A Chamber Study of Secondary Organic Aerosol (SOA) Formed by Ozonolysis of d-Limonene in the Presence of NO

Chen, Fei; Zhou, Hao; Gao, Jixi; Hopke, Philip K.

doi:10.4209/aaqr.2016.01.0029

Cited by 15 publications

(6 citation statements)

References 51 publications

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“…SOA data (see Table S1) were compiled from 12 published chamber studies (e.g., Chen et al, 2017;Griffin et al, 1999;Kim and Paulson, 2013;Kourtchev et al, 2014;Ng et al, 2007;Yu et al, 1999) in which α-pinene or limonene was used as a precursor and final SOA mass, SOA yield, and reacted hydrocarbon concentration (HC) were reported (at least two of the three quantities). For the α-pinene photooxidation data, there is an apparent cluster around an SOA yield of 0.2 for SOA mass < 150 µg m -3 with which the model agrees (Fig.…”

Section: Model-measurement Comparisonmentioning

confidence: 99%

Using GECKO-A to derive mechanistic understanding of SOA formation from the ubiquitous but understudied camphene

Afreh

Aumont

Camredon

et al. 2020

Preprint

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Abstract. Camphene, a dominant monoterpene emitted from both biogenic and pyrogenic sources, has been significantly understudied, particularly in regard to secondary organic aerosol (SOA) formation. When camphene represents a significant fraction of emissions, the lack of model parameterizations for camphene can result in inadequate representation of gas-phase chemistry and underprediction of SOA formation. In this work, the first mechanistic study of SOA formation from camphene was performed using the Generator for Explicit Chemistry and Kinetics of Organics in the Atmosphere (GECKO-A). GECKO-A was used to generate gas-phase chemical mechanisms for camphene and two well-studied monoterpenes, α-pinene and limonene; and to predict SOA mass formation and composition based on gas/particle partitioning theory. The model simulations represented observed trends in published gas-phase reaction pathways and SOA yields well under chamber-relevant photooxidation and dark ozonolysis conditions. For photooxidation conditions, 70 % of the simulated α-pinene oxidation products remained in the gas phase compared to 50 % for limonene; supporting model predictions and observations of limonene having higher SOA yields than α-pinene under equivalent conditions. The top 10 simulated particle-phase products in the α-pinene and limonene simulations represented 37–50 % of the SOA mass formed and 6–27 % of the hydrocarbon mass reacted. To facilitate comparison of camphene with α-pinene and limonene, model simulations were run under idealized atmospheric conditions, wherein the gas-phase oxidant levels were controlled. Metrics for comparison included: gas-phase reactivity profiles, time-evolution of SOA mass and yields, and physicochemical property distributions of gas- and particle-phase products. The controlled-reactivity simulations demonstrated that: (1) in the early stages of oxidation, camphene is predicted to form very low volatility products, lower than α-pinene and limonene, which condense at low mass loadings; and (2) the final simulated SOA yield for camphene (46 %) was relatively high, in between α-pinene (25 %) and limonene (74 %). A 50 / 50 (α-pinene / limonene) mixture was then used as a surrogate to represent SOA formation from camphene; while simulated SOA mass and yield were well represented, the volatility distribution of the particle-phase products was not. To demonstrate the potential importance of including a parameterized representation of SOA formation by camphene in air quality models, SOA mass and yield were predicted for three wildland fire fuels based on measured monoterpene distributions, and published SOA parameterizations for α-pinene and limonene. Using the 50 / 50 surrogate mixture to represent camphene increased predicted SOA mass by 43–50 % for black spruce and by 56–108 % for Douglas fir. This first detailed modeling study of the gas-phase oxidation of camphene and subsequent SOA formation provides an opportunity for future measurement-model comparisons and lays the foundation for developing chemical mechanism and SOA parameterizations for camphene that are suitable for air quality modeling.

