Kinetics and Mechanisms of the Tropospheric Reactions of Menthol, Borneol, Fenchol, Camphor, and Fenchone with Hydroxyl Radicals (OH) and Chlorine Atoms (Cl)

Ceacero-Vega, Antonio A.; Ballesteros, Bernabé; Bejan, Iustinian; Barnes, Ian; Jiménez, Elena; Albaladejo, José

doi:10.1021/jp212076g

Cited by 26 publications

(14 citation statements)

References 63 publications

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“…Both natural and anthropogenic sources emit fenchone to the troposphere, where it is removed mainly through reactions with OH radicals. 10 Structurally, fenchone is a substituted norbornane with a ketone functional group and three additional methyl groups. Although several monoterpenoids have been investigated by rotational spectroscopy, such as carvone, 11 limonene, 11 thymol, 12 menthone, 13 linalool, 14 and others, 15 there is much less information on monoterpenoids derived from norbornane with a [2.2.1] bicyclic structure.…”

Section: Introductionmentioning

confidence: 99%

Structure of fenchone by broadband rotational spectroscopy

Loru

Bermúdez

Sanz

2016

The Journal of Chemical Physics

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The bicyclic terpenoid fenchone (C10H16O, 1,3,3-trimethylbicyclo[2.2.1]heptan-2-one) has been investigated by chirped pulse Fourier transform microwave spectroscopy in the 2-8 GHz frequency region. The parent species and all heavy atom isotopologues have been observed in their natural abundance. The experimental rotational constants of all isotopic species observed have been determined and used to obtain the substitution (rs) and effective (r0) structures of fenchone. Calculations at the B3LYP, M06-2X, and MP2 levels of theory with different basis sets were carried out to check their performance against experimental results. The structure of fenchone has been compared with those of norbornane (bicyclo[2.2.1]heptane) and the norbornane derivatives camphor (1,7,7-trimethylbicyclo[2.2.1]heptan-2-one) and camphene (3,3-dimethyl-2-methylenebicyclo[2.2.1]heptane), both with substituents at C2. The structure of fenchone is remarkably similar to those of camphor and camphene. Comparison with camphor allows identification of changes in ∠CCC angles due to the different position of the methyl groups. All norbornane derivatives display similar structural changes with respect to norbornane. These changes mainly affect the bond lengths and angles of the six-membered rings, indicating that the substituent at C2 drives structural adjustments to minimise ring strain after its introduction.

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Section: Introductionmentioning

confidence: 99%

Structure of fenchone by broadband rotational spectroscopy

Loru

Bermúdez

Sanz

2016

The Journal of Chemical Physics

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“…To estimate the lifetime associated with wet deposition, Eq. (6) proposed by (Chen et al, 2003) was used:…”

Section: Atmospheric Implicationsmentioning

confidence: 99%

Atmospheric fate of a series of saturated alcohols: kinetic and mechanistic study

et al. 2020

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Abstract. The atmospheric fate of a series of saturated alcohols (SAs) was evaluated through kinetic and reaction product studies with the main atmospheric oxidants. These SAs are alcohols that could be used as fuel additives. Rate coefficients (in cm3 molecule−1 s−1) measured at ∼298 K and atmospheric pressure (720±20 Torr) were as follows: k1 ((E)-4-methylcyclohexanol + Cl) = (3.70±0.16) ×10-10, k2 ((E)-4-methylcyclohexanol + OH) = (1.87±0.14) ×10-11, k3 ((E)-4-methylcyclohexanol + NO3) = (2.69±0.37) ×10-15, k4 (3,3-dimethyl-1-butanol + Cl) = (2.69±0.16) ×10-10, k5 (3,3-dimethyl-1-butanol + OH) = (5.33±0.16) ×10-12, k6 (3,3-dimethyl-2-butanol + Cl) = (1.21±0.07) ×10-10, and k7 (3,3-dimethyl-2-butanol + OH) = (10.50±0.25) ×10-12. The main products detected in the reaction of SAs with Cl atoms (in the absence/presence of NOx), OH radicals, and NO3 radicals were (E)-4-methylcyclohexanone for the reactions of (E)-4-methylcyclohexanol, 3,3-dimethylbutanal for the reactions of 3,3-dimethyl-1-butanol, and 3,3-dimethyl-2-butanone for the reactions of 3,3-dimethyl-2-butanol. Other products such as formaldehyde, 2,2-dimethylpropanal, and acetone have also been identified in the reactions of Cl atoms and OH radicals with 3,3-dimethyl-1-butanol and 3,3-dimethyl-2-butanol. In addition, the molar yields of the reaction products were estimated. The products detected indicate a hydrogen atom abstraction mechanism at different sites on the carbon chain of alcohol in the case of Cl reactions and a predominant site in the case of OH and NO3 reactions, confirming the predictions of structure–activity relationship (SAR) methods. Tropospheric lifetimes (τ) of these SAs have been calculated using the experimental rate coefficients. Lifetimes are in the range of 0.6–2 d for OH reactions, 7–13 d for NO3 radical reactions, and 1–3 months for Cl atoms. In coastal areas, the lifetime due to the reaction with Cl decreases to hours. The calculated global tropospheric lifetimes, and the polyfunctional compounds detected as reaction products in this work, imply that SAs could contribute to the formation of ozone and nitrated compounds at local, regional, and even global scales. Therefore, the use of saturated alcohols as additives in diesel blends should be considered with caution.

