scholarly journals Volatility of organic aerosol and its components in the Megacity of Paris

2015 ◽  
Vol 15 (16) ◽  
pp. 22263-22289 ◽  
Author(s):  
A. Paciga ◽  
E. Karnezi ◽  
E. Kostenidou ◽  
L. Hildebrandt ◽  
M. Psichoudaki ◽  
...  
Keyword(s):  
Organic Aerosol ◽  
Basis Set ◽  
Transfer Model ◽  
Collaborative Project ◽  
Aerosol Mass Spectrometer ◽  
Aerosol Mass ◽  
Combining Data ◽  
Wide Range ◽  
Volatile Organic ◽  
Order Of Magnitude

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.

scholarly journals Volatility of organic aerosol and its components in the megacity of Paris

2016 ◽  
Vol 16 (4) ◽  
pp. 2013-2023 ◽  
Author(s):  
Andrea Paciga ◽  
Eleni Karnezi ◽  
Evangelia Kostenidou ◽  
Lea Hildebrandt ◽  
Magda Psichoudaki ◽  
...  
Keyword(s):  
Organic Aerosol ◽  
Basis Set ◽  
Transfer Model ◽  
Collaborative Project ◽  
Aerosol Mass Spectrometer ◽  
Aerosol Mass ◽  
Combining Data ◽  
Wide Range ◽  
Order Of Magnitude ◽  
Effective Saturation

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.

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 ◽  
...  
Keyword(s):  
Relative Humidity ◽  
Phase State ◽  
Steel Substrate ◽  
Phase Changes ◽  
Aerosol Mass Spectrometer ◽  
Oxidation Level ◽  
Aerosol Mass ◽  
Wide Range ◽  
Volatile Organic ◽  
Semi Solid

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.

scholarly journals Summertime aerosol volatility measurements in Beijing, China

2019 ◽  
Author(s):  
Weiqi Xu ◽  
Conghui Xie ◽  
Eleni Karnezi ◽  
Qi Zhang ◽  
Junfeng Wang ◽  
...  
Keyword(s):  
Aerosol Particles ◽  
High Mass ◽  
Transfer Model ◽  
Organic Nitrates ◽  
Aerosol Mass Spectrometer ◽  
Aerosol Mass ◽  
Metallic Salts ◽  
Volatile Organic ◽  
Effective Saturation ◽  
Beijing China

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.

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

2012 ◽  
Vol 12 (16) ◽  
pp. 7517-7529 ◽  
Author(s):  
E. Saukko ◽  
A. T. Lambe ◽  
P. Massoli ◽  
T. Koop ◽  
J. P. Wright ◽  
...  
Keyword(s):  
Relative Humidity ◽  
Phase State ◽  
Steel Substrate ◽  
Amorphous Solid ◽  
Aerosol Mass Spectrometer ◽  
Oxidation Level ◽  
Aerosol Mass ◽  
Wide Range ◽  
Volatile Organic ◽  
Semi Solid

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.

scholarly journals Organic aerosol in the summertime Southeastern United States: Components and their link to volatility distribution, oxidation state and hygroscopicity

2017 ◽  
Author(s):  
Evangelia Kostenidou ◽  
Eleni Karnezi ◽  
James R. Hite Jr. ◽  
Aikaterini Bougiatioti ◽  
Kate Cerully ◽  
...  
Keyword(s):  
High Resolution ◽  
Mass Spectra ◽  
Organic Aerosol ◽  
Related Factor ◽  
Resolution Time ◽  
Positive Matrix ◽  
Evaporation Coefficient ◽  
Aerosol Mass Spectrometer ◽  
Aerosol Mass ◽  
Wide Range

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.

scholarly journals Organic aerosol in the summertime southeastern United States: components and their link to volatility distribution, oxidation state and hygroscopicity

2018 ◽  
Vol 18 (8) ◽  
pp. 5799-5819 ◽  
Author(s):  
Evangelia Kostenidou ◽  
Eleni Karnezi ◽  
James R. Hite Jr. ◽  
Aikaterini Bougiatioti ◽  
Kate Cerully ◽  
...  
Keyword(s):  
High Resolution ◽  
Mass Spectra ◽  
Organic Aerosol ◽  
Related Factor ◽  
Resolution Time ◽  
Positive Matrix ◽  
Evaporation Coefficient ◽  
Aerosol Mass Spectrometer ◽  
Aerosol Mass ◽  
Wide Range

