scholarly journals Composition and volatility of secondary organic aerosol (SOA) formed from oxidation of real tree emissions compared to simplified volatile organic compound (VOC) systems

2020 ◽  
Vol 20 (9) ◽  
pp. 5629-5644 ◽  
Author(s):  
Arttu Ylisirniö ◽  
Angela Buchholz ◽  
Claudia Mohr ◽  
Zijun Li ◽  
Luis Barreira ◽  
...  
Keyword(s):  
Chemical Composition ◽  
Scots Pine ◽  
Flow Reactor ◽  
Secondary Organic Aerosol ◽  
Organic Aerosol ◽  
Oxidation Products ◽  
Mass Yield ◽  
Chemical Complexity ◽  
Volatile Organic ◽  
Plant Emissions

Abstract. Secondary organic aerosol (SOA) is an important constituent of the atmosphere where SOA particles are formed chiefly by the condensation or reactive uptake of oxidation products of volatile organic compounds (VOCs). The mass yield in SOA particle formation, as well as the chemical composition and volatility of the particles, is determined by the identity of the VOC precursor(s) and the oxidation conditions they experience. In this study, we used an oxidation flow reactor to generate biogenic SOA from the oxidation of Scots pine emissions. Mass yields, chemical composition and volatility of the SOA particles were characterized and compared with SOA particles formed from oxidation of α-pinene and from a mixture of acyclic–monocyclic sesquiterpenes (farnesenes and bisabolenes), which are significant components of the Scots pine emissions. SOA mass yields for Scots pine emissions dominated by farnesenes were lower than for α-pinene but higher than for the artificial mixture of farnesenes and bisabolenes. The reduction in the SOA yield in the farnesene- and bisabolene-dominated mixtures is due to exocyclic C=C bond scission in these acyclic–monocyclic sesquiterpenes during ozonolysis leading to smaller and generally more volatile products. SOA particles from the oxidation of Scots pine emissions had similar or lower volatility than SOA particles formed from either a single precursor or a simple mixture of VOCs. Applying physical stress to the Scots pine plants increased their monoterpene, especially monocyclic β-phellandrene, emissions, which further decreased SOA particle volatility and increased SOA mass yield. Our results highlight the need to account for the chemical complexity and structure of real-world biogenic VOC emissions and stress-induced changes to plant emissions when modelling SOA production and properties in the atmosphere. These results emphasize that a simple increase or decrease in relative monoterpene and sesquiterpene emissions should not be used as an indicator of SOA particle volatility.

scholarly journals Composition and volatility of SOA formed from oxidation of real tree emissions compared to single VOC-systems

2019 ◽  
Author(s):  
Arttu Ylisirniö ◽  
Angela Buchholz ◽  
Claudia Mohr ◽  
Zijun Li ◽  
Luis Barreira ◽  
...  
Keyword(s):  
Chemical Composition ◽  
Scots Pine ◽  
Flow Reactor ◽  
Oxidation Products ◽  
Mass Yield ◽  
Chemical Complexity ◽  
Biogenic Voc ◽  
Volatile Products ◽  
Plant Emissions ◽  
Induced Changes

Abstract. Secondary organic aerosol (SOA) is an important constituent of the atmosphere where SOA particles are formed chiefly by the condensation or reactive uptake of oxidation products of volatile organic compounds (VOC). The mass yield in SOA particle formation, as well as the chemical composition and volatility of the particles are determined by the identity of the VOC precursor(s) and the oxidation conditions they experience. In this study, we used an oxidation flow reactor to generate biogenic SOA from the oxidation of Scots pine emissions. Mass yields, chemical composition, and volatility of the SOA particles were characterized and compared with SOA particles formed from oxidation of α-pinene and of a mixture of acyclic/monocyclic sesquiterpenes (farnesenes and bisabolenes), which are significant components of the Scots pine emissions. SOA mass yields for Scots pine emissions dominated by farnesenes were lower than for α-pinene, but higher than for the artificial mixture of farnesenes and bisabolenes. The reduction in the SOA yield in the farnesenes and bisabolenes dominated mixtures is due to C=C bond scission in these acyclic/monocyclic sesquiterpenes during ozonolysis leading to smaller and generally more volatile products. SOA particles from the oxidation of Scots pine emission had similar or lower volatility than SOA particles formed from either of single precursor. Applying physical stress to the Scots pine plants increased monoterpene emissions, which further decreased SOA particle volatility and increased SOA mass yield. Our results highlight the need to account for the chemical complexity and structure of real-world biogenic VOC emissions and stress-induced changes to plant emissions when modelling SOA production and properties in the atmosphere. These results emphasize that simple increase or decrease of relative monoterpene and sesquiterpene emissions should not be used as indicator of SOA particle volatility.

