representative monoterpenes (α-terpinene, γ-terpinene, terpinolene, d-limonene, α-pinene) with water, cis-pinonic acid (CPA) and octanoic acid (OA) on the surface of liquid microjets. Significantly, the relative yields of α-hydroxy-hydroperoxides production from CIs hydration at the gas–liquid interface—α-terpinene (1.00) ≫ d-limonene (0.18) > γ-terpinene (0.11) ∼ terpinolene (0.10) ≫ α-pinene (0.01)—do not track the rate constants of their gas-phase ozonolyses. Notably, in contrast with the inertness of the other CIs, the CIs derived from α-terpinene ozonolysis readily react with CPA and OA to produce C20 and C18 ester hydroperoxides, respectively. Present results reveal hitherto unknown structural effects on the reactivities of CIs at aqueous interfaces.
Monoterpene
Reactivity
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Ozonolysis of oleic acid in methanol, a reacting solvent, with subsequent decomposition of the ozonide products by hydrogen peroxide in formic acid, gives yields of principal dicarboxylic acid fission products exceeding 95% with a minimum of secondary acidic products. The method is highly reproducible and offers unique advantages in the total recovery of the dicarboxylic acids and the elimination of peroxidic materials. The principal non-acidic by-products were tentatively identified as the C s alcohols and their formyl esters.
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Dicarboxylic acid
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This chapter contains sections titled: Introduction Ozonolysis of Olefinic Compounds Ozonolysis of Acetylenes Ozonolysis of Aromatic Compounds Ozonolysis of Heterocycles Ozonolysis of Carbon–Heteroatom Double Bonds Ozonolysis in Synthesis Ozonolysis in Organic Analysis References
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Abstract 1‐Nonanol and alkyl 9‐hydroxynonanoates were more readily prepared by hydrogenation of the respective isolated aldehydes than by direct hydrogenation of products from reductive ozonolysis of oleate esters. Hydrogenation with nickel catalysts and aprotic solvents reduced the isolated aldehydes in good yield with a minimum of side reactions. Although the noble metal catalyst and hydroxylic solvent systems frequently used in similar reductions were also effective, they required a promoter that fortuitously catalyzed hydrolysis of acetals that formed during hydrogenation. Direct hydrogenation of the ozonolysis products resulted in side reactions and a mixture of products difficult to separate.
Noble metal
Catalytic hydrogenation
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Abstract. The effect of NO2 on secondary organic aerosol (SOA) formation from ozonolysis of α-pinene, β-pinene, Δ3-carene, and limonene was investigated using a dark flow-through reaction chamber. SOA mass yields were calculated for each monoterpene from ozonolysis with varying NO2 concentrations. Kinetics modeling of the first generation gas-phase chemistry suggests that differences in observed aerosol yields for different NO2 concentrations are consistent with NO3 formation and subsequent competition between O3 and NO3 to oxidize each monoterpene. α-pinene was the only monoterpene studied that showed a systematic decrease in both aerosol number concentration and mass concentration with increasing [NO2]. β-pinene and Δ3-carene produced fewer particles at higher [NO2], but both retained moderate mass yields. Limonene exhibited both higher number concentrations and greater mass concentrations at higher [NO2]. SOA from each experiment was collected and analyzed by HPLC-ESI-MS, enabling comparisons between product distributions for each system. In general, the systems influenced by NO3 oxidation contained more high molecular weight products (MW >400 amu), suggesting the importance of oligomerization mechanisms in NO3-initiated SOA formation. α-pinene, which showed anomalously low aerosol mass yields in the presence of NO2, showed no increase in these oligomer peaks, suggesting that lack of oligomer formation is a likely cause of α-pinene's near 0% yields with NO3. Through direct comparisons of mixed-oxidant systems, this work suggests that NO3 is likely to dominate nighttime oxidation pathways in most regions with both biogenic and anthropogenic influences. Therefore, accurately constraining SOA yields from NO3 oxidation, which vary substantially with the VOC precursor, is essential in predicting nighttime aerosol production.
Monoterpene
Pinene
Oligomer
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본 연구에서는 2014년 3월부터 11월까지 지리산 심원마을에서 enclosure chamber를 이용하여 소나무 잎과 가지에서 방산되는 monoterpene과 숲 공기 중의 monoterpene의 농도 변화와 물질에 대해서 시계열 분석을 하였다. 소나무 잎과 가지에서 방산되는 주요 monoterpene 물질은 α-pinene, β-myrcene, β-phellandrene, β-pinene으로 나타났다. monoterpene방산량은 6월부터 증가하기 시작하여 8월에 가장 높은 농도를 나타낸 후 감소하는 경향을 나타냈다. 시간별 monoterpene 방산량은 13:00∼14:00, 15:00∼16:00, 09:00∼10:00 순서로 높게 나타냈고 온도가 증가함에 따라 monoterpene의 농도는 증가하였고 특히 20℃ 이상에서 크게 증가하였다. 한편 숲 공기 중에 존재하는 monoterpene의 농도는 3월, 4월 증가해서 5월 최고점을 나타냈고 7월과 11월에 증가하는 경향을 나타냈다. 숲 공기 중 monoterpene의 주요 물질은 α-pinene, β-pinene, camphene으로 잎과 가지에서 방산되는 monoterpene 물질과 차이가 있었다. 소나무 잎과 가지에서 방산되는 monoterpene농도는 13:00∼14:00, 15:00∼16:00 순서로 높게 나타났으며 숲 공기 중에서는 09:00∼10:00에 높았던 농도가 감소하면서 13:00∼14:00 시간에 가장 낮은 농도를 나타냈으며 17:00∼18:00이 가장 높은 농도를 나타냈다.
Monoterpene
Myrcene
Camphene
Pinene
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Monoterpene
Particle (ecology)
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Monoterpene
Terpene
Sulfonic acid
Sulfonyl
Pinene
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Abstract The reaction between olefins and ozone to form aldehydes, ketones, carboxylic acids, etc., is known as the Criegee ozonolysis. This reaction occurs in three steps: formation of primary ozonides, splitting of primary ozonides, and formation of secondary ozonides. The study finds that the electron‐donating groups accelerate the reaction, and the electron‐withdrawing groups decrease the reaction rate. This reaction has application for structure determination as well as synthetic purposes and it is found that the ozonolysis of olefins is one of the major methods of forming aerosol.
Primary (astronomy)
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