Influence of aerosol acidity on the chemical composition of Secondary Organic Aerosol from β-caryophyllene

Abstract. The secondary organic aerosol (SOA) yield of β-caryophyllene photooxidation is enhanced by aerosol acidity. In the present study, the influence of aerosol acidity on the chemical composition of β-caryophyllene SOA is investigated using ultra performance liquid chromatography/electrospray ionization-time-of-flight mass spectrometry (UPLC/ESI-TOFMS). A number of first-, second- and higher-generation gas-phase products having carbonyl and carboxylic acid functional groups are detected in the particle phase. Particle-phase reaction products formed via hydration and organosulfate formation processes are also detected. Increase of acidity leads to different effects on the abundance of individual products; significantly, abundances of organosulfates are correlated with aerosol acidity. To our knowledge, this is the first detection of organosulfates and nitrated organosulfates derived from a sesquiterpene. The increase of certain particle-phase reaction products with increased acidity provides chemical evidence to support the acid-enhanced SOA yields. Based on the agreement between the chromatographic retention times and accurate mass measurements of chamber and field samples, three β-caryophyllene products (i.e., β-nocaryophyllon aldehyde, β-hydroxynocaryophyllon aldehyde, and β-dihydroxynocaryophyllon aldehyde) are identified as chemical tracers for β-caryophyllene SOA. These compounds are detected in both day and night ambient samples collected in downtown Atlanta, GA and rural Yorkville, GA during the 2008 August Mini-Intensive Gas and Aerosol Study (AMIGAS).

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Influence of aerosol acidity on the chemical composition of secondary organic aerosol from β-caryophyllene

Atmospheric Chemistry and Physics ◽

10.5194/acp-11-1735-2011 ◽

2011 ◽

Vol 11 (4) ◽

pp. 1735-1751 ◽

Cited By ~ 93

Author(s):

M. N. Chan ◽

J. D. Surratt ◽

A. W. H. Chan ◽

K. Schilling ◽

J. H. Offenberg ◽

...

Keyword(s):

Chemical Composition ◽

Secondary Organic Aerosol ◽

Phase Particle ◽

Organic Aerosol ◽

Chromatographic Retention ◽

Phase Reaction ◽

Particle Phase ◽

Reaction Products ◽

Aerosol Acidity ◽

Field Samples

Abstract. The secondary organic aerosol (SOA) yield of β-caryophyllene photooxidation is enhanced by aerosol acidity. In the present study, the influence of aerosol acidity on the chemical composition of β-caryophyllene SOA is investigated using ultra performance liquid chromatography/electrospray ionization-time-of-flight mass spectrometry (UPLC/ESI-TOFMS). A number of first-, second- and higher-generation gas-phase products having carbonyl and carboxylic acid functional groups are detected in the particle phase. Particle-phase reaction products formed via hydration and organosulfate formation processes are also detected. Increased acidity leads to different effects on the abundance of individual products; significantly, abundances of organosulfates are correlated with aerosol acidity. To our knowledge, this is the first detection of organosulfates and nitrated organosulfates derived from a sesquiterpene. The increase of certain particle-phase reaction products with increased acidity provides chemical evidence to support the acid-enhanced SOA yields. Based on the agreement between the chromatographic retention times and accurate mass measurements of chamber and field samples, three β-caryophyllene products (i.e., β-nocaryophyllon aldehyde, β-hydroxynocaryophyllon aldehyde, and β-dihydroxynocaryophyllon aldehyde) are suggested as chemical tracers for β-caryophyllene SOA. These compounds are detected in both day and night ambient samples collected in downtown Atlanta, GA and rural Yorkville, GA during the 2008 August Mini-Intensive Gas and Aerosol Study (AMIGAS).