scholarly journals Insights into the O : C dependent mechanisms controlling the evaporation of α-pinene secondary organic aerosol particles

2019 ◽  
Author(s):  
Angela Buchholz ◽  
Andrew T. Lambe ◽  
Arttu Ylisirniö ◽  
Zijun Li ◽  
Olli-Pekka Tikkanen ◽  
...  
Keyword(s):  
Flow Reactor ◽  
Secondary Organic Aerosol ◽  
Organic Aerosol ◽  
Oxidation Products ◽  
Particle Phase ◽  
Volatile Organic ◽  
Isothermal Evaporation ◽  
Key Factor ◽  
Clean Air ◽  
Measured Particle

Abstract. The volatility of oxidation products of volatile organic compounds (VOCs) in the atmosphere is a key factor to determine if they partition into the particle phase contributing to secondary organic aerosol (SOA) mass. Thus, linking volatility and measured particle composition will provide insights into SOA formation and its fate in the atmosphere. We produced a-pinene SOA with three different oxidation levels (characterised by average oxygen to carbon ratio, O : C = 0.53, 0.69, and 0.96) in an oxidation flow reactor. We investigated the particle volatility by isothermal evaporation in clean air as a function of relative humidity (RH 

scholarly journals Large contribution to secondary organic aerosol from isoprene cloud chemistry

2021 ◽  
Vol 7 (13) ◽  
pp. eabe2952
Author(s):  
Houssni Lamkaddam ◽  
Josef Dommen ◽  
Ananth Ranjithkumar ◽  
Hamish Gordon ◽  
Günther Wehrle ◽  
...  
Keyword(s):  
Radiative Forcing ◽  
Flow Reactor ◽  
Secondary Organic Aerosol ◽  
Cloud Droplet ◽  
Organic Aerosol ◽  
Global Scale ◽  
Oxidation Products ◽  
Oh Radicals ◽  
Large Contribution ◽  
Cloud Processing

Aerosols still present the largest uncertainty in estimating anthropogenic radiative forcing. Cloud processing is potentially important for secondary organic aerosol (SOA) formation, a major aerosol component: however, laboratory experiments fail to mimic this process under atmospherically relevant conditions. We developed a wetted-wall flow reactor to simulate aqueous-phase processing of isoprene oxidation products (iOP) in cloud droplets. We find that 50 to 70% (in moles) of iOP partition into the aqueous cloud phase, where they rapidly react with OH radicals, producing SOA with a molar yield of 0.45 after cloud droplet evaporation. Integrating our experimental results into a global model, we show that clouds effectively boost the amount of SOA. We conclude that, on a global scale, cloud processing of iOP produces 6.9 Tg of SOA per year or approximately 20% of the total biogenic SOA burden and is the main source of SOA in the mid-troposphere (4 to 6 km).

scholarly journals Temperature and volatile organic compound concentrations as controlling factors for chemical composition of <i>α</i>-pinene-derived secondary organic aerosol

2021 ◽  
Vol 21 (15) ◽  
pp. 11545-11562
Author(s):  
Louise N. Jensen ◽  
Manjula R. Canagaratna ◽  
Kasper Kristensen ◽  
Lauriane L. J. Quéléver ◽  
Bernadette Rosati ◽  
...  
Keyword(s):  
Chemical Composition ◽  
Organic Compound ◽  
Organic Acids ◽  
Organic Acid ◽  
Elemental Composition ◽  
Volatile Organic Compound ◽  
Secondary Organic Aerosol ◽  
Organic Aerosol ◽  
Oxidation Level ◽  
Volatile Organic

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.

scholarly journals In situ secondary organic aerosol formation from ambient pine forest air using an oxidation flow reactor

2015 ◽  
Vol 15 (21) ◽  
pp. 30409-30471 ◽  
Author(s):  
B. B. Palm ◽  
P. Campuzano-Jost ◽  
A. M. Ortega ◽  
D. A. Day ◽  
L. Kaser ◽  
...  
Keyword(s):  
Organic Compounds ◽  
Flow Reactor ◽  
Secondary Organic Aerosol ◽  
Ambient Air ◽  
Organic Aerosol ◽  
Pine Forest ◽  
Oxidation Products ◽  
Oh Radicals ◽  
Aerosol Formation ◽  
Photochemical Aging

