Side-by-Side Comparison of Hydroperoxide and Corresponding Alcohol as Hydrogen-Bond Donors

Møller, Kristian H.; Tram, Camilla Mia; Kjaergaard, Henrik G.

doi:10.1021/acs.jpca.7b01323

Cited by 30 publications

(38 citation statements)

References 76 publications

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“…In these data these VOC mixing ratios are, with the exception of isoprene, not largely temperature dependent, with many of these HOMs forming under negligible or zero insolation and therefore very low OH q concentrations. These nighttime HOMs will not be derived from the oxidation of aromatics, however, as rates of oxidation of alkylbenzenes by O 3 and NO q 3 are negligible (Molteni et al, 2018). These nighttime HOMs will therefore mostly be derived from biogenic emissions which undergo more rapid nocturnal oxidation and are likely transported from inland by the land breeze during night (Millán, 2014;Querol et al, 2017).…”

Section: Hom Composition and Sourcesmentioning

confidence: 99%

“…Operating under the assumption that C 5 , C 6 , C 7 , C 8 , and C 9 HOMs primarily arise from isoprene, benzene toluene, and C 2 -alkylbenzene and C 3 -alkylbenzene oxidation respectively (Massoli et al, 2018;Molteni et al, 2018;Wang et al, 2017), HOM signals plotted against the parent VOC concentration indicate their dependence upon that VOC. Here, a C 7 HOM is thought to follow the formula C 7 H 8-12 O 5-10 N 0-2 .…”

Section: Hom Composition and Sourcesmentioning

confidence: 99%

“…LVOCs and ELVOCs (3 × 10 −5 < C * < 0.3 µg m −3 and 3 × 10 −9 < C * (300 K) < 3 × 10 −5 µg m −3 respectively) have a greater contribution from molecules with higher DBE, i.e. C 10 H 10 O 8 arising most likely from PAH oxidation (Molteni et al, 2018) and C 10 H 15 O 7 N, a common molecule arising from monoterpene oxidation in the presence of NO x . The contribution of molecules with carbon number ≤ 9 to these LVOCs is modest, and ELVOCs are entirely comprised of molecules with carbon numbers ≥ 10 and are dominated by DBEs of 8 and 4, attributable to PAH and monoterpene oxidation respectively.…”

Section: Hom Composition and Sourcesmentioning

confidence: 99%

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Molecular insights into new particle formation in Barcelona, Spain

et al. 2020

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Abstract. Atmospheric aerosols contribute some of the greatest uncertainties to estimates of global radiative forcing and have significant effects on human health. New particle formation (NPF) is the process by which new aerosols of sub-2 nm diameter form from gas-phase precursors and contributes significantly to particle numbers in the atmosphere, accounting for approximately 50 % of cloud condensation nuclei globally. Here, we study summertime NPF in urban Barcelona in north-eastern Spain utilising particle counting instruments down to 1.9 nm and a Nitrate Chemical Ionisation Atmospheric Pressure interface Time of Flight Mass Spectrometer (CI-APi-ToF). The rate of formation of new particles is seen to increase linearly with sulfuric acid concentration, although particle formation rates fall short of chamber studies of H2SO4–DMA–H2O while exceeding those of H2SO4–BioOxOrg–H2O nucleation, although a role of highly oxygenated molecules (HOMs) cannot be ruled out. The sulfuric acid dimer : monomer ratio is significantly lower than that seen in experiments involving sulfuric acid and dimethylamine (DMA) in chambers, indicating that stabilisation of sulfuric acid clusters by bases is weaker in this dataset than in chambers, either due to rapid evaporation due to high summertime temperatures or limited pools of stabilising amines. Such a mechanism cannot be verified in these data, as no higher-order H2SO4–amine clusters nor H2SO4–HOM clusters were measured. The high concentrations of HOMs arise from isoprene, alkylbenzene, monoterpene and polycyclic aromatic hydrocarbon (PAH) oxidation, with alkylbenzenes providing greater concentrations of HOMs due to significant local sources. The concentration of these HOMs shows a dependence on temperature. The organic compounds measured primarily fall into the semivolatile organic compound (SVOC) volatility class arising from alkylbenzene and isoprene oxidation. Low-volatility organic compounds (LVOCs) largely arise from oxidation of alkylbenzenes, PAHs and monoterpenes, whereas extremely low-volatility organic compounds (ELVOCs) arise from primarily PAH and monoterpene oxidation. New particle formation without growth past 10 nm is also observed, and on these days oxygenated organic concentrations are lower than on days with growth by a factor of 1.6, and thus high concentrations of low-volatility oxygenated organics which primarily derive from traffic-emitted volatile organic compounds (VOCs) appear to be a necessary condition for the growth of newly formed particles in Barcelona. These results are consistent with prior observations of new particle formation from sulfuric acid–amine reactions in both chambers and the real atmosphere and are likely representative of the urban background of many European Mediterranean cities. A role for HOMs in the nucleation process cannot be confirmed or ruled out, and there is strong circumstantial evidence of the participation of HOMs across multiple volatility classes in particle growth.