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Examining the effects of anthropogenic emissions on isoprene-derived secondary organic aerosol formation during the 2013 Southern Oxidant and Aerosol Study (SOAS) at the Look Rock, Tennessee ground site

Atmospheric Chemistry and Physics ◽

10.5194/acp-15-8871-2015 ◽

2015 ◽

Vol 15 (15) ◽

pp. 8871-8888 ◽

Cited By ~ 128

Author(s):

S. H. Budisulistiorini ◽

X. Li ◽

S. T. Bairai ◽

J. Renfro ◽

Y. Liu ◽

...

Keyword(s):

Mass Spectrometry ◽

Secondary Organic Aerosol ◽

Organic Aerosol ◽

Anthropogenic Emissions ◽

Strongly Correlated ◽

Particle Phase ◽

Aerosol Formation ◽

Aerosol Acidity ◽

Southeastern Us

Abstract. A suite of offline and real-time gas- and particle-phase measurements was deployed at Look Rock, Tennessee (TN), during the 2013 Southern Oxidant and Aerosol Study (SOAS) to examine the effects of anthropogenic emissions on isoprene-derived secondary organic aerosol (SOA) formation. High- and low-time-resolution PM2.5 samples were collected for analysis of known tracer compounds in isoprene-derived SOA by gas chromatography/electron ionization-mass spectrometry (GC/EI-MS) and ultra performance liquid chromatography/diode array detection-electrospray ionization-high-resolution quadrupole time-of-flight mass spectrometry (UPLC/DAD-ESI-HR-QTOFMS). Source apportionment of the organic aerosol (OA) was determined by positive matrix factorization (PMF) analysis of mass spectrometric data acquired on an Aerodyne Aerosol Chemical Speciation Monitor (ACSM). Campaign average mass concentrations of the sum of quantified isoprene-derived SOA tracers contributed to ~ 9 % (up to 28 %) of the total OA mass, with isoprene-epoxydiol (IEPOX) chemistry accounting for ~ 97 % of the quantified tracers. PMF analysis resolved a factor with a profile similar to the IEPOX-OA factor resolved in an Atlanta study and was therefore designated IEPOX-OA. This factor was strongly correlated (r2 > 0.7) with 2-methyltetrols, C5-alkene triols, IEPOX-derived organosulfates, and dimers of organosulfates, confirming the role of IEPOX chemistry as the source. On average, IEPOX-derived SOA tracer mass was ~ 26 % (up to 49 %) of the IEPOX-OA factor mass, which accounted for 32 % of the total OA. A low-volatility oxygenated organic aerosol (LV-OOA) and an oxidized factor with a profile similar to 91Fac observed in areas where emissions are biogenic-dominated were also resolved by PMF analysis, whereas no primary organic aerosol (POA) sources could be resolved. These findings were consistent with low levels of primary pollutants, such as nitric oxide (NO ~ 0.03 ppb), carbon monoxide (CO ~ 116 ppb), and black carbon (BC ~ 0.2 μg m−3). Particle-phase sulfate is fairly correlated (r2 ~ 0.3) with both methacrylic acid epoxide (MAE)/hydroxymethyl-methyl-α-lactone (HMML)- (henceforth called methacrolein (MACR)-derived SOA tracers) and IEPOX-derived SOA tracers, and more strongly correlated (r2 ~ 0.6) with the IEPOX-OA factor, in sum suggesting an important role of sulfate in isoprene SOA formation. Moderate correlation between the MACR-derived SOA tracer 2-methylglyceric acid with sum of reactive and reservoir nitrogen oxides (NOy; r2 = 0.38) and nitrate (r2 = 0.45) indicates the potential influence of anthropogenic emissions through long-range transport. Despite the lack of a clear association of IEPOX-OA with locally estimated aerosol acidity and liquid water content (LWC), box model calculations of IEPOX uptake using the simpleGAMMA model, accounting for the role of acidity and aerosol water, predicted the abundance of the IEPOX-derived SOA tracers 2-methyltetrols and the corresponding sulfates with good accuracy (r2 ~ 0.5 and ~ 0.7, respectively). The modeling and data combined suggest an anthropogenic influence on isoprene-derived SOA formation through acid-catalyzed heterogeneous chemistry of IEPOX in the southeastern US. However, it appears that this process was not limited by aerosol acidity or LWC at Look Rock during SOAS. Future studies should further explore the extent to which acidity and LWC as well as aerosol viscosity and morphology becomes a limiting factor of IEPOX-derived SOA, and their modulation by anthropogenic emissions.

