scholarly journals Kinetics, SOA yields and chemical composition of secondary organic aerosol from β-caryophyllene ozonolysis with and without nitrogen oxides between 213 and 313 K

2022 ◽  
Author(s):  
Linyu Gao ◽  
Junwei Song ◽  
Claudia Mohr ◽  
Wei Huang ◽  
Magdalena Vallon ◽  
...  

Abstract. β-caryophyllene (BCP) is one of the most important sesquiterpenes (SQTs) in the atmosphere, with a large potential contribution to secondary organic aerosol (SOA) formation mainly from reactions with ozone (O3) and nitrate radicals (NO3). In this work, we study the temperature dependence of the kinetics of BCP ozonolysis, SOA yields, and SOA chemical composition in the dark and in the absence and presence of nitrogen oxides including nitrate radicals (NO3). We cover a temperature range of 213 K – 313 K, representative of tropospheric conditions. The oxidized components in both gas and particle phases were characterized on a molecular level by a Chemical Ionization Mass Spectrometer equipped with a Filter Inlet for Gases and AEROsols using iodide as the reagent ion (FIGAERO-iodide-CIMS). The batch mode experiments were conducted in the 84.5 m3 aluminium simulation chamber AIDA at the Karlsruhe Institute of Technology (KIT). In the absence of nitrogen oxides, the temperature-dependent rate coefficient of the endocyclic double bond in BCP reacting with ozone between 243 – 313 K are negatively correlated with temperature, corresponding to the following Arrhenius equation: k = (1.6 ± 0.4)  × 10−15 × exp((559 ± 97)/T). The SOA yields increase from 16 ± 5 % to 37 ± 11% with temperatures decreasing from 313 K to 243 K at a total organic particle mass of 10 µg m−3. The variation of the ozonolysis temperature leads to substantial impact on the abundance of individual organic molecules. In the absence of nitrogen oxides, monomers C14-15H22-24O3-7 (37.4 %), dimers C28-30H44-48O5-9 (53.7 %) and trimers C41-44H62-66O9-11 (8.6 %) are abundant in the particle phase at 213 K. At 313 K, we observed more oxidized monomers (mainly C14-15H22-24O6-9, 67.5 %) and dimers (mainly C27-29H42-44O9-11, 27.6 %), including highly oxidized molecules (HOMs, C14H22O7,9, C15H22O7,9 C15H24O7,9) which can be formed via hydrogen shift mechanisms, but no significant trimers. In presence of nitrogen oxides, the organonitrate fraction increased from 3 % at 213 K to 12 % and 49 % at 243 K and 313 K, respectively. Most of the organonitrates were monomers with C15 skeletons and only one nitrate group. Higher oxygenated organonitrates were observed at higher temperatures, with their signal-weighted O : C atomic ratio increasing from 0.41 to 0.51 from 213 K to 313 K. New dimeric and trimeric organic species without nitrogen atoms (C20, C35) were formed in presence of nitrogen oxides at 298–313 K indicating potential new reaction pathways. Overall, our results show that increasing temperatures lead to a relatively small decrease of the rate coefficient of the endocyclic double bond in BCP reacting with ozone, but to a strong decrease in SOA yields. In contrast, the formation of HOMs and organonitrates increases significantly with temperature.

2021 ◽  
Vol 21 (19) ◽  
pp. 14907-14925
Author(s):  
Cheng Wu ◽  
David M. Bell ◽  
Emelie L. Graham ◽  
Sophie Haslett ◽  
Ilona Riipinen ◽  
...  

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.


2006 ◽  
Vol 110 (31) ◽  
pp. 9665-9690 ◽  
Author(s):  
Jason D. Surratt ◽  
Shane M. Murphy ◽  
Jesse H. Kroll ◽  
Nga L. Ng ◽  
Lea Hildebrandt ◽  
...  

2016 ◽  
Author(s):  
L. Li ◽  
P. Tang ◽  
S. Nakao ◽  
D. R. Cocker III

Abstract. The molecular structure of volatile organic compounds (VOC) determines their oxidation pathway, directly impacting secondary organic aerosol (SOA) formation. This study comprehensively investigates the impact of molecular structure on SOA formation from the photooxidation of twelve different eight to nine carbon aromatic hydrocarbons under low NOx conditions. The effects of the alkyl substitute number, location, carbon chain length and branching structure on the photooxidation of aromatic hydrocarbons are demonstrated by analyzing SOA yield, chemical composition and physical properties. Aromatic hydrocarbons, categorized into five groups, show a yield order of ortho (o-xylene and o-ethyltoluene) > one substitute (ethylbenzene, propylbenzene and isopropylbenzene) > meta (m-xylene and m-ethyltoluene) > three substitute (trimethylbenzenes) > para (p-xylene and p-ethyltoluene). SOA yields of aromatic hydrocarbon photooxidation do not monotonically decrease when increasing alkyl substitute number. The ortho position promotes SOA formation while the para position suppresses aromatic oxidation and SOA formation. Observed SOA chemical composition and volatility confirm that higher yield is associated with further oxidation. SOA chemical composition also suggests that aromatic oxidation increases with increasing alkyl substitute chain length and branching structure. Further, carbon dilution theory developed by Li et al. (2015a) is extended in this study to serve as a standard method to determine the extent of oxidation of an alkyl substituted aromatic hydrocarbon.


2021 ◽  
Vol 21 (15) ◽  
pp. 11545-11562
Author(s):  
Louise N. Jensen ◽  
Manjula R. Canagaratna ◽  
Kasper Kristensen ◽  
Lauriane L. J. Quéléver ◽  
Bernadette Rosati ◽  
...  

