scholarly journals Humidity-dependent phase state of SOA particles from biogenic and anthropogenic precursors

2012 ◽  
Vol 12 (2) ◽  
pp. 4447-4476 ◽  
Author(s):  
E. Saukko ◽  
A. T. Lambe ◽  
P. Massoli ◽  
J. P. Wright ◽  
D. R. Croasdale ◽  
...  

Abstract. The physical phase state (solid, semi-solid, or liquid) of secondary organic aerosol (SOA) particles has important implications for a number of atmospheric processes. We report the phase state of SOA particles spanning a wide range of oxygen to carbon ratios (O/C), used here as a surrogate for SOA oxidation level, produced in a flow tube reactor by photo-oxidation of various atmospherically relevant surrogate anthropogenic and biogenic volatile organic compounds (VOCs). The phase state of laboratory-generated SOA was determined by the particle bounce behavior after inertial impaction on a polished steel substrate. The measured bounce fraction was evaluated as a function of relative humidity and SOA oxidation level (O/C) measured by an Aerodyne high resolution time of flight aerosol mass spectrometer (HR-ToF AMS). The main findings of the study are: (1) Biogenic and anthropogenic SOA particles are found to be solid or semi-solid until a relative humidity of at least 50 % RH at impaction is reached. (2) Long-chain alkanes produce liquid SOA particles when generated at low oxidation level of O/C<0.2, but at higher oxidation levels they solidify. (3) Increasing sulphuric acid (H2SO4) within the SOA particles reduces the threshold of humidity-induced phase changes. (4) The bounce behavior of the various SOA systems did not show a consistent linear relationship with the particle O/C. Rather, the molar mass of the gas-phase VOC precursor showed a positive correlation with the resistance to the RH-induced phase change of the formed SOA particles.

2012 ◽  
Vol 12 (16) ◽  
pp. 7517-7529 ◽  
Author(s):  
E. Saukko ◽  
A. T. Lambe ◽  
P. Massoli ◽  
T. Koop ◽  
J. P. Wright ◽  
...  

Abstract. The physical phase state (solid, semi-solid, or liquid) of secondary organic aerosol (SOA) particles has important implications for a number of atmospheric processes. We report the phase state of SOA particles spanning a wide range of oxygen to carbon ratios (O / C), used here as a surrogate for SOA oxidation level, produced in a flow tube reactor by photo-oxidation of various atmospherically relevant surrogate anthropogenic and biogenic volatile organic compounds (VOCs). The phase state of laboratory-generated SOA was determined by the particle bounce behavior after inertial impaction on a polished steel substrate. The measured bounce fraction was evaluated as a function of relative humidity and SOA oxidation level (O / C) measured by an Aerodyne high resolution time of flight aerosol mass spectrometer (HR-ToF AMS). The main findings of the study are: (1) biogenic and anthropogenic SOA particles are found to be amorphous solid or semi-solid based on the measured bounced fraction (BF), which was typically higher than 0.6 on a 0 to 1 scale. A decrease in the BF is observed for most systems after the SOA is exposed to relative humidity of at least 80% RH, corresponding to a RH at impaction of 55%. (2) Long-chain alkanes have a low BF (indicating a "liquid-like", less viscous phase) particles at low oxidation levels (BF < 0.2 ± 0.05 for O / C = 0.1). However, BF increases substantially upon increasing oxidation. (3) Increasing the concentration of sulphuric acid (H2SO4) in solid SOA particles (here tested for longifolene SOA) causes a decrease in BF levels. (4) In the majority of cases the bounce behavior of the various SOA systems did not show correlation with the particle O / C. Rather, the molar mass of the gas-phase VOC precursor showed a positive correlation with the resistance to the RH-induced phase change of the formed SOA particles.


2015 ◽  
Vol 15 (16) ◽  
pp. 22263-22289 ◽  
Author(s):  
A. Paciga ◽  
E. Karnezi ◽  
E. Kostenidou ◽  
L. Hildebrandt ◽  
M. Psichoudaki ◽  
...  