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Particle Size Dependence of Biogenic Secondary Organic Aerosol Molecular Composition

10.5194/acp-2017-53 ◽

2017 ◽

Cited By ~ 1

Author(s):

Peijun Tu ◽

Murray V. Johnston

Keyword(s):

Particle Size ◽

Secondary Organic Aerosol ◽

Volume Ratio ◽

Organic Aerosol ◽

Phase Reaction ◽

Particle Phase ◽

Relative Signal Intensity ◽

Volatile Products ◽

Phase Chemistry ◽

Limited Process

Abstract. Formation of secondary organic aerosol (SOA) is initiated by the oxidation of volatile organic compounds (VOCs) in the gas phase. Mass transfer to the particle phase is thought to occur primarily by a combination of condensation of non-volatile products and partitioning of semi-volatile products, though particle phase chemistry may also play a role if it transforms semi-volatile reactants into non-volatile products. In principle, changes in particle composition as a function of particle size allow the relative contributions of e.g. condensation (a surface-limited process) and particle phase reaction (a volume-limited process) to be distinguished. In this work, SOA was produced by β-pinene ozonolysis in a flow tube reactor. Aerosol exiting the reactor was size-selected with a differential mobility analyser, and individual particle sizes between 35 and 110 nm in diameter were characterized by on- and off- line mass spectrometry. Both the average oxygen-to-carbon (O / C) ratio and carbon oxidation state (OSc) were found to decrease with increasing particle size, while the relative signal intensity of oligomers increased with increasing particle size. These results are consistent with oligomer formation in the particle phase i.e. accretion reactions, which become more favoured as the surface-to-volume ratio of the particle decreases. Analysis of a series of polydisperse SOA samples showed similar dependencies: as the mass loading increased (and average surface-to-volume ratio decreased), the average O / C ratio and OSc decreased while the relative intensity of oligomer ions increased. The results illustrate the potential impact that particle phase chemistry can have on biogenic SOA formation and the particle size range where this chemistry becomes important.

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Chemical aging of <i>m</i>-xylene secondary organic aerosol: laboratory chamber study

Atmospheric Chemistry and Physics Discussions ◽

10.5194/acpd-11-24969-2011 ◽

2011 ◽

Vol 11 (9) ◽

pp. 24969-25010 ◽

Cited By ~ 4

Author(s):

C. L. Loza ◽

P. S. Chhabra ◽

L. D. Yee ◽

J. S. Craven ◽

R. C. Flagan ◽

...

Keyword(s):