Abstract. The volatility distribution of the organic aerosol (OA) and its sources during the Southern Oxidant and Aerosol Study (SOAS; Centreville, Alabama) was constrained using measurements from an Aerodyne high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS) and a thermodenuder (TD). 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 epoxydiol (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 to its low enthalpy of vaporization according to the model. 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.

scholarly journals Ozonolysis of α-pinene: parameterization of secondary organic aerosol mass fraction

2007 ◽  
Vol 7 (1) ◽  
pp. 1941-1967 ◽  
Author(s):  
R. K. Pathak ◽  
A. A. Presto ◽  
T. E. Lane ◽  
C. O. Stanier ◽  
N. M. Donahue ◽  
...  
Keyword(s):  
Mass Fraction ◽  
Organic Aerosol ◽  
Basis Set ◽  
Smog Chamber ◽  
Equilibrium Partitioning ◽  
Research Teams ◽  
Aerosol Mass ◽  
Wide Range ◽  
Mass Fractions ◽  
Dry Conditions

Abstract. Existing parameterizations tend to underpredict the α-pinene aerosol mass fraction (AMF) by a factor of 2–5 at low organic aerosol concentrations (<5 μg m−3). A wide range of smog chamber results obtained at various conditions (low/high NOx, presence/absence of UV radiation, dry/humid conditions, and temperatures ranging from 15–40°C) collected by various research teams during the last decade are used to derive new parameterizations of the SOA formation from α-pinene ozonolysis. Parameterizations are developed by fitting experimental data to a basis set of saturation concentrations (from 10−2 to 104 μg m−3) using an absorptive equilibrium partitioning model. Separate parameterizations for α-pinene SOA mass fractions are developed for: 1) Low NOx, dark, and dry conditions, 2) Low NOx, UV, and dry conditions, 3) Low NOx, dark, and high RH conditions, 4) High NOx, dark, and dry conditions, 5) High NOx, UV, and dry conditions. According to the proposed parameterizations the α-pinene SOA mass fractions in an atmosphere with 5 μg m−3 of organic aerosol range from 0.032 to 0.1 for reacted α-pinene concentrations in the 1 ppt to 5 ppb range.

scholarly journals Ozonolysis of α-pinene: parameterization of secondary organic aerosol mass fraction

2007 ◽  
Vol 7 (14) ◽  
pp. 3811-3821 ◽  
Author(s):  
R. K. Pathak ◽  
A. A. Presto ◽  
T. E. Lane ◽  
C. O. Stanier ◽  
N. M. Donahue ◽  
...  
Keyword(s):  
Mass Fraction ◽  
Organic Aerosol ◽  
Basis Set ◽  
Smog Chamber ◽  
Equilibrium Partitioning ◽  
Research Teams ◽  
Aerosol Mass ◽  
Wide Range ◽  
Mass Fractions ◽  
Dry Conditions

Abstract. Existing parameterizations tend to underpredict the α-pinene aerosol mass fraction (AMF) or yield by a factor of 2–5 at low organic aerosol concentrations (<5 µg m−3). A wide range of smog chamber results obtained at various conditions (low/high NOx, presence/absence of UV radiation, dry/humid conditions, and temperatures ranging from 15–40°C) collected by various research teams during the last decade are used to derive new parameterizations of the SOA formation from α-pinene ozonolysis. Parameterizations are developed by fitting experimental data to a basis set of saturation concentrations (from 10−2 to 104 µg m−3) using an absorptive equilibrium partitioning model. Separate parameterizations for α-pinene SOA mass fractions are developed for: 1) Low NOx, dark, and dry conditions, 2) Low NOx, UV, and dry conditions, 3) Low NOx, dark, and high RH conditions, 4) High NOx, dark, and dry conditions, 5) High NOx, UV, and dry conditions. According to the proposed parameterizations the α-pinene SOA mass fractions in an atmosphere with 5 µg m−3 of organic aerosol range from 0.032 to 0.1 for reacted α-pinene concentrations in the 1 ppt to 5 ppb range.

scholarly journals Organic aerosol components observed in worldwide datasets from aerosol mass spectrometry

