scholarly journals Comparison of secondary organic aerosol formation from toluene on initially wet and dry ammonium sulfate particles at moderate relative humidity

2018 ◽  
Vol 18 (8) ◽  
pp. 5677-5689 ◽  
Author(s):  
Tengyu Liu ◽  
Dan Dan Huang ◽  
Zijun Li ◽  
Qianyun Liu ◽  
ManNin Chan ◽  
...  
Keyword(s):  
Relative Humidity ◽  
Ammonium Sulfate ◽  
Functional Groups ◽  
Flow Reactor ◽  
Secondary Organic Aerosol ◽  
Organic Aerosol ◽  
Aerosol Formation ◽  
Seed Particles ◽  
The Difference ◽  
Wet Particles

Abstract. The formation of secondary organic aerosol (SOA) has been widely studied in the presence of dry seed particles at low relative humidity (RH). At higher RH, initially dry seed particles can exist as wet particles due to water uptake by the seeds as well as the SOA. Here, we investigated the formation of SOA from the photooxidation of toluene using an oxidation flow reactor in the absence of NOx under a range of OH exposures on initially wet or dry ammonium sulfate (AS) seed particles at an RH of 68 %. The ratio of the SOA yield on wet AS seeds to that on dry AS seeds, the relative SOA yield, decreased from 1.31 ± 0.02 at an OH exposure of 4.66 × 1010 molecules cm−3 s to 1.01 ± 0.01 at an OH exposure of 5.28 × 1011 molecules cm−3 s. This decrease may be due to the early deliquescence of initially dry AS seeds after being coated by highly oxidized toluene-derived SOA. SOA formation lowered the deliquescence RH of AS and resulted in the uptake of water by both AS and SOA. Hence the initially dry AS seeds contained aerosol liquid water (ALW) soon after SOA formed, and the SOA yield and ALW approached those of the initially wet AS seeds as OH exposure and ALW increased, especially at high OH exposure. However, a higher oxidation state of the SOA on initially wet AS seeds than that on dry AS seeds was observed at all levels of OH exposure. The difference in mass fractions of m ∕ z 29, 43 and 44 of SOA mass spectra, obtained using an aerosol mass spectrometer (AMS), indicated that SOA formed on initially wet seeds may be enriched in earlier-generation products containing carbonyl functional groups at low OH exposures and later-generation products containing acidic functional groups at high exposures. Our results suggest that inorganic dry seeds become at least partially deliquesced particles during SOA formation and hence that ALW is inevitably involved in the SOA formation at moderate RH. More laboratory experiments conducted with a wide variety of SOA precursors and inorganic seeds under different NOx and RH conditions are warranted.

scholarly journals Comparison of secondary organic aerosol formation from toluene on initially wet and dry ammonium sulfate particles

2017 ◽  
Author(s):  
Tengyu Liu ◽  
Dan Dan Huang ◽  
Zijun Li ◽  
Qianyun Liu ◽  
ManNin Chan ◽  
...  
Keyword(s):  
Ammonium Sulfate ◽  
Functional Groups ◽  
Flow Reactor ◽  
Secondary Organic Aerosol ◽  
Large Fraction ◽  
Organic Aerosol ◽  
Aerosol Formation ◽  
Seed Particles ◽  
The Difference ◽  
Wet Particles

Abstract. The formation of secondary organic aerosol (SOA) has been widely studied in the presence of dry seed particles at low relative humidity (RH). At higher RH, seed particles can exist as dry or wet particles. Here, we investigated the formation of SOA from the photooxidation of toluene using an oxidation flow reactor under a range of OH exposures on initially wet or dry ammonium sulfate (AS) seed particles at an RH of 68 %. At an OH exposure of 4.66 × 1010 molecules cm -3 s, the ratio of the SOA yield on wet AS seeds to that on dry AS seeds was 1.31 ± 0.02. However, this ratio decreased to 1.01 ± 0.01 at an OH exposure of 5.28 × 1011 molecules cm -3 s. The decrease in the ratios of SOA yields as the increase of OH exposure may be due to the early deliquescence of initially dry AS seeds after coated by highly oxidized toluene-derived SOA. SOA formation lowered the deliquescence RH of AS and resulted in the uptake of water by both AS and SOA. Hence the initially dry AS seeds contained aerosol liquid water (ALW) soon after a large fraction of SOA formed and the SOA yield and ALW approached those of the initially wet AS seeds as OH exposure and ALW increased. However, a higher oxidation state of the SOA on initially wet AS seeds than that on dry AS seeds was observed at all levels of OH exposure. The difference in mass fractions of m/z 29, 43 and 44 of SOA mass spectra indicated that SOA formed on initially wet seeds may be enriched in earlier-generation products containing carbonyl functional groups at low OH exposures and later-generation products containing acidic functional groups at high exposures. Our results suggest that AS dry seeds soon turn to at least partially deliquesced particles during SOA formation and more studies on the interplay of SOA formation and ALW are warranted.

