scholarly journals Ozonolysis of α-phellandrene – Part 2: Compositional analysis of secondary organic aerosol highlights the role of stabilised Criegee intermediates

2017 ◽  
Author(s):  
Felix A. Mackenzie-Rae ◽  
Helen J. Wallis ◽  
Andrew R. Rickard ◽  
Kelly Pereira ◽  
Sandra M. Saunders ◽  
...  
Keyword(s):  
Second Generation ◽  
Secondary Organic Aerosol ◽  
Indirect Evidence ◽  
Compositional Analysis ◽  
Particle Growth ◽  
Organic Aerosol ◽  
Companion Paper ◽  
Formation Mechanisms ◽  
Criegee Intermediates ◽  
First And Second Generation

Abstract. The molecular composition of secondary organic aerosol (SOA) generated from the ozonolysis of α-phellandrene is investigated for the first time using high pressure liquid chromatography coupled to high-resolution Quadrupole-Orbitrap tandem mass spectrometry. In total, 21 prominent products or isomeric product groups were identified using both positive and negative ionisation modes, with potential formation mechanisms discussed. The aerosol was found to be composed primarily of polyfunctional first- and second-generation species containing one or more carbonyl, acid, alcohol and hydroperoxide functionalities, with the products significantly more complex than those proposed from basic gas-phase chemistry in the companion paper (Mackenzie-Rae et al., 2017a). Mass spectra show a large number of dimeric products are also formed. Both direct scavenging evidence using formic acid, and indirect evidence from double bond equivalency factors, suggests the dominant oligomerisation mechanism is the bimolecular reaction of stabilised Criegee intermediates (SCIs) with non-radical ozonolysis products. Saturation vapour concentration estimates suggest monomeric species cannot explain the rapid nucleation burst of fresh aerosol observed in chamber experiments, hence dimeric species are believed to be responsible for new particle formation, with detected first- and second-generation products driving further particle growth in the system. Ultimately, identification of the major constituents and formation pathways of α-phellandrene SOA leads to a greater understanding of the atmospheric processes and implications of monoterpene emissions and SCIs, especially around Eucalypt forests regions where α-phellandrene is primarily emitted.

scholarly journals Ozonolysis of <i>α</i>-phellandrene – Part 2: Compositional analysis of secondary organic aerosol highlights the role of stabilised Criegee intermediates

2018 ◽  
Vol 18 (7) ◽  
pp. 4673-4693 ◽  
Author(s):  
Felix A. Mackenzie-Rae ◽  
Helen J. Wallis ◽  
Andrew R. Rickard ◽  
Kelly L. Pereira ◽  
Sandra M. Saunders ◽  
...  
Keyword(s):  
Second Generation ◽  
Secondary Organic Aerosol ◽  
Indirect Evidence ◽  
Compositional Analysis ◽  
Particle Growth ◽  
Organic Aerosol ◽  
Water Soluble ◽  
Formation Mechanisms ◽  
Criegee Intermediates ◽  
First And Second Generation

Abstract. The molecular composition of the water-soluble fraction of secondary organic aerosol (SOA) generated from the ozonolysis of α-phellandrene is investigated for the first time using high-pressure liquid chromatography coupled to high-resolution quadrupole–Orbitrap tandem mass spectrometry. In total, 21 prominent products or isomeric product groups were identified using both positive and negative ionisation modes, with potential formation mechanisms discussed. The aerosol was found to be composed primarily of polyfunctional first- and second-generation species containing one or more carbonyl, acid, alcohol and hydroperoxide functionalities, with the products significantly more complex than those proposed from basic gas-phase chemistry in the companion paper (Mackenzie-Rae et al., 2017). Mass spectra show a large number of dimeric products are also formed. Both direct scavenging evidence using formic acid and indirect evidence from double bond equivalency factors suggest the dominant oligomerisation mechanism is the bimolecular reaction of stabilised Criegee intermediates (SCIs) with non-radical ozonolysis products. Saturation vapour concentration estimates suggest monomeric species cannot explain the rapid nucleation burst of fresh aerosol observed in chamber experiments; hence, dimeric species are believed to be responsible for new particle formation, with detected first- and second-generation products driving further particle growth in the system. Ultimately, identification of the major constituents and formation pathways of α-phellandrene SOA leads to a greater understanding of the atmospheric processes and implications of monoterpene emissions and SCIs, especially around eucalypt forests where α-phellandrene is primarily emitted.

scholarly journals Quantification of the role of stabilized Criegee intermediates in the formation of aerosols in limonene ozonolysis