Abstract. Ambient air was oxidized by OH radicals in an oxidation flow reactor (OFR) located in a montane pine forest during the BEACHON-RoMBAS campaign to study biogenic secondary organic aerosol (SOA) formation and aging. High OH concentrations and short residence times allowed for semi-continuous cycling through a large range of OH exposures ranging from hours to weeks of equivalent (eq.) atmospheric aging. A simple model is derived and used to account for the relative time scales of condensation of low volatility organic compounds (LVOCs) onto particles, condensational loss to the walls, and further reaction to produce volatile, non-condensing fragmentation products. More SOA production was observed in the OFR at nighttime (average 4 μg m-3 when LVOC fate corrected) compared to daytime (average 1 μg m-3 when LVOC fate corrected), with maximum formation observed at 0.4–1.5 eq. days of photochemical aging. SOA formation followed a similar diurnal pattern to monoterpenes, sesquiterpenes, and toluene + p-cymene concentrations, including a substantial increase just after sunrise at 07:00 LT. Higher photochemical aging (> 10 eq. days) led to a decrease in new SOA formation and a loss of preexisting OA due to heterogeneous oxidation followed by fragmentation and volatilization. When comparing two different commonly used methods of OH production in OFRs (OFR185 and OFR254), similar amounts of SOA formation were observed. We recommend the OFR185 mode for future forest studies. Concurrent gas-phase measurements of air after OH oxidation illustrate the decay of primary VOCs, production of small oxidized organic compounds, and net production at lower ages followed by net consumption of terpenoid oxidation products as photochemical age increased. New particle formation was observed in the reactor after oxidation, especially during times when precursor gas concentrations and SOA formation were largest. Approximately 6 times more SOA was formed in the reactor from OH oxidation than could be explained by the VOCs measured in ambient air. Several recently-developed instruments quantified ambient semi- and intermediate-volatility organic compounds (S/IVOCs) that were not detected by a PTR-TOF-MS. An SOA yield of 24–80 % from those compounds can explain the observed SOA, suggesting that these typically unmeasured S/IVOCs play a substantial role in ambient SOA formation. Our results allow ruling out condensation sticking coefficients much lower than 1. Our measurements help clarify the magnitude of SOA formation in forested environments, and demonstrate methods for interpretation of ambient OFR measurements.

scholarly journals Insights into the O : C-dependent mechanisms controlling the evaporation of <i>α</i>-pinene secondary organic aerosol particles

2019 ◽  
Vol 19 (6) ◽  
pp. 4061-4073 ◽  
Author(s):  
Angela Buchholz ◽  
Andrew T. Lambe ◽  
Arttu Ylisirniö ◽  
Zijun Li ◽  
Olli-Pekka Tikkanen ◽  
...  
Keyword(s):  
Thermal Desorption ◽  
Flow Reactor ◽  
Secondary Organic Aerosol ◽  
Direct Consequence ◽  
Organic Aerosol ◽  
Oxidation Products ◽  
Desorption Temperature ◽  
Key Factor ◽  
High Volatility ◽  
Semi Solid

Abstract. The volatility of oxidation products of volatile organic compounds (VOCs) in the atmosphere is a key factor to determine if they partition into the particle phase contributing to secondary organic aerosol (SOA) mass. Thus, linking volatility and measured particle composition will provide insights into SOA formation and its fate in the atmosphere. We produced α-pinene SOA with three different oxidation levels (characterized by average oxygen-to-carbon ratio; O:C‾=0.53, 0.69, and 0.96) in an oxidation flow reactor. We investigated the particle volatility by isothermal evaporation in clean air as a function of relative humidity (RH <2 %, 40 %, and 80 %) and used a filter-based thermal desorption method to gain volatility and chemical composition information. We observed reduced particle evaporation for particles with increasing O:C‾ ratio, indicating that particles become more resilient to evaporation with oxidative aging. Particle evaporation was increased in the presence of water vapour and presumably particulate water; at the same time the resistance of the residual particles to thermal desorption was increased as well. For SOA with O:C‾=0.96, the unexpectedly large increase in mean thermal desorption temperature and changes in the thermogram shapes under wet conditions (80 % RH) were an indication of aqueous phase chemistry. For the lower O:C‾ cases, some water-induced composition changes were observed. However, the enhanced evaporation under wet conditions could be explained by the reduction in particle viscosity from the semi-solid to liquid-like range, and the observed higher desorption temperature of the residual particles is a direct consequence of the increased removal of high-volatility and the continued presence of low-volatility compounds.

scholarly journals Effect of oxidant concentration, exposure time, and seed particles on secondary organic aerosol chemical composition and yield