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Section: Model-measurement Comparisonmentioning

confidence: 99%

Using GECKO-A to derive mechanistic understanding of SOA formation from the ubiquitous but understudied camphene

Afreh

Aumont

Camredon

et al. 2020

Preprint

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show abstract

“…Chen and Hopke (2010) and Chen et al (2011Chen et al ( , 2017 studied ROS formation from the ozonolysis of limonene using a similar chemical assay with an offline filter sampling and sonication and filter extraction method. Like the current study, both short-lived and long-lived ROS are reported.…”

Section: Comparison To Other Studies Of Ros Formation In Soamentioning

confidence: 99%

Multiphase composition changes and reactive oxygen species formation during limonene oxidation in the new Cambridge Atmospheric Simulation Chamber (CASC)

et al. 2017

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Abstract. The chemical composition of organic aerosols influences their impacts on human health and the climate system. Aerosol formation from gas-to-particle conversion and in-particle reaction was studied for the oxidation of limonene in a new facility, the Cambridge Atmospheric Simulation Chamber (CASC). Health-relevant oxidising organic species produced during secondary organic aerosol (SOA) formation were quantified in real time using an Online Particlebound Reactive Oxygen Species Instrument (OPROSI). Two categories of reactive oxygen species (ROS) were identified based on time series analysis: a short-lived component produced during precursor ozonolysis with a lifetime of the order of minutes, and a stable component that was longlived on the experiment timescale ( ∼ 4 h). Individual organic species were monitored continuously over this time using Extractive Electrospray Ionisation (EESI) Mass Spectrometry (MS) for the particle phase and Proton Transfer Reaction (PTR) MS for the gas phase. Many first-generation oxidation products are unsaturated, and we observed multiphase aging via further ozonolysis reactions. Volatile products such as C 9 H 14 O (limonaketone) and C 10 H 16 O 2 (limonaldehyde) were observed in the gas phase early in the experiment, before reacting again with ozone. Loss of C 10 H 16 O 4 (7-hydroxy limononic acid) from the particle phase was surprisingly slow. A combination of reduced C=C reactivity and viscous particle formation (relative to other SOA systems) may explain this, and both scenarios were tested in the Pretty Good Aerosol Model (PG-AM). A range of characterisation measurements were also carried out to benchmark the chamber against existing facilities. This work demonstrates the utility of CASC, particularly for understanding the reactivity and health-relevant properties of organic aerosols using novel, highly time-resolved techniques.

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“…Nitrogen oxides (NO x ) emitted from automobile and coal-fired power plant cause a variety of environmental problems, such as acid rain, photochemical smog, secondary organic aerosols and ozone depletion (Chen et al, 2017;Huang et al, 2017). To reduce air pollution resulted from NO x , advances in NO x removal technology have drawn much attention and been quite rapid.…”

Section: Introductionmentioning

confidence: 99%

NO Adsorption and Oxidation on Mn Doped CeO2 (111) Surfaces: A DFT+U Study

Liu¹,

Zheng²,

Wang³

et al. 2018

Aerosol Air Qual. Res.

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The adsorption of NO molecules on Mn-doped CeO 2 (111) surfaces for NO oxidation has been studied by employing the periodic density functional theory plus U (DFT+U) method. Through our calculations, it is demonstrated how Mn-doped CeO 2 with superior NO oxidation activity benefits from the high mobility of the oxygen near the Mn cations. On unreduced Mn-doped CeO 2 (111) surfaces, the NO molecule preferentially interacted with the first neighboring O of the Mn cation, with the N also bonding to an Mn cation (E ads = -3.30 eV) or Ce cation (E ads = -2.90 eV). When NO adsorbs on the surface of defective Mn-doped CeO 2 with O 2 adsorbed in advance, an ONOO* four atoms species is formed on the surface (E ads = -2.51 eV and -2.02 eV), which is an intermediate and can decompose into NO 2 , NO 2 * and O*. The adsorption structure with higher adsorption energy has a closer geometry to NO 2 , indicating a deeper oxidation of NO. The calculation results indicate that the presence of Mn only has a strong effect on the nearby oxygen atoms and that the Mndoped CeO 2 surface has similar properties to a noble metal in NO oxidation catalysis. In DOS plots, the spin of the electron state of the adsorption structures involving the oxidation of NO is symmetric, indicating that electron transfer occurs from the slab to NO and strong covalent bonds are formed between N and O on the slab, which can also be confirmed by the charge density difference plots.

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A Chamber Study of Secondary Organic Aerosol (SOA) Formed by Ozonolysis of d-Limonene in the Presence of NO

Cited by 15 publications

References 51 publications

Using GECKO-A to derive mechanistic understanding of SOA formation from the ubiquitous but understudied camphene

Using GECKO-A to derive mechanistic understanding of SOA formation from the ubiquitous but understudied camphene

Multiphase composition changes and reactive oxygen species formation during limonene oxidation in the new Cambridge Atmospheric Simulation Chamber (CASC)

NO Adsorption and Oxidation on Mn Doped CeO2 (111) Surfaces: A DFT+U Study

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