2020 ◽  
Author(s):  
Yiwei Gong ◽  
Zhongming Chen
Keyword(s):  
Second Generation ◽  
Tropospheric Chemistry ◽  
Formation Mechanisms ◽  
High Humidity ◽  
Effect Of Water ◽  
Criegee Intermediates ◽  
Low Humidity ◽  
First And Second Generation ◽  
Stabilized Criegee Intermediates

Abstract. Stabilized Criegee intermediates (SCIs) have the potential to oxidize trace species and to produce secondary organic aerosols (SOA), making them important factors in tropospheric chemistry. This study quantitatively investigates the performance of SCIs in SOA formation at different relative humidity (RH), and the first- and second-generation oxidations of endo- and exo-cyclic double bonds ozonated in limonene ozonolysis are studied separately. Through regulating SCIs scavengers, the yields and rate constants of SCIs in reaction system were derived, and the amounts of SCIs were calculated. The amount of SOA decreased by more than 20 % under low-humidity conditions (10–50 % RH), compared to that under dry conditions due to the reactions of SCIs with water, while the inhibitory effect of water on SOA formation was not observed under high-humidity conditions (60–90 % RH). When using excessive SCIs scavengers to exclude SCIs reactions, it was found that the effect of water on SOA formation with the presence of SCIs was different from that without the presence of SCIs, suggesting that SCIs reactions were relevant to the non-monotonic impact of water. The fractions of SCIs contribution to SOA were similar between dry and high-humidity conditions, where the SCIs reactions accounted for ~ 63 % and ~ 73 % in SOA formation in the first- and second-generation oxidation, however, marked differences in SOA formation mechanisms were observed. SOA formation showed a positive correlation with the amount of SCIs, and the SOA formation potential of SCIs under high-humidity conditions was more significant than that under dry and low-humidity conditions. It was estimated that 20–30 % of SCIs could convert into SOA under high-humidity conditions, while this value decreased nearly by half under dry and low-humidity conditions. The contributions of limonene-derived SCIs to SOA in atmosphere were evaluated, and it was estimated that the contribution of SCIs to SOA was the lowest under low-humidity conditions. Under high-humidity conditions, the contribution of limonene-derived SCIs to SOA was (8.21 ± 0.15) × 10−2 μg m−3 h−1 in forest, (6.66 ± 0.12) × 10−2 μg m−3 h−1 in urban area, and (3.95 ± 0.72) × 10−1 μg m−3 h−1 in indoor area. Water was an uncertainty on the role of SCIs playing in SOA formation, and the contribution of SCIs to SOA formation needed consideration even under high RH in the atmosphere.

scholarly journals Quantification of the role of stabilized Criegee intermediates in the formation of aerosols in limonene ozonolysis

2021 ◽  
Vol 21 (2) ◽  
pp. 813-829
Author(s):  
Yiwei Gong ◽  
Zhongming Chen
Keyword(s):  
Second Generation ◽  
Reaction System ◽  
Tropospheric Chemistry ◽  
Formation Mechanisms ◽  
High Humidity ◽  
Effect Of Water ◽  
Criegee Intermediates ◽  
Low Humidity ◽  
First And Second Generation ◽  
Stabilized Criegee Intermediates

Abstract. Stabilized Criegee intermediates (SCIs) have the potential to oxidize trace species and to produce secondary organic aerosols (SOAs), making them important factors in tropospheric chemistry. This study quantitatively investigates the performance of SCIs in SOA formation at different relative humidity (RH) levels, and the first- and second-generation oxidations of endo- and exocyclic double bonds ozonated in limonene ozonolysis are studied separately. Through regulating SCI scavengers, the yields and rate constants of SCIs in a reaction system were derived, and the quantities of SCIs were calculated. The quantity of SOAs decreased by more than 20 % under low-humidity conditions (10 % RH–50 % RH), compared to that under dry conditions, due to the reactions of SCIs with water, while the inhibitory effect of water on SOA formation was not observed under high-humidity conditions (60 % RH–90 % RH). When using excessive SCI scavengers to exclude SCI reactions, it was found that the effect of water on SOA formation with the presence of SCIs was different from that without the presence of SCIs, suggesting that SCI reactions were relevant to the non-monotonic impact of water. The fractions of the SCI contribution to SOAs were similar between dry and high-humidity conditions, where the SCI reactions accounted for ∼ 63 % and ∼ 73 % in SOA formation in the first- and second-generation oxidation; however, marked differences in SOA formation mechanisms were observed. SOA formation showed a positive correlation with the quantity of SCIs, and the SOA formation potential of SCIs under high-humidity conditions was more significant than that under dry and low-humidity conditions. It was estimated that 20 %–30 % of SCIs could be converted into SOAs under high-humidity conditions, while this value decreased by nearly half under dry and low-humidity conditions. The typical contribution of limonene-derived SCIs to SOA formation is calculated to be (8.21 ± 0.15) × 10−2 µg m−3 h−1 in forest, (4.26 ± 0.46) × 10−2 µg m−3 h−1 in urban areas, and (2.52 ± 0.28) × 10−1 µg m−3 h−1 in indoor areas. Water is an uncertainty in the role SCIs play in SOA formation, and the contribution of SCIs to SOA formation needs consideration even under high RH in the atmosphere.