Gas Phase ◽

Secondary Organic Aerosol ◽

Organic Aerosol ◽

Chemical Mechanism ◽

Ionization Mass ◽

Phase Reaction ◽

Particle Phase ◽

Chemical Aging ◽

Volatile Products ◽

Fragmentation Chemistry

Abstract. Secondary organic aerosol (SOA) can reside in the atmosphere for a week or more. While its initial formation from the gas-phase oxidation of volatile organic compounds tends to take place in the first few hours after emission, SOA can continue to evolve chemically over its atmospheric lifetime. Simulating this chemical aging over an extended time in the laboratory has proven to be challenging. We present here a procedure for studying SOA aging in laboratory chambers that is applied to achieve 36 h of oxidation. The formation and evolution of SOA from the photooxidation of m-xylene under low-NOx conditions and in the presence of either neutral or acidic seed particles is studied. In SOA aging, increasing molecular functionalization leads to less volatile products and an increase in SOA mass, whereas gas-phase or particle-phase fragmentation chemistry results in more volatile products and a loss of SOA. The challenge is to discern from measured chamber variables the extent to which these processes are important for a given SOA system. In the experiments conducted, m-xylene SOA mass increased over the initial 12-h of photooxidation and decreased beyond that time. The oxidation of the SOA, as manifested in the O:C elemental ratio and fraction of organic ion detected at m/z 44 measured by the Aerodyne aerosol mass spectrometer, decreased during the first 5 h of reaction, reached a minimum, and then increased continuously until the 36 h termination. This behavior is consistent with an initial period in which, as the mass of SOA increases, products of higher volatility partition to the aerosol phase, followed by an aging period in which gas- and particle-phase reaction products become increasingly more oxidized. After about 12–13 h, the SOA mass reaches a maximum and decreases, suggesting the existence of fragmentation chemistry. When irradiation is stopped 12.4 h into one experiment, and OH generation ceases, no loss of SOA is observed, indicating that the loss of SOA is either light- or OH-induced. Chemical ionization mass spectrometry measurements of low-volatility m-xylene oxidation products exhibit behavior indicative of continuous photooxidation chemistry. A condensed chemical mechanism of m-xylene oxidation under low-NOx conditions is capable of reproducing the general behavior of gas-phase evolution observed here. Moreover, order of magnitude analysis of the mechanism suggests that gas-phase OH reaction of low volatility SOA precursors is the dominant pathway of aging in the m-xylene system although OH reaction with particle surfaces cannot be ruled out.

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Kinetic modeling of formation and evaporation of secondary organic aerosol from NO<sub>3</sub> oxidation of pure and mixed monoterpenes

Atmospheric Chemistry and Physics ◽

10.5194/acp-20-15513-2020 ◽

2020 ◽

Vol 20 (24) ◽

pp. 15513-15535

Author(s):

Thomas Berkemeier ◽

Masayuki Takeuchi ◽

Gamze Eris ◽

Nga L. Ng

Keyword(s):

Kinetic Model ◽

Gas Phase ◽

Secondary Organic Aerosol ◽

Organic Aerosol ◽

Chemical Mechanism ◽

Phase Reaction ◽

Particle Phase ◽

Environmental Chamber ◽

Gas Phase Chemistry ◽

Phase Chemistry

Abstract. Organic aerosol constitutes a major fraction of the global aerosol burden and is predominantly formed as secondary organic aerosol (SOA). Environmental chambers have been used extensively to study aerosol formation and evolution under controlled conditions similar to the atmosphere, but quantitative prediction of the outcome of these experiments is generally not achieved, which signifies our lack in understanding of these results and limits their portability to large-scale models. In general, kinetic models employing state-of-the-art explicit chemical mechanisms fail to describe the mass concentration and composition of SOA obtained from chamber experiments. Specifically, chemical reactions including the nitrate radical (NO3) are a source of major uncertainty for assessing the chemical and physical properties of oxidation products. Here, we introduce a kinetic model that treats gas-phase chemistry, gas–particle partitioning, particle-phase oligomerization, and chamber vapor wall loss and use it to describe the oxidation of the monoterpenes α-pinene and limonene with NO3. The model can reproduce aerosol mass and nitration degrees in experiments using either pure precursors or their mixtures and infers volatility distributions of products, branching ratios of reactive intermediates and particle-phase reaction rates. The gas-phase chemistry in the model is based on the Master Chemical Mechanism (MCM) but trades speciation of single compounds for the overall ability of quantitatively describing SOA formation by using a lumped chemical mechanism. The complex branching into a multitude of individual products in MCM is replaced in this model with product volatility distributions and detailed peroxy (RO2) and alkoxy (RO) radical chemistry as well as amended by a particle-phase oligomerization scheme. The kinetic parameters obtained in this study are constrained by a set of SOA formation and evaporation experiments conducted in the Georgia Tech Environmental Chamber (GTEC) facility. For both precursors, we present volatility distributions of nitrated and non-nitrated reaction products that are obtained by fitting the kinetic model systematically to the experimental data using a global optimization method, the Monte Carlo genetic algorithm (MCGA). The results presented here provide new mechanistic insight into the processes leading to formation and evaporation of SOA. Most notably, the model suggests that the observed slow evaporation of SOA could be due to reversible oligomerization reactions in the particle phase. However, the observed non-linear behavior of precursor mixtures points towards a complex interplay of reversible oligomerization and kinetic limitations of mass transport in the particle phase, which is explored in a model sensitivity study. The methodologies described in this work provide a basis for quantitative analysis of multi-source data from environmental chamber experiments but also show that a large data pool is needed to fully resolve uncertainties in model parameters.