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“…VOCs from biogenic emission sources (BVOCs) are estimated to contribute 75 %-90 % of the total VOCs (Guenther et al, 1995;Lamarque et al, 2010, Carlton et al, 2009Claeys et al, 2004). BVOC oxidation by reaction with ozone, hydroxyl radical or nitrate radical has been estimated to contribute up to 50 % of SOA worldwide (Chung and Seinfeld, 2002;Hoffmann et al, 1997) with implications for air quality, climate and human health (Chung and Seinfeld, 2002;Fiore et al, 2012;Forster et al, 2007;Lohmann and Feichter, 2005).…”

Section: Introductionmentioning

confidence: 99%

Oligomer and highly oxygenated organic molecule formation from oxidation of oxygenated monoterpenes emitted by California sage plants

et al. 2020

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Abstract. Plants emit a diverse range of biogenic volatile organic compounds (BVOCs) whose oxidation leads to secondary organic aerosol (SOA) formation. The majority of studies of biogenic SOA have focused on single or simple multicomponent BVOC mixtures thought to be representative of Northern hemispheric deciduous or mixed forest conditions. Gaps remain in our understanding of SOA formation from complex mixtures of real plant emissions in other environments. Towards the goal of understanding SOA in other regions, we conducted the first comprehensive study of SOA from oxygenated monoterpenes. These are the dominant emissions from the most common plant species in southern California's coastal sage ecosystem: black sage (Salvia mellifera) and California sagebrush (Artemisia californica). Emissions from sage plants, as well as single compounds representing their major emissions (camphor, camphene and eucalyptol), were oxidised in an Aerodyne potential aerosol mass oxidation flow reactor (PAM-OFR). The chemical composition of SOA was characterised using a high-resolution time-of-flight iodide-anion chemical-ionisation mass spectrometer equipped with a Filter Inlet for Gases and AEROsols (FIGAERO-I-HR-ToF-CIMS) under low- and medium-NOx conditions. SOA from oxygenated monoterpenes showed a higher-order oligomer content and a greater presence of highly oxygenated organic molecules (HOMs) than non-oxygenated monoterpenes, with HOM contributing 27 %–47 % and 12 %–14 % of SOA product signal from oxygenated and non-oxygenated monoterpenes respectively. This study highlights the potential importance of oxygenated monoterpene emissions for SOA formation in woody shrub ecosystems.

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Kinetics and Mechanisms of the Tropospheric Reactions of Menthol, Borneol, Fenchol, Camphor, and Fenchone with Hydroxyl Radicals (OH) and Chlorine Atoms (Cl)

Cited by 26 publications

References 63 publications

Structure of fenchone by broadband rotational spectroscopy

Structure of fenchone by broadband rotational spectroscopy

Atmospheric fate of a series of saturated alcohols: kinetic and mechanistic study

Oligomer and highly oxygenated organic molecule formation from oxidation of oxygenated monoterpenes emitted by California sage plants

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