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 Enhancement of Secondary Organic Aerosol Formation and its Oxidation State by SO<sub>2</sub> during Photooxidation of 2-Methoxyphenol

2018 ◽  
Author(s):  
Changgeng Liu ◽  
Tianzeng Chen ◽  
Yongchun Liu ◽  
Jun Liu ◽  
Hong He ◽  
...  
Keyword(s):  
Oxidation State ◽  
Secondary Organic Aerosol ◽  
Organic Aerosol ◽  
Wood Smoke ◽  
Organic Nitrates ◽  
Carbon Oxidation ◽  
Formation Processes ◽  
Aerosol Formation ◽  
Product Model ◽  
Seed Particles

Abstract. 2-Methoxyphenol (guaiacol) is derived from the lignin pyrolysis and taken as a potential tracer for wood smoke emissions. In this work, the effect of SO2 at atmospheric levels (0–56 ppb) on secondary organic aerosol (SOA) formation and its oxidation state during guaiacol photooxidation was investigated in the presence of various inorganic seed particles (NaCl and (NH4)2SO4). Without SO2 and seed particles, SOA yields (9.46–26.37 %) obtained at different guaiacol concentration (138.83–2197.36 μg m−3) could be well expressed by a one-product model. The presence of SO2 resulted in enhancing SOA yield by 14.05–23.66 %. With (NH4)2SO4 and NaCl seed particles, SOA yield was enhanced by 23.06 % and 29.57 %, respectively, which further increased significantly to 29.78–53.47 % in the presence of SO2, suggesting that SO2 and seed particles have a synergetic contribution to SOA formation. It should be noted that SO2 was found to be in favor of increasing the carbon oxidation state (OSC) of SOA, indicating that the functionalization reaction should be more dominant than oligomerization reaction. In addition, the average N/C ratio of SOA was 0.037, which revealed that NOx participated in the photooxidation process, consequently leading to the formation of organic nitrates. The experimental results demonstrate the importance of SO2 on the formation processes of SOA and organosulfates, and also are helpful to further understand SOA formation from the atmospheric photooxidation of guaiacol and its subsequent impacts on air quality and climate.

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 Chamber investigation of the formation and transformation of secondary organic aerosol in mixtures of biogenic and anthropogenic volatile organic compounds

2022 ◽  
Author(s):  
Aristeidis Voliotis ◽  
Mao Du ◽  
Yu Wang ◽  
Yunqi Shao ◽  
M. Rami Alfarra ◽  
...  
Keyword(s):  
Secondary Organic Aerosol ◽  
Organic Aerosol ◽  
Phase Behaviour ◽  
Ternary Mixtures ◽  
Base Case ◽  
Formation Potential ◽  
Seed Particles ◽  
Volatile Organic ◽  
The Difference ◽  
Initial Reactivity