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Examining the effects of anthropogenic emissions on isoprene-derived secondary organic aerosol formation during the 2013 Southern Oxidant and Aerosol Study (SOAS) at the Look Rock, Tennessee, ground site

Atmospheric Chemistry and Physics Discussions ◽

10.5194/acpd-15-7365-2015 ◽

2015 ◽

Vol 15 (5) ◽

pp. 7365-7417 ◽

Cited By ~ 7

Author(s):

S. H. Budisulistiorini ◽

X. Li ◽

S. T. Bairai ◽

J. Renfro ◽

Y. Liu ◽

...

Keyword(s):

Mass Spectrometry ◽

Secondary Organic Aerosol ◽

Organic Aerosol ◽

Anthropogenic Emissions ◽

Strongly Correlated ◽

Particle Phase ◽

Aerosol Formation ◽

Aerosol Acidity ◽

Southeastern Us

Abstract. A suite of offline and real-time gas- and particle-phase measurements was deployed at Look Rock, Tennessee (TN), during the 2013 Southern Oxidant and Aerosol Study (SOAS) to examine the effects of anthropogenic emissions on isoprene-derived secondary organic aerosol (SOA) formation. High- and low-time resolution PM2.5 samples were collected for analysis of known tracer compounds in isoprene-derived SOA by gas chromatography/electron ionization-mass spectrometry (GC/EI-MS) and ultra performance liquid chromatography/diode array detection-electrospray ionization-high-resolution quadrupole time-of-flight mass spectrometry (UPLC/DAD-ESI-HR-QTOFMS). Source apportionment of the organic aerosol (OA) was determined by positive matrix factorization (PMF) analysis of mass spectrometric data acquired on an Aerodyne Aerosol Chemical Speciation Monitor (ACSM). Campaign average mass concentrations of the sum of quantified isoprene-derived SOA tracers contributed to ~9% (up to 26%) of the total OA mass, with isoprene-epoxydiol (IEPOX) chemistry accounting for ~97% of the quantified tracers. PMF analysis resolved a factor with a profile similar to the IEPOX-OA factor resolved in an Atlanta study and was therefore designated IEPOX-OA. This factor was strongly correlated (r2>0.7) with 2-methyltetrols, C5-alkene triols, IEPOX-derived organosulfates, and dimers of organosulfates, confirming the role of IEPOX chemistry as the source. On average, IEPOX-derived SOA tracer mass was ~25% (up to 47%) of the IEPOX-OA factor mass, which accounted for 32% of the total OA. A low-volatility oxygenated organic aerosol (LV-OOA) and an oxidized factor with a profile similar to 91Fac observed in areas where emissions are biogenic-dominated were also resolved by PMF analysis, whereas no primary organic aerosol (POA) sources could be resolved. These findings were consistent with low levels of primary pollutants, such as nitric oxide (NO~0.03ppb), carbon monoxide (CO~116 ppb), and black carbon (BC~0.2 μg m−3). Particle-phase sulfate is fairly correlated (r2~0.3) with both MAE- and IEPOX-derived SOA tracers, and more strongly correlated (r2~0.6) with the IEPOX-OA factor, in sum suggesting an important role of sulfate in isoprene SOA formation. Moderate correlation between the methacrylic acid epoxide (MAE)-derived SOA tracer 2-methylglyceric acid with sum of reactive and reservoir nitrogen oxides (NOy; r2=0.38) and nitrate (r2=0.45) indicates the potential influence of anthropogenic emissions through long-range transport. Despite the lack of a~clear association of IEPOX-OA with locally estimated aerosol acidity and liquid water content (LWC), box model calculations of IEPOX uptake using the simpleGAMMA model, accounting for the role of acidity and aerosol water, predicted the abundance of the IEPOX-derived SOA tracers 2-methyltetrols and the corresponding sulfates with good accuracy (r2~0.5 and ~0.7, respectively). The modeling and data combined suggest an anthropogenic influence on isoprene-derived SOA formation through acid-catalyzed heterogeneous chemistry of IEPOX in the southeastern US. However, it appears that this process was not limited by aerosol acidity or LWC at Look Rock during SOAS. Future studies should further explore the extent to which acidity and LWC becomes a limiting factor of IEPOX-derived SOA, and their modulation by anthropogenic emissions.