scholarly journals Arctic marine secondary organic aerosol contributes significantly to summertime particle size distributions in the Canadian Arctic Archipelago

2019 ◽  
Vol 19 (5) ◽  
pp. 2787-2812 ◽  
Author(s):  
Betty Croft ◽  
Randall V. Martin ◽  
W. Richard Leaitch ◽  
Julia Burkart ◽  
Rachel Y.-W. Chang ◽  
...  
Keyword(s):  
Particle Size ◽  
Size Distribution ◽  
Secondary Organic Aerosol ◽  
Canadian Arctic ◽  
Particle Growth ◽  
Organic Aerosol ◽  
The Arctic ◽  
Canadian Arctic Archipelago ◽  
Size Distributions ◽  
Fractional Error

Abstract. Summertime Arctic aerosol size distributions are strongly controlled by natural regional emissions. Within this context, we use a chemical transport model with size-resolved aerosol microphysics (GEOS-Chem-TOMAS) to interpret measurements of aerosol size distributions from the Canadian Arctic Archipelago during the summer of 2016, as part of the “NETwork on Climate and Aerosols: Addressing key uncertainties in Remote Canadian Environments” (NETCARE) project. Our simulations suggest that condensation of secondary organic aerosol (SOA) from precursor vapors emitted in the Arctic and near Arctic marine (ice-free seawater) regions plays a key role in particle growth events that shape the aerosol size distributions observed at Alert (82.5∘ N, 62.3∘ W), Eureka (80.1∘ N, 86.4∘ W), and along a NETCARE ship track within the Archipelago. We refer to this SOA as Arctic marine SOA (AMSOA) to reflect the Arctic marine-based and likely biogenic sources for the precursors of the condensing organic vapors. AMSOA from a simulated flux (500 µgm-2day-1, north of 50∘ N) of precursor vapors (with an assumed yield of unity) reduces the summertime particle size distribution model–observation mean fractional error 2- to 4-fold, relative to a simulation without this AMSOA. Particle growth due to the condensable organic vapor flux contributes strongly (30 %–50 %) to the simulated summertime-mean number of particles with diameters larger than 20 nm in the study region. This growth couples with ternary particle nucleation (sulfuric acid, ammonia, and water vapor) and biogenic sulfate condensation to account for more than 90 % of this simulated particle number, which represents a strong biogenic influence. The simulated fit to summertime size-distribution observations is further improved at Eureka and for the ship track by scaling up the nucleation rate by a factor of 100 to account for other particle precursors such as gas-phase iodine and/or amines and/or fragmenting primary particles that could be missing from our simulations. Additionally, the fits to the observed size distributions and total aerosol number concentrations for particles larger than 4 nm improve with the assumption that the AMSOA contains semi-volatile species: the model–observation mean fractional error is reduced 2- to 3-fold for the Alert and ship track size distributions. AMSOA accounts for about half of the simulated particle surface area and volume distributions in the summertime Canadian Arctic Archipelago, with climate-relevant simulated summertime pan-Arctic-mean top-of-the-atmosphere aerosol direct (−0.04 W m−2) and cloud-albedo indirect (−0.4 W m−2) radiative effects, which due to uncertainties are viewed as an order of magnitude estimate. Future work should focus on further understanding summertime Arctic sources of AMSOA.

scholarly journals A biogenic secondary organic aerosol source of cirrus ice nucleating particles

2020 ◽  
Vol 11 (1) ◽  
Author(s):  
Martin J. Wolf ◽  
Yue Zhang ◽  
Maria A. Zawadowicz ◽  
Megan Goodell ◽  
Karl Froyd ◽  
...  
Keyword(s):  
Laboratory Experiments ◽  
Secondary Organic Aerosol ◽  
Global Climate ◽  
Compositional Analysis ◽  
Field Measurements ◽  
Organic Aerosol ◽  
Cloud Formation ◽  
Ambient Atmosphere ◽  
Atmospheric Conditions ◽  
Mass Fractions