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Section: Hom Composition and Sourcesmentioning

confidence: 99%

Section: Hom Composition and Sourcesmentioning

confidence: 99%

Section: Hom Composition and Sourcesmentioning

confidence: 99%

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Molecular insights into new particle formation in Barcelona, Spain

et al. 2020

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“…The ionization system charges molecules by adduct formation, such as in the case of organic compounds with two or more hydrogen bond donor groups (Hyttinen et al, 2015), or proton transfer in the case of strong acids like sulfuric acid. Hydroxyl or hydroperoxyl functionalities are both common hydrogen-bond-donating groups, with hydroperoxyl being the more efficient hydrogen bond donor (Møller et al, 2017). This instrument has been explained in great detail elsewhere (Junninen et al, 2010;Jokinen et al, 2012), but briefly the front end consists of a chemical ionization system where a 10 L min −1 sample flow is drawn in through the 1 m long 1 in.…”

Section: Chemical Ionizationmentioning

confidence: 99%

Observations of highly oxidized molecules and particle nucleation in the atmosphere of Beijing

et al. 2019

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Abstract. Particle nucleation is one of the main sources of atmospheric particulate matter by number, with new particles having great relevance for human health and climate. Highly oxidized multifunctional organic molecules (HOMs) have been recently identified as key constituents in the growth and, sometimes, in initial formation of new particles. While there have been many studies of HOMs in atmospheric chambers, flow tubes, and clean environments, analyses of data from polluted environments are scarce. Here, measurements of HOMs and particle size distributions down to small molecular clusters are presented alongside volatile organic compounds (VOCs) and trace-gas data from a campaign in June 2017, in Beijing. Many gas-phase HOMs have been characterized and their temporal trends and behaviours analysed in the context of new particle formation. The HOMs identified have a degree of oxidation comparable to that seen in other, cleaner, environments, likely due to an interplay between the higher temperatures facilitating rapid hydrogen abstractions and the higher concentrations of NOx and other RO2⚫ terminators ending the autoxidation sequence more rapidly. Our data indicate that alkylbenzenes, monoterpenes, and isoprene are important precursor VOCs for HOMs in Beijing. Many of the C5 and C10 compounds derived from isoprene and monoterpenes have a slightly greater degree of average oxidation state of carbon compared to those from other precursors. Most HOMs except for large dimers have daytime peak concentrations, indicating the importance of OH⚫ chemistry in the formation of HOMs, as O3 tends to be lower on days with higher HOM concentrations; similarly, VOC concentrations are lower on the days with higher HOM concentrations. The daytime peaks of HOMs coincide with the growth of freshly formed new particles, and their initial formation coincides with the peak in sulfuric acid vapours, suggesting that the nucleation process is sulfuric-acid-dependent, with HOMs contributing to subsequent particle growth.

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“…Hydroxyl or hydroperoxyl functionalities are both common hydrogen bond donating groups, with hydroperoxyl being the more efficient hydrogen bond donor (Møller et al, 2017). This instrument has been explained in great detail elsewhere (Jokinen et al, 2012;Junninen et al, 2010), but briefly, the front end consists of a chemical ionisation system where a 10 L min -1 sample flow is drawn in through the 1 m length 1" OD stainless steel tubing opening.…”

Section: Spectrometrymentioning

confidence: 99%

Molecular Insights into New Particle Formation in Barcelona, Spain

Brean¹,

Beddows²,

Shi³

et al. 2020

Preprint

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Abstract. Atmospheric aerosols contribute some of the greatest uncertainties to estimates of global radiative forcing, and have significant effects on human health. New particle formation (NPF) is the process by which new aerosols of sub-2 nm diameter form from gas-phase precursors and contributes significantly to particle numbers in the atmosphere, accounting for approximately 50 % of cloud condensation nuclei globally. Here, we study summertime NPF in urban Barcelona in NE Spain. The rate of formation of new particles is seen to increase linearly with sulphuric acid concentration in a manner similar to systems studied in chamber studies involving sulphuric acid, water and dimethylamine (DMA), as well as sulphuric acid, water and the oxidation products of pinanediol. The sulphuric acid dimer : monomer ratio is significantly lower than that seen in experiments involving sulphuric acid and DMA in chambers, indicating that stabilization of sulphuric acid clusters by bases is weaker in this dataset than in chambers, and thus another mechanism, likely involving the plentiful highly oxygenated organic molecules (HOMs) is plausible. The high concentrations of HOMs arise largely from both alkylbenzene and monoterpene oxidation, with the former providing greater concentrations of HOMs due to significant local sources. The concentration of these HOMs shows a dependence on both temperature and precursor VOC concentration. New particle formation without growth past 10 nm is also observed, and on these days the highly oxygenated organic compound concentration is significantly lower than on days with growth, and thus high concentrations of low volatility oxygenated organics appear to be a necessary condition for the growth of newly formed particles in Barcelona. These results are consistent with prior observations of new particle formation in both chambers and the real atmosphere, and these results are likely representative of the urban background of many European Mediterranean cities.

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Side-by-Side Comparison of Hydroperoxide and Corresponding Alcohol as Hydrogen-Bond Donors

Cited by 30 publications

References 76 publications

Molecular insights into new particle formation in Barcelona, Spain

Molecular insights into new particle formation in Barcelona, Spain

Observations of highly oxidized molecules and particle nucleation in the atmosphere of Beijing

Molecular Insights into New Particle Formation in Barcelona, Spain

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