Formation and chemical aging of secondary organic aerosol during the β-caryophyllene oxidation

Tasoglou, Antonios; Pandis, Spyros Ν.

doi:10.5194/acp-15-6035-2015

Cited by 50 publications

(60 citation statements)

References 38 publications

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“…Yields for limonene SOA mass loadings of 350 µg m −3 are around 0.31, which is lower than the experimental values of 0.58, measured by Lee et al (2006b). For β-caryophyllene, the modeled values are in good agreement with experimental measured yields in the range of mass loadings provided by Griffin (1999) and Tasoglou and Pandis (2015). Currently there are no experiments providing HOM yields from OH oxidation of β-caryophyllene, and hence those species are not included in PRAM.…”

Section: Bvocs -O 3 Chamber and Flow-tube Simulationsmentioning

confidence: 61%

Aerosol mass yields of selected biogenic volatile organic compounds – a theoretical study with nearly explicit gas-phase chemistry

et al. 2019

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Abstract. In this study we modeled secondary organic aerosol (SOA) mass loadings from the oxidation (by O3, OH and NO3) of five representative biogenic volatile organic compounds (BVOCs): isoprene, endocyclic bond-containing monoterpenes (α-pinene and limonene), exocyclic double-bond compound (β-pinene) and a sesquiterpene (β-caryophyllene). The simulations were designed to replicate an idealized smog chamber and oxidative flow reactors (OFRs). The Master Chemical Mechanism (MCM) together with the peroxy radical autoxidation mechanism (PRAM) were used to simulate the gas-phase chemistry. The aim of this study was to compare the potency of MCM and MCM + PRAM in predicting SOA formation. SOA yields were in good agreement with experimental values for chamber simulations when MCM + PRAM was applied, while a stand-alone MCM underpredicted the SOA yields. Compared to experimental yields, the OFR simulations using MCM + PRAM yields were in good agreement for BVOCs oxidized by both O3 and OH. On the other hand, a stand-alone MCM underpredicted the SOA mass yields. SOA yields increased with decreasing temperatures and NO concentrations and vice versa. This highlights the limitations posed when using fixed SOA yields in a majority of global and regional models. Few compounds that play a crucial role (>95 % of mass load) in contributing to SOA mass increase (using MCM + PRAM) are identified. The results further emphasized that incorporating PRAM in conjunction with MCM does improve SOA mass yield estimation.

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Section: Bvocs -O 3 Chamber and Flow-tube Simulationsmentioning

confidence: 61%

Aerosol mass yields of selected biogenic volatile organic compounds – a theoretical study with nearly explicit gas-phase chemistry

et al. 2019

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“…As for previous O 3 oxidation experiments in an OFR, representative SOA yields of 15 % for MT and 30 % for SQT were used . Due to the uncertainty in these yields, the lack of speciation of MT at the T3 site, and the lack of published yields for the variety of SQT that were speciated by the SV-TAG, these yield values were chosen to be generally representative of published values (e.g., Jaoui et al, 2003Jaoui et al, , 2013Ng et al, 2006;Pathak et al, 2007Pathak et al, , 2008Shilling et al, 2008;Winterhalter et al, 2009;Chen et al, 2012;Tasoglou and Pandis, 2015;Zhao et al, 2015).…”

Section: Predicting Soa Formation In the Ofrmentioning

confidence: 99%

Secondary organic aerosol formation from ambient air in an oxidation flow reactor in central Amazonia

Palm¹,

Sá²,

Day³

et al. 2018

Atmos. Chem. Phys.

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Abstract. Secondary organic aerosol (SOA) formation from ambient air was studied using an oxidation flow reactor (OFR) coupled to an aerosol mass spectrometer (AMS) during both the wet and dry seasons at the Observations and Modeling of the Green Ocean Amazon (GoAmazon2014/5) field campaign. Measurements were made at two sites downwind of the city of Manaus, Brazil. Ambient air was oxidized in the OFR using variable concentrations of either OH or O 3 , over ranges from hours to days (O 3 ) or weeks (OH) of equivalent atmospheric aging. The amount of SOA formed in the OFR ranged from 0 to as much as 10 µg m −3 , depending on the amount of SOA precursor gases in ambient air. Typically, more SOA was formed during nighttime than daytime, and more from OH than from O 3 oxidation. SOA yields of individual organic precursors under OFR conditions were measured by standard addition into ambient air and were confirmed to be consistent with published environmental chamber-derived SOA yields. Positive matrix factorization of organic aerosol (OA) after OH oxidation showed formation of typical oxidized OA factors and a loss of primary Published by Copernicus Publications on behalf of the European Geosciences Union. OA factors as OH aging increased. After OH oxidation in the OFR, the hygroscopicity of the OA increased with increasing elemental O : C up to O : C∼1.0, and then decreased as O : C increased further. Possible reasons for this decrease are discussed. The measured SOA formation was compared to the amount predicted from the concentrations of measured ambient SOA precursors and their SOA yields. While measured ambient precursors were sufficient to explain the amount of SOA formed from O 3 , they could only explain 10-50 % of the SOA formed from OH. This is consistent with previous OFR studies, which showed that typically unmeasured semivolatile and intermediate volatility gases (that tend to lack C=C bonds) are present in ambient air and can explain such additional SOA formation. To investigate the sources of the unmeasured SOA-forming gases during this campaign, multilinear regression analysis was performed between measured SOA formation and the concentration of gas-phase tracers representing different precursor sources. The majority of SOA-forming gases present during both seasons were of biogenic origin. Urban sources also contributed substantially in both seasons, while biomass burning sources were more important during the dry season. This study enables a better understanding of SOA formation in environments with diverse emission sources.