Abstract Atmospheric ice nucleating particles (INPs) influence global climate by altering cloud formation, lifetime, and precipitation efficiency. The role of secondary organic aerosol (SOA) material as a source of INPs in the ambient atmosphere has not been well defined. Here, we demonstrate the potential for biogenic SOA to activate as depositional INPs in the upper troposphere by combining field measurements with laboratory experiments. Ambient INPs were measured in a remote mountaintop location at –46 °C and an ice supersaturation of 30% with concentrations ranging from 0.1 to 70 L–1. Concentrations of depositional INPs were positively correlated with the mass fractions and loadings of isoprene-derived secondary organic aerosols. Compositional analysis of ice residuals showed that ambient particles with isoprene-derived SOA material can act as depositional ice nuclei. Laboratory experiments further demonstrated the ability of isoprene-derived SOA to nucleate ice under a range of atmospheric conditions. We further show that ambient concentrations of isoprene-derived SOA can be competitive with other INP sources. This demonstrates that isoprene and potentially other biogenically-derived SOA materials could influence cirrus formation and properties.

scholarly journals Synergetic formation of secondary inorganic and organic aerosol: Influence of SO<sub>2</sub> and/or NH<sub>3</sub> in the heterogeneous process

2016 ◽  
Author(s):  
Biwu Chu ◽  
Xiao Zhang ◽  
Yongchun Liu ◽  
Hong He ◽  
Yele Sun ◽  
...  
Keyword(s):  
Secondary Organic Aerosol ◽  
Synergistic Effects ◽  
Particle Growth ◽  
Organic Aerosol ◽  
Interactive Effects ◽  
Aerosol Formation ◽  
Secondary Aerosol ◽  
Heterogeneous Process ◽  
So2 Concentration ◽  
Inorganic And Organic

Abstract. The effects of SO2 and NH3 on secondary organic aerosol formation have rarely been investigated together, while the interactive effects between inorganic and organic species under highly complex pollution conditions remain uncertain. Here we studied the effects of SO2 and NH3 on secondary aerosol formation in the photooxidation system of toluene/NOx in the presence or absence of Al2O3 seed aerosols in a 2 m3 smog chamber. The presence of SO2 increased new particle formation and particle growth significantly, regardless of whether NH3 was present or not. Sulfate, organic aerosol, nitrate and ammonium were all found to increase linearly with increasing SO2 concentrations. The increases in these four species were more obvious under NH3-rich conditions, and the generation of nitrate, ammonium and organic aerosol increased more significantly than sulfate with respect to SO2 concentration, while sulfate was the most sensitive species under NH3-poor conditions. The synergistic effects between SO2 and NH3 in the heterogeneous process contributed greatly to secondary aerosol formation. Specifically, the generation of NH4NO3 was found to be highly dependent on the surface area concentration of suspended particles, and increased most significantly among the four species with respect to SO2 concentration under ammonia-rich conditions. Meanwhile, the absorbed NH3 might provide a liquid surface layer for the absorption and subsequent reaction of SO2 and organic products, and therefore, enhance sulfate and secondary organic aerosol (SOA) formation. This effect mainly occurred in the heterogeneous process and resulted in a significantly higher growth rate of seed aerosols compared to that without NH3. By applying positive matrix factorization (PMF) analysis to the AMS data, two factors were identified for the generated SOA. One factor, assigned to less-oxidized organic aerosol and some oligomers, increased with increasing SO2 under NH3-poor conditions, mainly due to the well-known acid catalytic effect of the acid products on SOA formation in the heterogeneous process. The other factor, assigned to the highly oxidized organic component and some nitrogen-containing organics (NOC), increased with SO2 under a NH3-rich environment, with NOC (organonitrates and NOC with reduced N) contributing most of the increase.