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Kinetic modeling of secondary organic aerosol formation: effects of particle- and gas-phase reactions of semivolatile products

Atmospheric Chemistry and Physics ◽

10.5194/acp-7-4135-2007 ◽

2007 ◽

Vol 7 (15) ◽

pp. 4135-4147 ◽

Cited By ~ 60

Author(s):

A. W. H. Chan ◽

J. H. Kroll ◽

N. L. Ng ◽

J. H. Seinfeld

Keyword(s):

Gas Phase ◽

Secondary Organic Aerosol ◽

Laboratory Data ◽

Organic Aerosol ◽

Formation Mechanisms ◽

Hydrocarbon Oxidation ◽

Phase Reaction ◽

Particle Phase ◽

Aerosol Formation ◽

Kinetics Of

Abstract. The distinguishing mechanism of formation of secondary organic aerosol (SOA) is the partitioning of semivolatile hydrocarbon oxidation products between the gas and aerosol phases. While SOA formation is typically described in terms of partitioning only, the rate of formation and ultimate yield of SOA can also depend on the kinetics of both gas- and aerosol-phase processes. We present a general equilibrium/kinetic model of SOA formation that provides a framework for evaluating the extent to which the controlling mechanisms of SOA formation can be inferred from laboratory chamber data. With this model we examine the effect on SOA formation of gas-phase oxidation of first-generation products to either more or less volatile species, of particle-phase reaction (both first- and second-order kinetics), of the rate of parent hydrocarbon oxidation, and of the extent of reaction of the parent hydrocarbon. The effect of pre-existing organic aerosol mass on SOA yield, an issue of direct relevance to the translation of laboratory data to atmospheric applications, is examined. The importance of direct chemical measurements of gas- and particle-phase species is underscored in identifying SOA formation mechanisms.

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Kinetic modeling of Secondary Organic Aerosol formation: effects of particle- and gas-phase reactions of semivolatile products

Atmospheric Chemistry and Physics Discussions ◽

10.5194/acpd-7-7051-2007 ◽

2007 ◽

Vol 7 (3) ◽

pp. 7051-7085 ◽

Cited By ~ 1

Author(s):

A. W. H. Chan ◽

J. H. Kroll ◽

N. L. Ng ◽

J. H. Seinfeld

Keyword(s):

Gas Phase ◽

Secondary Organic Aerosol ◽

Laboratory Data ◽

Organic Aerosol ◽

Formation Mechanisms ◽

Hydrocarbon Oxidation ◽

Phase Reaction ◽

Particle Phase ◽

Aerosol Formation ◽

Kinetics Of

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Photolytically induced changes in composition and volatility of biogenic secondary organic aerosol from nitrate radical oxidation during night-to-day transition

Atmospheric Chemistry and Physics ◽

10.5194/acp-21-14907-2021 ◽

2021 ◽

Vol 21 (19) ◽

pp. 14907-14925

Author(s):

Cheng Wu ◽

David M. Bell ◽

Emelie L. Graham ◽

Sophie Haslett ◽

Ilona Riipinen ◽

...