Abstract. Using a mass transfer model and the volatility basis set, we estimate the volatility distribution for the organic aerosol (OA) components during summer and winter in Paris, France as part of the collaborative project MEGAPOLI. The concentrations of the OA components as a function of temperature were measured combining data from a thermodenuder and an aerosol mass spectrometer (AMS) with Positive Matrix Factorization (PMF) analysis. The hydrocarbon-like organic aerosol (HOA) had similar volatility distributions for the summer and winter campaigns with half of the material in the saturation concentration bin of 10 μg m−3 and another 35–40 % consisting of low and extremely low volatility organic compounds (LVOCs and ELVOCs, respectively). The winter cooking OA (COA) was more than an order of magnitude less volatile than the summer COA. The low volatility oxygenated OA (LV-OOA) factor detected in the summer had the lowest volatility of all the derived factors and consisted almost exclusively of ELVOCs. The volatility for the semi-volatile oxygenated OA (SV-OOA) was significantly higher than that of the LV-OOA, containing both semi-volatile organic components (SVOCs) and LVOCs. The oxygenated OA (OOA) factor in winter consisted of SVOCs (45 %), LVOCs (25 %) and ELVOCs (30 %). The volatility of marine OA (MOA) was higher than that of the other factors containing around 60 % SVOCs. The biomass burning OA (BBOA) factor contained components with a wide range of volatilities with significant contributions from both SVOCs (50 %) and LVOCs (30 %). Finally, combining the O : C ratio and volatility distributions of the various factors, we incorporated our results into the two-dimensional volatility basis set (2D-VBS). Our results show that the factors cover a broad spectrum of volatilities with no direct link between the average volatility and average O : C of the OA components. Agreement between our findings and previous publications is encouraging for our understanding of the evolution of atmospheric OA.


2020 ◽  
Author(s):  
Hongyu Guo ◽  
Pedro Campuzano-Jost ◽  
Benjamin A. Nault ◽  
Douglas A. Day ◽  
Jason C. Schroder ◽  
...  

Abstract. Aerosol intercomparisons are inherently complex, as they convolve instrument-dependent detection efficiencies vs. size (which often change with pressure, temperature, or humidity) and variations on the sampled aerosol population, in addition to differences in chemical detection principles (e.g., including inorganic-only nitrate vs. inorganic plus organic nitrate for two instruments). The NASA Atmospheric Tomography Mission (ATom) spanned four separate aircraft deployments, which sampled the remote marine troposphere from 86° S to 82° N over different seasons with a wide range of aerosol concentrations and compositions. Aerosols were quantified with a set of carefully characterized and calibrated instruments, some based on particle sizing and some on composition measurements. This study aims to provide a critical evaluation of the size-related factors impacting aerosol intercomparisons, and of aerosol quantification during ATom, with a focus on the Aerosol Mass Spectrometer (AMS). The volume determined from physical sizing instruments is compared in detail with that derived from the chemical measurements of the AMS and the Single Particle Soot Photometer (SP2). Special attention was paid to characterize the upper end of the AMS size-dependent transmission with in-field calibrations, which we show to be critical for accurate comparisons across instruments with inevitably different size cuts. Observed differences between campaigns emphasize the importance of characterizing AMS transmission for each instrument and field study for meaningful interpretation of instrument comparisons. Good agreement was found between the composition-based volume (including AMS-quantified sea salt) and that derived from the size spectrometers. The very clean conditions during most of ATom resulted in substantial statistical noise (i.e., precision error), which we show to be substantially reduced by averaging at several-minute time intervals. The AMS captured, on average, 95 ± 15 % of the standard PM1 volume. These results support the absence of significant unknown biases and the appropriateness of the accuracy estimates for AMS total mass/volume for the mostly aged air masses encountered in ATom. The particle size ranges that contribute chemical composition information to the AMS and complementary composition instruments are investigated, to inform their use in future studies.


2014 ◽  
Vol 7 (12) ◽  
pp. 4507-4516 ◽  
Author(s):  
M. D. Willis ◽  
A. K. Y. Lee ◽  
T. B. Onasch ◽  
E. C. Fortner ◽  
L. R. Williams ◽  
...  