Abstract. This work investigates the individual and combined effects of temperature and volatile organic compound precursor concentrations on the chemical composition of particles formed in the dark ozonolysis of α-pinene. All experiments were conducted in a 5 m3 Teflon chamber at an initial ozone concentration of 100 ppb and initial α-pinene concentrations of 10 and 50 ppb, respectively; at constant temperatures of 20, 0, or −15 ∘C; and at changing temperatures (ramps) from −15 to 20 and from 20 to −15 ∘C. The chemical composition of the particles was probed using a high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS). A four-factor solution of a positive matrix factorization (PMF) analysis of the combined HR-ToF-AMS data is presented. The PMF analysis and the elemental composition analysis of individual experiments show that secondary organic aerosol particles with the highest oxidation level are formed from the lowest initial α-pinene concentration (10 ppb) and at the highest temperature (20 ∘C). A higher initial α-pinene concentration (50 ppb) and/or lower temperature (0 or −15 ∘C) results in a lower oxidation level of the molecules contained in the particles. With respect to the carbon oxidation state, particles formed at 0 ∘C are more comparable to particles formed at −15 ∘C than to those formed at 20 ∘C. A remarkable observation is that changes in temperature during particle formation result in only minor changes in the elemental composition of the particles. Thus, the temperature at which aerosol particle formation is induced seems to be a critical parameter for the particle elemental composition. Comparison of the HR-ToF-AMS-derived estimates of the content of organic acids in the particles based on m/z 44 in the mass spectra show good agreement with results from off-line molecular analysis of particle filter samples collected from the same experiments. Higher temperatures are associated with a decrease in the absolute mass concentrations of organic acids (R-COOH) and organic acid functionalities (-COOH), while the organic acid functionalities account for an increasing fraction of the measured particle mass.


2020 ◽  
Author(s):  
Yunle Chen ◽  
Masayuki Takeuchi ◽  
Theodora Nah ◽  
Lu Xu ◽  
Manjula R. Canagaratna ◽  
...  

Abstract. The formation and evolution of secondary organic aerosol (SOA) was investigated at Yorkville, GA, in late summer (mid-August ~ mid-October, 2016). Organic aerosol (OA) composition was measured using two on-line mass spectrometry instruments, the high-resolution time-of-flight aerosol mass spectrometer (AMS) and the Filter Inlet for Gases and AEROsols coupled to a high-resolution time-of-flight iodide-adduct chemical ionization mass spectrometer (FIGAERO-CIMS). Through analysis of speciated organics data from FIGAERO-CIMS and factorization analysis of data obtained from both instruments, we observed notable SOA formation from isoprene and monoterpenes during both day and night. Specifically, in addition to isoprene epoxydiols (IEPOX) uptake, we identified isoprene SOA formation via hydroxyl hydroperoxide oxidation (ISOPOOH oxidation via non-IEPOX pathways) and isoprene organic nitrate formation via photooxidation in the presence of NOx and nitrate radical oxidation. Monoterpenes were found to be the most important SOA precursors at night. We observed significant contributions from highly-oxidized acid-like compounds to the aged OA factor from FIGAERO-CIMS. Taken together, our results showed that FIGAERO-CIMS measurements are highly complementary to the extensively used AMS factorization analysis, and together they provide more comprehensive insights into OA sources and composition.


2016 ◽  
Vol 50 (10) ◽  
pp. 4997-5006 ◽  
Author(s):  
Rebecca M. Harvey ◽  
Adam P. Bateman ◽  
Shashank Jain ◽  
Yong Jie Li ◽  
Scot Martin ◽  
...  

2019 ◽  
Vol 3 (6) ◽  
pp. 922-934 ◽  
Author(s):  
Taekyu Joo ◽  
Jean C. Rivera-Rios ◽  
Masayuki Takeuchi ◽  
Matthew J. Alvarado ◽  
Nga Lee Ng

2017 ◽  
Author(s):  
Julia Montoya ◽  
Jeremy R. Horne ◽  
Mallory L. Hinks ◽  
Lauren T. Fleming ◽  
Veronique Perraud ◽  
...  

Abstract. Indole is a heterocyclic compound emitted by various plant species under stressed conditions or during flowering events. The formation, optical properties, and chemical composition of secondary organic aerosol (SOA) formed by low-NOx photooxidation of indole were investigated. The SOA yield (1.1 ± 0.3) was estimated from measuring the particle mass concentration with a scanning mobility particle sizer (SMPS) and correcting it for the wall loss effects. The SOA particles were collected on filters and analysed offline with UV-Vis spectrophotometry to measure the mass absorption coefficient (MAC) of the bulk sample. The samples were visibly brown and had MAC values of ~7 m2/g at λ = 300 nm and ~2 m2/g at λ = 400 nm, comparable to strongly absorbing brown carbon emitted from biomass burning. The chemical composition of SOA was examined with several mass spectrometry methods. The direct analysis in real time mass spectrometry (DART-MS) and nanospray desorption electrospray high resolution mass spectrometry (nano-DESI-HRMS) were used to provide information about the overall distribution of SOA compounds. High performance liquid chromatography, coupled to photodiode array spectrophotometry and high resolution mass spectrometry (HPLC-PDA-HRMS) was used to identify chromophoric compounds. Indole derivatives, such as tryptanthrin, indirubin, indigo dye, and indoxyl red were found to contribute significantly to the visible absorption spectrum of indole SOA. The potential effect of indole SOA on air quality was explored with the airshed model, which found elevated concentrations of indole SOA during the afternoon hours contributing considerably to the total organic aerosol under selected scenarios. Because of its high MAC values, indole SOA can contribute to decreased visibility and poor air quality.


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