Abstract. A comprehensive investigation of the photochemical secondary organic aerosol (SOA) formation and transformation in mixtures of anthropogenic (o-cresol) and biogenic (α-pinene and isoprene) volatile organic compound (VOC) precursors in the presence of NOx and inorganic seed particles was conducted. Initial iso-reactivity was used to enable direct comparison across systems, adjusting the initial reactivity of the systems towards the assumed dominant oxidant (OH). Comparing experiments conducted in single precursor systems at various initial reactivity levels (referenced to a nominal base case VOC reactivity) and their binary and ternary mixtures, we show that the molecular interactions from the mixing of the precursors can be investigated and discuss limitations in their interpretation. The observed average SOA yields in descending order were found for the α-pinene (32 ± 7 %), α-pinene/o-cresol (28 ± 9 %), α-pinene at ½ initial reactivity (21 ± 5 %), α-pinene/isoprene (16 ± 1 %), α-pinene at ⅓ initial reactivity (15 ± 4 %), o-cresol (13 ± 3 %), α-pinene/o-cresol/isoprene (11 ± 4%), o-cresol at ½ initial reactivity (11 ± 3 %), o-cresol/isoprene (6 ± 2 %) and isoprene systems (0 ± 0 %). We find a clear suppression of the SOA yield from α-pinene when it is mixed with isoprene, whilst the addition of isoprene to o-cresol may enhance the mixture’s SOA formation potential, however, the difference was too small to be unequivocal. The α-pinene/o-cresol system yield appeared to be increased compared to that calculated based on the additivity, whilst in the α-pinene/o-cresol/isoprene system the measured and predicted yield were comparable. However, in mixtures where more than one precursor contributes to the SOA mass it is unclear whether changes in the SOA formation potential are attributable to physical or chemical interactions, since the reference basis for the comparison is complex. Online and offline chemical composition and SOA particle volatility, water uptake and “phase” behaviour measurements that were used to interpret the SOA formation and behaviour are introduced and detailed elsewhere.

scholarly journals Sensitivities of the absorptive partitioning model of secondary organic aerosol formation to the inclusion of water

2008 ◽  
Vol 8 (6) ◽  
pp. 20311-20348 ◽  
Author(s):  
M. Barley ◽  
D. O. Topping ◽  
G. McFiggans ◽  
M. E. Jenkin
Keyword(s):  
Relative Humidity ◽  
Secondary Organic Aerosol ◽  
Organic Aerosol ◽  
Organic Component ◽  
Condensed Phases ◽  
Aerosol Formation ◽  
Ambient Relative Humidity ◽  
Highly Sensitive ◽  
Volatile Organic ◽  
Secondary Organic Aerosol Formation

Abstract. Depending on the assumptions about the participation of water in absorptive partitioning, the prediction of the distribution of semi-volatile organic component between the gaseous and condensed phases is shown to be highly sensitive to the ambient relative humidity and the formulation of the partitioning model used. Further sensitivities to the assumed pre-existing particulate loading and to parameterised organic component non-ideality are explored and shown to contribute significantly to the variation in predicted secondary organic particulate loading.

scholarly journals Temperature dependence of secondary organic aerosol yield from the ozonolysis of β-pinene

2006 ◽  
Vol 6 (5) ◽  
pp. 10275-10297 ◽  
Author(s):  
C. Stenby ◽  
U. Pöschl ◽  
P. von Hessberg ◽  
M. Bilde ◽  
O. J. Nielsen ◽  
...  
Keyword(s):  
Temperature Dependence ◽  
Gas Phase ◽  
Flow Reactor ◽  
Secondary Organic Aerosol ◽  
Measurement Data ◽  
Organic Aerosol ◽  
Reaction Products ◽  
Aerosol Formation ◽  
Product Model ◽  
High Particle

Abstract. The temperature dependence of secondary organic aerosol (SOA) formation from ozonolysis of β-pinene was studied in a flow reactor at 263–303 K and 1007 hPa. The observed SOA yields were of similar magnitude as predicted by a two-product model based on detailed gas phase chemistry (Jenkin, 2004), reaching maximum values of 0.22–0.39 at high particle mass concentrations. However, the measurement data exhibited significant deviations (up to 50%) from the predicted linear dependence on inverse temperature. When fitting the measurement data with a two-product model, we found that both the partitioning coefficients (Kom,i) and the stoichiometric yields (αi) of the low-volatile and semi-volatile species vary with temperature. The results indicate that not only the reaction product vapour pressures but also the relative contributions of different gas-phase or multiphase reaction channels are dependent on temperature. We suggest that the modelling of secondary organic aerosol formation in the atmosphere needs to take into account the effects of temperature on the pathways and kinetics of the involved chemical reactions as well as on the gas-particle partitioning of the reaction products.