2015 ◽  
Vol 15 (6) ◽  
pp. 3063-3075 ◽  
Author(s):  
A. T. Lambe ◽  
P. S. Chhabra ◽  
T. B. Onasch ◽  
W. H. Brune ◽  
J. F. Hunter ◽  
...  
Keyword(s):  
Chemical Composition ◽  
Gas Phase ◽  
Flow Reactor ◽  
Secondary Organic Aerosol ◽  
Organic Aerosol ◽  
Short Exposure ◽  
Heterogeneous Oxidation ◽  
Seed Particles ◽  
Aerosol Mass ◽  
Environmental Chambers

Abstract. We performed a systematic intercomparison study of the chemistry and yields of secondary organic aerosol (SOA) generated from OH oxidation of a common set of gas-phase precursors in a Potential Aerosol Mass (PAM) continuous flow reactor and several environmental chambers. In the flow reactor, SOA precursors were oxidized using OH concentrations ranging from 2.0 × 108 to 2.2 × 1010 molec cm−3 over exposure times of 100 s. In the environmental chambers, precursors were oxidized using OH concentrations ranging from 2 × 106 to 2 × 107 molec cm−3 over exposure times of several hours. The OH concentration in the chamber experiments is close to that found in the atmosphere, but the integrated OH exposure in the flow reactor can simulate atmospheric exposure times of multiple days compared to chamber exposure times of only a day or so. In most cases, for a specific SOA type the most-oxidized chamber SOA and the least-oxidized flow reactor SOA have similar mass spectra, oxygen-to-carbon and hydrogen-to-carbon ratios, and carbon oxidation states at integrated OH exposures between approximately 1 × 1011 and 2 × 1011 molec cm−3 s, or about 1–2 days of equivalent atmospheric oxidation. This observation suggests that in the range of available OH exposure overlap for the flow reactor and chambers, SOA elemental composition as measured by an aerosol mass spectrometer is similar whether the precursor is exposed to low OH concentrations over long exposure times or high OH concentrations over short exposure times. This similarity in turn suggests that both in the flow reactor and in chambers, SOA chemical composition at low OH exposure is governed primarily by gas-phase OH oxidation of the precursors rather than heterogeneous oxidation of the condensed particles. In general, SOA yields measured in the flow reactor are lower than measured in chambers for the range of equivalent OH exposures that can be measured in both the flow reactor and chambers. The influence of sulfate seed particles on isoprene SOA yield measurements was examined in the flow reactor. The studies show that seed particles increase the yield of SOA produced in flow reactors by a factor of 3 to 5 and may also account in part for higher SOA yields obtained in the chambers, where seed particles are routinely used.

scholarly journals Aging of secondary organic aerosol from small aromatic VOCs: changes in chemical composition, mass yield, volatility and hygroscopicity

2014 ◽  
Vol 14 (22) ◽  
pp. 31441-31481 ◽  
Author(s):  
L. Hildebrandt Ruiz ◽  
A. L. Paciga ◽  
K. Cerully ◽  
A. Nenes ◽  
N. M. Donahue ◽  
...  
Keyword(s):  
Oxidation State ◽  
Secondary Organic Aerosol ◽  
Organic Aerosol ◽  
Clear Correlation ◽  
Carbon Oxidation ◽  
Mass Yield ◽  
Initial Formation ◽  
Chemical Aging ◽  
Photo Oxidation ◽  
Volatile Organic

Abstract. Secondary organic aerosol (SOA) is transformed after its initial formation, but this chemical aging of SOA is poorly understood. Experiments were conducted in the Carnegie Mellon environmental chamber to form and transform SOA from the photo-oxidation of toluene and other small aromatic volatile organic compounds (VOCs) in the presence of NOx. The effects of chemical aging on organic aerosol (OA) composition, mass yield, volatility and hygroscopicity were explored. Higher exposure to the hydroxyl radical resulted in different OA composition, average carbon oxidation state OSC) and mass yield. The OA oxidation state generally increased during photo-oxidation, and the final OA OS C ranged from −0.29 to 0.45 in the performed experiments. The volatility of OA formed in these different experiments varied by as much as a factor of 30, demonstrating that the OA formed under different oxidizing conditions can have significantly different saturation concentration. There was no clear correlation between hygroscopicity and oxidation state for this relatively hygroscopic SOA.

scholarly journals Secondary Organic Aerosol Reduced by Mixture of Atmospheric Vapours

2020 ◽  
Author(s):  
Thomas Mentel ◽  
Gordon McFiggans ◽  
Jürgen Wildt ◽  
Astrid Kiendler-Scharr ◽  
Keyword(s):  
Secondary Organic Aerosol ◽  
Organic Aerosol ◽  
Oh Radicals ◽  
Peroxy Radicals ◽  
Model Calculations ◽  
Volatile Organic ◽  
Single Precursor ◽  
Real Atmosphere ◽  
Isoprene Oxidation ◽  
Plant Emissions