Abstract. The soot-particle aerosol mass spectrometer (SP-AMS) uses an intra-cavity infrared laser to vaporize refractory black carbon (rBC) containing particles, making the particle beam–laser beam overlap critical in determining the collection efficiency (CE) for rBC and associated non-refractory particulate matter (NR-PM). This work evaluates the ability of the SP-AMS to quantify rBC and NR-PM mass in internally mixed particles with different thicknesses of organic coating. Using apparent relative ionization efficiencies for uncoated and thickly coated rBC particles, we report measurements of SP-AMS sensitivity to NR-PM and rBC, for Regal Black, the recommended particulate calibration material. Beam width probe (BWP) measurements are used to illustrate an increase in sensitivity for highly coated particles due to narrowing of the particle beam, which enhances the CE of the SP-AMS by increasing the laser beam–particle beam overlap. Assuming complete overlap for thick coatings, we estimate CE for bare Regal Black particles of 0.6 ± 0.1, which suggests that previously measured SP-AMS sensitivities to Regal Black were underestimated by up to a factor of 2. The efficacy of the BWP measurements is highlighted by studies at a busy road in downtown Toronto and at a non-roadside location, which show particle beam widths similar to, but greater than that of bare Regal Black and coated Regal Black, respectively. Further BWP measurements at field locations will help to constrain the range of CE for fresh and aged rBC-containing particles. The ability of the SP-AMS to quantitatively assess the composition of internally mixed particles is validated through measurements of laboratory-generated organic coated particles, which demonstrate that the SP-AMS can quantify rBC and NR-PM over a wide range of particle compositions and rBC core sizes.


2016 ◽  
Vol 16 (4) ◽  
pp. 2631-2640 ◽  
Author(s):  
Guohua Zhang ◽  
Xinhui Bi ◽  
Ning Qiu ◽  
Bingxue Han ◽  
Qinhao Lin ◽  
...  

Abstract. Knowledge on the microphysical properties of atmospheric aerosols is essential to better evaluate their radiative forcing. This paper presents an estimate of the real part of the refractive indices (n) and effective densities (ρeff) of chemically segregated atmospheric aerosols in Guangzhou, China. Vacuum aerodynamic diameter, chemical compositions, and light-scattering intensities of individual particles were simultaneously measured by a single-particle aerosol mass spectrometer (SPAMS) during the fall of 2012. On the basis of Mie theory, n at a wavelength of 532 nm and ρeff were estimated for 17 particle types in four categories: organics (OC), elemental carbon (EC), internally mixed EC and OC (ECOC), and Metal-rich. The results indicate the presence of spherical or nearly spherical shapes for the majority of particle types, whose partial scattering cross-section versus sizes were well fitted to Mie theoretical modeling results. While sharing n in a narrow range (1.47–1.53), majority of particle types exhibited a wide range of ρeff (0.87–1.51 g cm−3). The OC group is associated with the lowest ρeff (0.87–1.07 g cm−3), and the Metal-rich group with the highest ones (1.29–1.51 g cm−3). It is noteworthy that a specific EC type exhibits a complex scattering curve versus size due to the presence of both compact and irregularly shaped particles. Overall, the results on the detailed relationship between physical and chemical properties benefits future research on the impact of aerosols on visibility and climate.


2016 ◽  
Vol 16 (4) ◽  
pp. 2013-2023 ◽  
Author(s):  
Andrea Paciga ◽  
Eleni Karnezi ◽  
Evangelia Kostenidou ◽  
Lea Hildebrandt ◽  
Magda Psichoudaki ◽  
...  

Abstract. Using a mass transfer model and the volatility basis set, we estimate the volatility distribution for the organic aerosol (OA) components during summer and winter in Paris, France as part of the collaborative project MEGAPOLI. The concentrations of the OA components as a function of temperature were measured combining data from a thermodenuder and an aerosol mass spectrometer (AMS) with Positive Matrix Factorization (PMF) analysis. The hydrocarbon-like organic aerosol (HOA) had similar volatility distributions for the summer and winter campaigns with half of the material in the saturation concentration bin of 10 µg m−3 and another 35–40 % consisting of low and extremely low volatility organic compounds (LVOCs with effective saturation concentrations C* of 10−3–0.1 µg m−3 and ELVOCs C* less or equal than 10−4 µg m−3, respectively). The winter cooking OA (COA) was more than an order of magnitude less volatile than the summer COA. The low-volatility oxygenated OA (LV-OOA) factor detected in the summer had the lowest volatility of all the derived factors and consisted almost exclusively of ELVOCs. The volatility for the semi-volatile oxygenated OA (SV-OOA) was significantly higher than that of the LV-OOA, containing both semi-volatile organic components (SVOCs with C* in the 1–100 µg m−3 range) and LVOCs. The oxygenated OA (OOA) factor in winter consisted of SVOCs (45 %), LVOCs (25 %) and ELVOCs (30 %). The volatility of marine OA (MOA) was higher than that of the other factors containing around 60 % SVOCs. The biomass burning OA (BBOA) factor contained components with a wide range of volatilities with significant contributions from both SVOCs (50 %) and LVOCs (30 %). Finally, combining the bulk average O : C ratios and volatility distributions of the various factors, our results are placed into the two-dimensional volatility basis set (2D-VBS) framework. The OA factors cover a broad spectrum of volatilities with no direct link between the average volatility and average O : C of the OA components.