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“…These VOCs can undergo numerous oxidation reactions, forming lower-volatility compounds, which can partition into particulate-phase-forming SOA. Once formed, the chemical composition of SOA can continue to evolve via absorptive partitioning (Donahue et al, 2006;Pankow, 1994a, b), reactive uptake of organic gases (Czoschke et al, 2003;Gaston et al, 2014;Iinuma et al, 2004;Jang et al, 2002;Kroll et al, 2005;Riva et al, 2017), heterogenous oxidation by gasphase radicals (George and Abbatt, 2010a, b;Kroll et al, 2015; and in particle-phase reactions (Gao et al, 2004;Heaton et al, 2007;Kalberer et al, 2004;Tolocka et al, 2004).…”

Section: Introductionmentioning

confidence: 99%

A new aerosol flow reactor to study secondary organic aerosol

et al. 2019

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Abstract. Gas-particle equilibrium partitioning is a fundamental concept used to describe the growth and loss of secondary organic aerosol (SOA). However, recent literature has suggested that gas-particle partitioning may be kinetically limited, preventing volatilization from the aerosol phase as a result of the physical state of the aerosol (e.g. glassy, viscous). Experimental measurements of diffusion constants within viscous aerosol are limited and do not represent the complex chemical composition observed in SOA (i.e. multicomponent mixtures). Motivated by the need to address fundamental questions regarding the effect of the physical state and chemical composition of a particle on gas-particle partitioning, we present the design and operation of a newly built 0.3 m3 continuous-flow reactor (CFR), which can be used as a tool to gain considerable insights into the composition and physical state of SOA. The CFR was used to generate SOA from the photo-oxidation of α-pinene, limonene, β-caryophyllene and toluene under different experimental conditions (i.e. relative humidity, VOC and VOC∕NOx ratios). Up to 102 mg of SOA mass was collected per experiment, allowing the use of highly accurate compositional- and single-particle analysis techniques, which are not usually accessible due to the large quantity of organic aerosol mass required for analysis. A suite of offline analytical techniques was used to determine the chemical composition and physical state of the generated SOA, including attenuated total reflectance infrared spectroscopy; carbon, hydrogen, nitrogen, and sulfur (CHNS) elemental analysis; 1H and 1H-13C nuclear magnetic resonance spectroscopy (NMR); ultra-performance liquid chromatography ultra-high-resolution mass spectrometry (UHRMS); high-performance liquid chromatography ion-trap mass spectrometry (HPLC-ITMS); and an electrodynamic balance (EDB). The oxygen-to-carbon (O∕C) and hydrogen-to-carbon (H∕C) ratios of generated SOA samples (determined using a CHNS elemental analyser) displayed good agreement with literature values and were consistent with the characteristic Van Krevelen diagram trajectory, with an observed slope of −0.41. The elemental composition of two SOA samples formed in separate replicate experiments displayed excellent reproducibility, with the O∕C and H∕C ratios of the SOA samples observed to be within error of the analytical instrumentation (instrument accuracy ±0.15 % to a reference standard). The ability to use a highly accurate CHNS elemental analyser to determine the elemental composition of the SOA samples allowed us to evaluate the accuracy of reported SOA elemental compositions using UHRMS (a commonly used technique). In all of the experiments investigated, the SOA O∕C ratios obtained for each SOA sample using UHRMS were lower than the O∕C ratios obtained from the CHNS analyser (the more accurate and non-selective technique). The average difference in the ΔO∕C ratios ranged from 19 % to 45 % depending on the SOA precursor and formation conditions. α-pinene SOA standards were generated from the collected SOA mass using semi-preparative HPLC-ITMS coupled to an automated fraction collector, followed by 1H NMR spectroscopy. Up to 35.8±1.6 % (propagated error of the uncertainty in the slope of the calibrations graphs) of α-pinene SOA was quantified using this method; a considerable improvement from most previous studies. Single aerosol droplets were generated from the collected SOA samples and trapped within an EDB at different temperatures and relative humidities to investigate the dynamic changes in their physiochemical properties. The volatilization of organic components from toluene and β-caryophyllene SOA particles at 0 % relative humidity was found to be kinetically limited, owing to particle viscosity. The unconventional use of a newly built CFR, combined with comprehensive offline chemical characterization and single-particle measurements, offers a unique approach to further our understanding of the relationship between SOA formation conditions, chemical composition and physiochemical properties.

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Formation and chemical aging of secondary organic aerosol during the β-caryophyllene oxidation

Cited by 50 publications

References 38 publications

Aerosol mass yields of selected biogenic volatile organic compounds – a theoretical study with nearly explicit gas-phase chemistry

Aerosol mass yields of selected biogenic volatile organic compounds – a theoretical study with nearly explicit gas-phase chemistry

Secondary organic aerosol formation from ambient air in an oxidation flow reactor in central Amazonia

A new aerosol flow reactor to study secondary organic aerosol

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