Keyword(s):

Chemical Composition ◽

Mass Spectrometer ◽

Secondary Organic Aerosol ◽

Light Exposure ◽

Organic Aerosol ◽

Ionization Mass ◽

Peroxy Radicals ◽

Particle Phase ◽

Night Time ◽

Radical Oxidation

Abstract. Night-time reactions of biogenic volatile organic compounds (BVOCs) and nitrate radicals (NO3) can lead to the formation of NO3-initiated biogenic secondary organic aerosol (BSOANO3). Here, we study the impacts of light exposure on the chemical composition and volatility of BSOANO3 formed in the dark from three precursors (isoprene, α-pinene, and β-caryophyllene) in atmospheric simulation chamber experiments. Our study represents BSOANO3 formation conditions where reactions between peroxy radicals (RO2 + RO2) and between RO2 and NO3 are favoured. The emphasis here is on the identification of particle-phase organonitrates (ONs) formed in the dark and their changes during photolytic ageing on timescales of ∼ 1 h. The chemical composition of particle-phase compounds was measured with a chemical ionization mass spectrometer with a filter inlet for gases and aerosols (FIGAERO-CIMS) and an extractive electrospray ionization time-of-flight mass spectrometer (EESI-TOF). Volatility information on BSOANO3 was derived from FIGAERO-CIMS desorption profiles (thermograms) and a volatility tandem differential mobility analyser (VTDMA). During photolytic ageing, there was a relatively small change in mass due to evaporation (< 5 % for the isoprene and α-pinene BSOANO3, and 12 % for the β-caryophyllene BSOANO3), but we observed significant changes in the chemical composition of the BSOANO3. Overall, 48 %, 44 %, and 60 % of the respective total signal for the isoprene, α-pinene, and β-caryophyllene BSOANO3 was sensitive to photolytic ageing and exhibited decay. The photolabile compounds include both monomers and oligomers. Oligomers can decompose into their monomer units through photolysis of the bonds (e.g. likely O–O) between them. Fragmentation of both oligomers and monomers also happened at other positions, causing the formation of compounds with shorter carbon skeletons. The cleavage of the nitrate functional group from the carbon chain was likely not a main degradation pathway in our experiments. In addition, photolytic degradation of compounds changes their volatility and can lead to evaporation. We use different methods to assess bulk volatilities and discuss their changes during both dark ageing and photolysis in the context of the chemical changes that we observed. We also reveal large uncertainties in saturation vapour pressure estimated from parameterizations for the ON oligomers with multiple nitrate groups. Overall, our results suggest that photolysis causes photodegradation of a substantial fraction of BSOANO3, changes both the chemical composition and the bulk volatility of the particles, and might be a potentially important loss pathway of BSOANO3 during the night-to-day transition.

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

Atmospheric Chemistry and Physics ◽

10.5194/acp-21-11467-2021 ◽

2021 ◽

Vol 21 (14) ◽

pp. 11467-11487

Author(s):

Isaac Kwadjo Afreh ◽

Bernard Aumont ◽

Marie Camredon ◽

Kelley Claire Barsanti

Keyword(s):

Air Quality ◽

Gas Phase ◽

Secondary Organic Aerosol ◽

Organic Aerosol ◽

Mechanistic Study ◽

Phase Reaction ◽

Particle Phase ◽

Aerosol Formation ◽

Model Simulations ◽

Chemical Mechanisms

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, as well as 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, and peroxy radicals reacted equally with HO2 and NO. 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 % α-pinene + 50 % 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 highlights opportunities for future measurement–model comparisons and lays a foundation for developing chemical mechanisms and SOA parameterizations for camphene that are suitable for air quality modeling.

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