2019 ◽  
Author(s):  
Weiqi Xu ◽  
Conghui Xie ◽  
Eleni Karnezi ◽  
Qi Zhang ◽  
Junfeng Wang ◽  
...  

Abstract. Volatility plays a key role in affecting mass concentrations and lifetime of aerosol particles in the atmosphere, yet our knowledge of aerosol volatility in relatively polluted environment, e.g., north China remains poor. Here aerosol volatility in Beijing in summer 2017 and 2018 was measured using a thermodenuder (TD) coupled with an Aerodyne high-resolution aerosol mass spectrometer (AMS) and a soot particle AMS. Our results showed overall similar thermograms for most non-refractory aerosol species compared with those reported in previous studies. However, high mass fraction remaining and NO+/NO2+ ratio for chloride and nitrate, respectively above 200 °C indicated the presence of considerable metallic salts and organic nitrates in Beijing. The volatility distributions of organic aerosol (OA) and four OA factors that were resolved from positive matrix factorization were estimated using a mass transfer model. The ambient OA comprised mainly semi-volatile organic compounds (SVOC, 63 %) with an average effective saturation concentration (C*) of 0.55 µg m−3, suggesting overall more volatile properties than OA in megacities of Europe and US. Further analysis showed that the freshly oxidized secondary OA (LO-OOA) was the most volatile OA factor (SVOC = 70 %) followed by hydrocarbon-like OA (HOA). In contrast, the volatility of more oxidized SOA (MO-OOA) was comparable to that of cooking OA with SVOC on average accounting for 60.2 %. We also compared the volatility of ambient and black carbon–containing OA. Our results showed that the BC-containing primary OA (POA) was much more volatile than ambient POA (C*= 0.69 µg m−3 vs. 0.37 µg m−3), while the BC-containing SOA was much less volatile, highlighting the very different composition and properties between BC-containing and ambient aerosol particles.


2011 ◽  
Vol 11 (7) ◽  
pp. 21489-21532 ◽  
Author(s):  
◽  
T. Tritscher ◽  
A. P. Praplan ◽  
P. F. DeCarlo ◽  
B. Temime-Roussel ◽  
...  

Abstract. The aging of secondary organic aerosol (SOA) by photooxidation in the aqueous phase was experimentally investigated. To simulate multiphase processes, the following experiments were sequentially performed in a smog chamber and in an aqueous phase photoreactor: (1) Gas-phase photooxidation of three different volatile organic compounds (VOC): isoprene, α-pinene, and 1,3,5-trimethylbenzene (TMB) in the presence of NOx, leading to the formation of SOA which was subjected to on-line physical and chemical analysis; (2) particle-to-liquid transfer of water soluble species of SOA using filter sampling and aqueous extraction; (3) aqueous-phase photooxidation of the obtained water extracts; and (4) nebulization of the solutions for a repetition of the on-line characterization. SOA concentrations in the chamber measured with a scanning mobility particle sizer (SMPS) were higher than 200 μg m−3, as the experiments were conducted under high initial concentrations of volatile organic compounds (VOC) and NOx. The aging of SOA through aqueous phase processing was investigated by measuring the physical and chemical properties of the particles online before and after processing using a high resolution time-of-flight aerosol mass spectrometer (AMS) and a hygroscopicity tandem differential mobility analyzer (H-TDMA). It was shown that, after aqueous phase processing, the particles were significantly more hygroscopic, and contained more fragmentation ions at m/z = 44 and less ions at m/z = 43, thus showing a significant impact on SOA aging for the three different precursors. Additionally, the particles were analyzed with a thermal desorption atmospheric pressure ionization aerosol mass spectrometer (TD-API-AMS). Comparing the smog chamber SOA composition and non processed nebulized aqueous extracts with this technique revealed that sampling, extraction and/or nebulization did not significantly impact the chemical composition of SOA formed from isoprene and α-pinene, whereas it affected that formed from TMB. For the two first precursors, the aqueous phase chemical composition of SOA was further investigated using offline measurements, i.e. ion chromatography coupled to a mass spectrometer (IC-MS) and an atmospheric pressure chemical ionization mass spectrometer (APCI-MS) equipped with high pressure liquid chromatography (HPLC-MS). These analyses showed that aqueous phase processing enhanced the formation of some compounds already present in the SOA, thus confirming the aging effect of aqueous phase processes. For isoprene experiments, additional new compounds, likely oligomers, were formed through aqueous phase photooxidation, and their possible origins are discussed.