scholarly journals Secondary organic aerosol formation from OH-initiated oxidation of <i>m</i>-xylene: effects of relative humidity on yield and chemical composition

2019 ◽  
Author(s):  
Qun Zhang ◽  
Yongfu Xu ◽  
Long Jia
Keyword(s):  
Relative Humidity ◽  
Mass Spectrometer ◽  
Secondary Organic Aerosol ◽  
Organic Aerosol ◽  
Chemical Mechanism ◽  
Oh Radicals ◽  
Aerosol Formation ◽  
Scanning Mobility Particle Sizer ◽  
Significant Discrepancy ◽  
Liquid Chromatograph

Abstract. The effect of relative humidity (RH) on the secondary organic aerosol (SOA) formation from the photooxidation of m-xylene initiated by OH radicals in the absence of seed particles was investigated in a smog chamber. The SOA yields were determined based on the particle mass concentrations measured with a scanning mobility particle sizer (SMPS) and reacted m-xylene concentrations measured with a gas chromatograph-mass spectrometer (GC-MS). The SOA components were analyzed using Fourier transform infrared spectrometer (FTIR) and ultrahigh performance liquid chromatograph-electrospray ionization-high-resolution mass spectrometer (UPLC-ESI-HRMS). A significant discrepancy was observed in SOA mass concentration and yield variation with the RH conditions. The SOA yield is 13.8 % and 0.8 % at low RH (13.7 %) and high RH (79.1 %), respectively, with the difference being over an order of magnitude. The relative increase of C-O-C at high RH from the FTIR analysis of functional groups indicates that the oligomers from carbonyl compounds cannot well explain the suppression of SOA yield. Highly oxygenated molecules (HOMs) were observed to be suppressed in the HRMS spectra. The chemical mechanism for explaining the RH effects on SOA formation from m-xylene-OH system is proposed based on the analysis of both FTIR and HRMS measurements as well as Master Chemical Mechanism (MCM) simulations. The reduced SOA at high RH is mainly ascribed to the less formation of oligomers and the suppression of RO2 autoxidation. As a result, high RH can obstruct the oligomerization and autoxidation that contribute to the SOA formation.

scholarly journals Rate constant and secondary organic aerosol formation from the gas-phase reaction of eugenol with hydroxyl radicals

2019 ◽  
Vol 19 (3) ◽  
pp. 2001-2013 ◽  
Author(s):  
Changgeng Liu ◽  
Yongchun Liu ◽  
Tianzeng Chen ◽  
Jun Liu ◽  
Hong He
Keyword(s):  
Rate Constant ◽  
Flow Reactor ◽  
Secondary Organic Aerosol ◽  
Relative Rate ◽  
Organic Aerosol ◽  
Organic Nitrates ◽  
Phase Reaction ◽  
Aerosol Formation ◽  
Product Model ◽  
Formation Potential

Abstract. Methoxyphenols are an important organic component of wood-burning emissions and considered to be potential precursors of secondary organic aerosol (SOA). In this work, the rate constant and SOA formation potential for the OH-initiated reaction of 4-allyl-2-methoxyphenol (eugenol) were investigated for the first time in an oxidation flow reactor (OFR). The rate constant was 8.01±0.40×10-11 cm3 molecule−1 s−1, determined by the relative rate method. The SOA yield first increased and then decreased as a function of OH exposure and was also dependent on eugenol concentration. The maximum SOA yields (0.11–0.31) obtained at different eugenol concentrations could be expressed well by a one-product model. The carbon oxidation state (OSC) increased linearly and significantly as OH exposure rose, indicating that a high oxidation degree was achieved for SOA. In addition, the presence of SO2 (0–198 ppbv) and NO2 (0–109 ppbv) was conducive to increasing SOA yield, for which the maximum enhancement values were 38.6 % and 19.2 %, respectively. The N∕C ratio (0.032–0.043) indicated that NO2 participated in the OH-initiated reaction, subsequently forming organic nitrates. The results could be helpful for further understanding the SOA formation potential from the atmospheric oxidation of methoxyphenols and the atmospheric aging process of smoke plumes from biomass burning emissions.

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