2009 ◽  
Vol 9 (6) ◽  
pp. 27745-27789 ◽  
Author(s):  
N. L. Ng ◽  
M. R. Canagaratna ◽  
Q. Zhang ◽  
J. L. Jimenez ◽  
J. Tian ◽  
...  
Keyword(s):  
Mass Spectra ◽  
Organic Aerosol ◽  
Aerosol Mass Spectrometer ◽  
Common Features ◽  
Aerosol Mass ◽  
Aerosol Mass Spectrometry ◽  
Wide Range ◽  
Triangular Region ◽  
The Common ◽  
Photochemical Aging

Abstract. In this study we present results from the factor analysis of 43 aerosol mass spectrometer (AMS) datasets and provide an overview of worldwide organic aerosol (OA) components and their evolution in the atmosphere. At most sites, the OA can be separated into oxygenated OA (OOA), hydrocarbon-like OA (HOA), and sometimes other components such as biomass burning OA (BBOA). In many analyses, the OOA can be further deconvolved into low-volatility OOA (LV-OOA) and semi-volatile OOA (SV-OOA). A wide range of f44 (ratio of m/z 44 to total signal in the component mass spectrum) and O:C ratios are observed for both LV-OOA (0.17±0.04, 0.73±0.14) and SV-OOA (0.07±0.04, 0.35±0.14) components, reflecting the fact that there is a continuum of OOA properties in ambient aerosol. Differences in the mass spectra of these components are characterized in terms of the two main ions m/z 44 (CO2+) and m/z 43 (mostly C2H3O+). The LV-OOA component spectra have higher f44 and lower f43 than SV-OOA. The OOA components (OOA, LV-OOA, and SV-OOA) from all sites cluster within a well defined triangular region in the f44 vs. f43 space, which can be used as a standardized means of comparing and characterizing any OOA components (laboratory or ambient) observed with the AMS. Examination of the OOA components in this triangular space indicates that OOA component spectra become increasingly similar to each other and to fulvic acid and HULIS sample spectra as f44 (a surrogate for O:C and an indicator of photochemical aging) increases. This indicates that ambient OA converges towards highly aged LV-OOA with atmospheric oxidation. The common features of the transformation between SV-OOA and LV-OOA at multiple sites potentially enables a simplified description of the oxidation of OA in the atmosphere. Comparison of laboratory SOA data with ambient OOA indicates that laboratory SOA are more similar to SV-OOA, and rarely become as oxidized as ambient LV-OOA, likely due to the higher loadings employed in the experiments and/or limited oxidant exposure in most chamber experiments.

scholarly journals Physicochemical properties and origin of organic groups detected in boreal forest using an aerosol mass spectrometer

2010 ◽  
Vol 10 (4) ◽  
pp. 2063-2077 ◽  
Author(s):  
T. Raatikainen ◽  
P. Vaattovaara ◽  
P. Tiitta ◽  
P. Miettinen ◽  
J. Rautiainen ◽  
...  
Keyword(s):  
Growth Factors ◽  
Mass Spectrometer ◽  
Organic Aerosol ◽  
Submicron Particles ◽  
Hygroscopic Growth ◽  
Aerosol Mass Spectrometer ◽  
Aerosol Mass ◽  
Hygroscopic Properties ◽  
Inorganic Species ◽  
Wide Range

Abstract. An Aerodyne quadrupole aerosol mass spectrometer (Q-AMS) was deployed in Hyytiälä, a forested rural measurement site in southern Finland, during a 2-week measurement campaign in spring 2005. Q-AMS measures mass concentrations of non-refractory species including sulphate, nitrate, ammonium and organics from submicron particles. A positive matrix factorization method was used in identifying two oxygenated organic aerosol (OOA) groups from the measured total organic mass. The properties of these groups were estimated from their diurnal concentration cycles and correlations with additional data such as air mass history, particle number size distributions, hygroscopic and ethanol growth factors and particle volatility. It was found that the aged and highly oxidized background organic aerosol (OOA1 or LV-OOA) species have a wide range of hygroscopic growth factors and volatilization temperatures, but on the average OOA1 is the less volatile and more hygroscopic organic group. Hygroscopic properties and volatilities of the OOA1 species are correlated so that the less volatile species have higher hygroscopic growth factors. The other, less oxidized organic aerosol group (OOA2 or SV-OOA) is more volatile and non-hygroscopic. Trajectory analysis showed that OOA1 and the inorganic species are mainly long-range transported anthropogenic pollutions. OOA2 species and its precursor gases have short atmospheric life times, so they are from local sources. These results span the range of previous observations of oxygen content, volatility and hygroscopic growth factor, simultaneously coupling all three measurements for the first time.

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