2014 ◽  
Vol 7 (5) ◽  
pp. 5223-5249 ◽  
Author(s):  
M. D. Willis ◽  
A. K. Y. Lee ◽  
T. B. Onasch ◽  
E. C. Fortner ◽  
L. R. Williams ◽  
...  

Abstract. The soot-particle aerosol mass spectrometer (SP-AMS) uses an intra-cavity infrared laser to vaporize refractory black carbon (rBC) containing particles, making the particle beam–laser beam overlap critical in determining the collection efficiency (CE) for rBC and associated non-refractory particulate matter (NR-PM). This work evaluates the ability of the SP-AMS to quantify rBC and NR-PM mass in internally mixed particles with different thicknesses of organic coating. Using apparent relative ionization efficiencies for uncoated and thickly coated rBC particles, we report measurements of SP-AMS sensitivity to NR-PM and rBC, for Regal Black, the recommended particulate calibration material. Beam width probe (BWP) measurements are used to illustrate an increase in sensitivity for highly coated particles due to narrowing of the particle beam, which enhances the CE of the SP-AMS by increasing the laser beam–particle beam overlap. Assuming complete overlap for thick coatings, we estimate CE for bare Regal Black particles of 0.6 ± 0.1, which suggests that previously measured SP-AMS sensitivities to Regal Black were underestimated by up to a factor of two. The efficacy of the BWP measurements is highlighted by studies at a busy road in downtown Toronto and at a non-roadside location, which show particle beam widths similar to, but greater than that of bare Regal Black and coated Regal Black, respectively. Further BWP measurements at field locations will help to constrain the range of CE for fresh and aged rBC-containing particles. The ability of the SP-AMS to quantitatively assess the composition of internally mixed particles is validated through measurements of laboratory-generated organic coated particles, which demonstrate that the SP-AMS can quantify rBC and NR-PM over a wide range of particle compositions and rBC core sizes.


2017 ◽  
Author(s):  
Evangelia Kostenidou ◽  
Eleni Karnezi ◽  
James R. Hite Jr. ◽  
Aikaterini Bougiatioti ◽  
Kate Cerully ◽  
...  

Abstract. The volatility distribution of the organic aerosol (OA) and its sources during the Southern Oxidant and Aerosol Study (SOAS; Centerville, Alabama) was constrained using measurements from an Aerodyne High-Resolution Time-of-Flight Aerosol Mass Spectrometer (HR-ToF-AMS) and a thermodenuder. Positive Matrix Factorization (PMF) analysis was applied on both the ambient and thermodenuded high resolution mass spectra, leading to four factors: more oxidized oxygenated OA (MO-OOA), less oxidized oxygenated OA (LO-OOA), an isoprene epoxydiols (IEPOX) related factor (Isoprene-OA) and biomass burning OA (BBOA). BBOA had the highest mass fraction remaining (MFR) at 100 °C, followed by the isoprene-OA, and the LO-OOA. Surprisingly the MO-OOA evaporated the most in the TD. The estimated effective vaporization enthalpies assuming an evaporation coefficient equal to unity were 58 ± 13 kJ mol−1 for the LO-OOA, 89 ± 10 kJ mol−1 for the MO-OOA, 55 ± 11 kJ mol−1 for the BBOA, and 63 ± 15 kJ mol−1 for the Isoprene-OA. The estimated volatility distribution of all factors covered a wide range including both semi-volatile and low-volatility components. BBOA had the lowest average volatility of all factors, even though it had the lowest O : C ratio among all factors. LO-OOA was the more volatile factor and its high MFR was due according to the model to its low enthalpy of vaporization. The Isoprene-OA factor had intermediate volatility, quite higher than suggested by a few other studies. The analysis suggests that deducing the volatility of a factor only from its MFR could lead to erroneous conclusions. The oxygen content of the factors can be combined with their estimated volatility and hygroscopicity to provide a better view of their physical properties.


Sign in / Sign up

Export Citation Format

Share Document