Stability of α-Pinene and <scp>d</scp>-Limonene Ozonolysis Secondary Organic Aerosol Compounds Toward Hydrolysis and Hydration

Wong, Cynthia M.; Vite, Daniel; Nizkorodov, Sergey A.

doi:10.1021/acsearthspacechem.1c00171

Cited by 15 publications

(17 citation statements)

References 49 publications

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“…The molecular formulas and most likely identities for these products appear in parentheses. , The five most abundant dimer peaks have monoisotopic molecular masses of 354.204 Da (C 19 H 30 O 6 ), 368.184 Da (C 19 H 28 O 7 ), 338.209 Da (C 19 H 30 O 5 ), 358.163 Da (C 17 H 26 O 8 ), and 370.199 Da (C 19 H 30 O 7 ). These most abundant monomers and dimers have been commonly observed in both lab-generated and ambient SOA samples, confirming that, despite the high mass loadings in the flow tube reactor, our starting SOA material is representative of the typical α-pinene SOA. − …”

Section: Resultssupporting

confidence: 68%

Highly Acidic Conditions Drastically Alter the Chemical Composition and Absorption Coefficient of α-Pinene Secondary Organic Aerosol

Wong

Liu

Nizkorodov

2022

ACS Earth Space Chem.

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Secondary organic aerosols (SOA), formed through the gas-phase oxidation of volatile organic compounds (VOCs), can reside in the atmosphere for many days. The formation of SOA takes place rapidly within hours after VOC emissions, but SOA can undergo much slower physical and chemical processes throughout their lifetime in the atmosphere. The acidity of atmospheric aerosols spans a wide range, with the most acidic particles having negative pH values, which can promote acid-catalyzed reactions. The goal of this work is to elucidate poorly understood mechanisms and rates of acid-catalyzed aging of mixtures of representative SOA compounds. SOA were generated by the ozonolysis of α-pinene in a continuous flow reactor and then collected using a foil substrate. SOA samples were extracted and aged by exposure to varying concentrations of aqueous H 2 SO 4 for 1−2 days. Chemical analysis of fresh and aged samples was conducted using ultra-performance liquid chromatography coupled with photodiode array spectrophotomety and high-resolution mass spectrometry. In addition, UV−vis spectrophotometry and fluorescence spectrophotometry were used to examine the changes in optical properties before and after aging. We observed that SOA that aged in moderately acidic conditions (pH from 0 to 4) experienced small changes in composition, while SOA that aged in a highly acidic environment (pH from −1 to 0) experienced more dramatic changes in composition, including the formation of compounds containing sulfur. Additionally, at highly acidic conditions, light-absorbing and fluorescent compounds appeared, but their identities could not be ascertained due to their small relative abundance. This study shows that acidity is a major driver of SOA aging, resulting in a large change in the chemical composition and optical properties of aerosols in regions where high concentrations of H 2 SO 4 persist, such as upper troposphere and lower stratosphere.

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Section: Resultssupporting

confidence: 68%

Highly Acidic Conditions Drastically Alter the Chemical Composition and Absorption Coefficient of α-Pinene Secondary Organic Aerosol

Wong

Liu

Nizkorodov

2022

ACS Earth Space Chem.

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“…Aerosols are known to play a key role in climate and air quality, with high concentrations leading to adverse health effects (e.g., cardiovascular disease, lung cancers). − Aerosols also cause reduced visibility and haze conditions associated with urban air pollution . α-Pinene, C 10 H 16 , is the most abundant atmospheric monoterpene with an average estimated emission of 66 Tg yr –1 .…”

Section: Introductionmentioning

confidence: 99%

Heterogeneous Reactions of α-Pinene on Mineral Surfaces: Formation of Organonitrates and α-Pinene Oxidation Products