Simulating the Formation of Secondary Organic Aerosol from the Photooxidation of Aromatic Hydrocarbons

2005 ◽  
Vol 2 (1) ◽  
pp. 35 ◽  
Author(s):  
David Johnson ◽  
Michael E. Jenkin ◽  
Klaus Wirtz ◽  
Montserrat Martin-Reviejo
Keyword(s):  
Aromatic Hydrocarbons ◽  
Secondary Organic Aerosol ◽  
Organic Aerosol ◽  
Particulate Material ◽  
Chemical Mechanism ◽  
Formation Mechanisms ◽  
Particle Phase ◽  
Radiative Balance ◽  
Aerosol Mass ◽  
Automobile Use

Environmental Context. Atmospheric particulate material can affect the radiative balance of the atmosphere and is believed to be detrimental to human health. Secondary organic aerosols (SOA), which make a significant contribution to the total atmospheric burden of fine particulate material, are formed in situ following the photochemical transformation of organic pollutants into relatively less-volatile, oxygenated compounds which can subsequently transfer from the gas phase to a particle phase. SOA formation from the atmospheric photooxidation of aromatic hydrocarbons—present, for example, as a result of automobile use—is believed to be important in the urban environment and yet the mechanisms are not well understood. For example, even the reasons for observed variations in the relative propensity for SOA formation, from the photooxidation of various simple aromatic hydrocarbons, are not clear. Abstract. The formation and composition of secondary organic aerosol (SOA) from the photooxidation of benzene, p-xylene, and 1,3,5-trimethylbenzene has been simulated using the Master Chemical Mechanism version 3.1 (MCM v3.1) coupled to a representation of the transfer of organic material from the gas to particle phase. The combined mechanism was tested against data obtained from a series of experiments conducted at the European Photoreactor (EUPHORE) outdoor smog chamber in Valencia, Spain. Simulated aerosol mass concentrations compared reasonably well with the measured SOA data only after absorptive partitioning coefficients were increased by a factor of between 5 and 30. The requirement of such scaling was interpreted in terms of the occurrence of unaccounted-for association reactions in the condensed organic phase leading to the production of relatively more nonvolatile species. Comparisons were made between the relative aerosol forming efficiencies of benzene, toluene, p-xylene, and 1,3,5-trimethylbenzene, and differences in the OH-initiated degradation mechanisms of these aromatic hydrocarbons. A strong, nonlinear relationship was observed between measured (reference) yields of SOA and (proportional) yields of unsaturated dicarbonyl aldehyde species resulting from ring-fragmenting pathways. This observation, and the results of the simulations, is strongly suggestive of the involvement of reactive aldehyde species in association reactions occurring in the aerosol phase, thus promoting SOA formation and growth. The effect of NOx concentrations on SOA formation efficiencies (and formation mechanisms) is discussed.

scholarly journals Novel Pathway of SO<sub>2</sub> Oxidation in the Atmosphere: Reactions with Monoterpene Ozonolysis Intermediates and Secondary Organic Aerosol

2017 ◽  
Author(s):  
Jianhuai Ye ◽  
Jonathan P. D. Abbatt ◽  
Arthur W. H. Chan
Keyword(s):  
Secondary Organic Aerosol ◽  
Synergistic Effects ◽  
Organic Aerosol ◽  
Experimental Chamber ◽  
Organic Peroxides ◽  
So2 Oxidation ◽  
Loss Mechanism ◽  
Alpha Pinene ◽  
Criegee Intermediates ◽  
Dry Conditions

Abstract. Ozonolysis of monoterpenes is an important source of atmospheric biogenic secondary organic aerosol (BSOA). While enhanced BSOA formation has been associated with sulfate-rich conditions, the underlying mechanisms remain poorly understood. In this work, the interactions between SO2 and reactive intermediates from monoterpene ozonolysis were investigated under different humidity conditions (10 % vs. 50 %). Chamber experiments were conducted with ozonolysis of alpha-pinene or limonene in the presence of SO2. Limonene SOA formation was enhanced in the presence of SO2, while no significant changes in SOA yields were observed during alpha-pinene ozonolysis. Under dry conditions, SO2 primarily reacted with stabilized Criegee Intermediates (sCI) produced from ozonolysis, but at 50 % RH, heterogeneous uptake of SO2 onto organic aerosol was found to be the dominant sink of SO2, likely owing to reactions between SO2 and organic peroxides. This SO2 loss mechanism to organic peroxides in SOA has not previously been identified in experimental chamber study. Organosulfates were detected and identified using electrospray ionization-ion mobility time of flight mass spectrometer (ESI-IMS-TOF) when SO2 was present in the experiments. Our results demonstrate the synergistic effects between BSOA formation and SO2 oxidation through sCI chemistry and SO2 uptake onto organic aerosol and illustrate the importance of considering the chemistry of organic and sulfur-containing compounds holistically to properly account for their reactive sinks.

Sign in / Sign up

Export Citation Format

Share Document