&lt;p&gt;Biogenic volatile organic compounds (VOC) are important secondary organic aerosol (SOA) precursors. Whilst isoprene dominates VOC plant emissions globally, its yield of SOA mass is found to be modest in comparison to that of monoterpenes (MT). Tracers from isoprene oxidation have been observed in particles showing that they condense from the gas phase and yet new particle formation is suppressed by the presence of isoprene in mixtures of plant emissions containing MT.&lt;/p&gt;&lt;p&gt;Experiments were performed in the JPAC chamber in J&amp;#252;lich. We showed that isoprene can suppress both the instantaneous mass formation and overall yield of monoterpenes in mixtures by two effects: oxidant and product scavenging. Isoprene scavenged OH radicals from reacting with MT (oxidant scavenging). Subsequently, the resulting isoprene peroxy radicals reacted with highly oxygenated peroxy radicals from MT oxidation (product scavenging). These effects from isoprene, also demonstrated using CO or CH&lt;sub&gt;4&lt;/sub&gt;, reduced the yield of low-volatility, highly oxygenated molecules (HOM) from MT that would otherwise form SOA.&lt;/p&gt;&lt;p&gt;Our results show that in mixtures changes in particle mass and number are not additive, and yields from single precursor experiments cannot simply be linearly combined. Reactive, modest SOA yield compounds are not necessarily net SOA producers and isoprene oxidation can suppress both SOA number and mass. Global model calculations support that OH scavenging and product scavenging can also operate in the real atmosphere. Our results highlight a need for more realistic consideration of SOA formation in the atmosphere analogous to the treatment of ozone formation, where interactions between the mechanistic pathways involving peroxy radicals are recognised to be essential.&lt;/p&gt;

scholarly journals Potential dual effect of anthropogenic emissions on the formation of biogenic secondary organic aerosol (BSOA)

2019 ◽  
Vol 19 (24) ◽  
pp. 15651-15671 ◽  
Author(s):  
Eetu Kari ◽  
Liqing Hao ◽  
Arttu Ylisirniö ◽  
Angela Buchholz ◽  
Ari Leskinen ◽  
...  
Keyword(s):  
Volatile Organic Compounds ◽  
Gas Phase ◽  
Organic Compounds ◽  
Vehicle Emissions ◽  
Secondary Organic Aerosol ◽  
Organic Aerosol ◽  
Anthropogenic Emissions ◽  
Mass Yield ◽  
Vehicle Exhaust ◽  
Volatile Organic

Abstract. The fraction of gasoline direct-injection (GDI) vehicles comprising the total vehicle pool is projected to increase in the future. However, thorough knowledge about the influence of GDI engines on important atmospheric chemistry processes is missing – namely, their contribution to secondary organic aerosol (SOA) precursor emissions, contribution to SOA formation, and potential role in biogenic–anthropogenic interactions. The objectives of this study were to (1) characterize emissions from modern GDI vehicles and investigate their role in SOA formation chemistry and (2) investigate biogenic–anthropogenic interactions related to SOA formation from a mixture of GDI-vehicle emissions and a model biogenic compound, α-pinene. Specifically, we studied SOA formation from modern GDI-vehicle emissions during the constant-load driving. In this study we show that SOA formation from GDI-vehicle emissions was observed in each experiment. Volatile organic compounds (VOCs) measured with the proton-transfer-reaction time-of-flight mass spectrometer (PTR-ToF-MS) could account for 19 %–42 % of total SOA mass generated in each experiment. This suggests that there were lower-volatility intermediate VOCs (IVOCs) and semi-volatile organic compounds (SVOCs) in the GDI-vehicle exhaust that likely contributed to SOA production but were not detected with the instrumentation used in this study. This study also demonstrates that two distinct mechanisms caused by anthropogenic emissions suppress α-pinene SOA mass yield. The first suppressing effect was the presence of NOx. This mechanism is consistent with previous reports demonstrating suppression of biogenic SOA formation in the presence of anthropogenic emissions. Our results indicate a possible second suppressing effect, and we suggest that the presence of anthropogenic gas-phase species may have suppressed biogenic SOA formation by alterations to the gas-phase chemistry of α-pinene. This hypothesized change in oxidation pathways led to the formation of α-pinene oxidation products that most likely did not have vapor pressures low enough to partition into the particle phase. Overall, the presence of gasoline-vehicle exhaust caused a more than 50 % suppression in α-pinene SOA mass yield compared to the α-pinene SOA mass yield measured in the absence of any anthropogenic influence.

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