Hettiarachchi

Grassian

2022

J. Phys. Chem. A

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Organonitrates (ON) are important components of secondary organic aerosols (SOAs). α-Pinene (C 10 H 16 ), the most abundant monoterpene in the troposphere, is a precursor for the formation of several of these compounds. ON from α-pinene can be produced in the gas phase via photochemical processes and/or following reactions with oxidizers including hydroxyl radical and ozone. Gas-phase nitrogen oxides (NO 2 , NO 3 ) are N sources for ON formation. Although gas-phase reactions of α-pinene that yield ON are fairly well understood, little is known about their formation through heterogeneous and multiphase pathways. In the current study, surface reactions of α-pinene with nitrogen oxides on hematite (α-Fe 2 O 3 ) and kaolinite (SiO 2 Al 2 O 3 (OH) 4 ) surfaces, common components of mineral dust, have been investigated. α-Pinene oxidizes upon adsorption on kaolinite, forming pinonaldehyde, which then dimerizes on the surface. Furthermore, α-pinene is shown to react with adsorbed nitrate species on these mineral surfaces producing multiple ON and other oxidation products. Additionally, gas-phase oxidation products of α-pinene on mineral surfaces are shown to more strongly adsorb on the surface compared to α-pinene. Overall, this study reveals the complexity of reactions of prevalent organic compounds such as α-pinene with adsorbed nitrate and nitrogen dioxide, revealing new heterogeneous reaction pathways for SOA formation that is mineralogy specific.

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“…A smaller m / z at 467.18 for C 19 H 33 NSO 10 (compound 19 without methanol units clustered) was also observed. The nonsulfated molecule of compound 15 , pinalic-3-acid, ,,− has been widely observed in the environment as well as in laboratory experiments. Similarly, compounds with similar molar weight/formula to compounds 16 , 17 , 18 , and 19 have been previously observed in both laboratory experiments and the field. ,,,,,,,,,− …”

Section: Resultsmentioning

confidence: 99%

Heterogeneous Formation of Organonitrates (ON) and Nitroxy-Organosulfates (NOS) from Adsorbed α-Pinene-Derived Organosulfates (OS) on Mineral Surfaces

Hettiarachchi

Grassian

2022

ACS Earth Space Chem.

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Organonitrates (ON) and nitroxy-organosulfates (NOS) are important components of secondary organic aerosols (SOAs). Gas-phase reactions of α-pinene (C 10 H 16 ), a primary precursor for several ON compounds, are fairly well understood although formation pathways for NOS largely remain unknown. NOS formation may occur via reactions of ON and organic peroxides with sulfates as well as through radical-initiated photochemical processes. Despite the fact that organosulfates (OS) represent a significant portion of the organic aerosol mass, ON and NOS formation from OS is less understood, especially through nighttime heterogeneous and multiphase chemistry pathways. In the current study, surface reactions of adsorbed αpinene-derived OS with nitrogen oxides on hematite and kaolinite surfaces, common components of mineral dust, have been investigated. α-Pinene reacts with sulfated mineral surfaces, forming a range of OS compounds on the surface. These OS compounds when adsorbed on mineral surfaces can further react with HNO 3 and NO 2 , producing several ON and NOS compounds as well as several oxidation products. Overall, this study reveals the complexity of reactions of prevalent organic compounds leading to the formation of OS, ON, and NOS via heterogeneous and multiphase reaction pathways on mineral surfaces. It is also shown that this chemistry is mineralogy-specific.

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Stability of α-Pinene and d-Limonene Ozonolysis Secondary Organic Aerosol Compounds Toward Hydrolysis and Hydration

Cited by 15 publications

References 49 publications

Highly Acidic Conditions Drastically Alter the Chemical Composition and Absorption Coefficient of α-Pinene Secondary Organic Aerosol

Highly Acidic Conditions Drastically Alter the Chemical Composition and Absorption Coefficient of α-Pinene Secondary Organic Aerosol

Heterogeneous Reactions of α-Pinene on Mineral Surfaces: Formation of Organonitrates and α-Pinene Oxidation Products

Heterogeneous Formation of Organonitrates (ON) and Nitroxy-Organosulfates (NOS) from Adsorbed α-Pinene-Derived Organosulfates (OS) on Mineral Surfaces

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