Single particle characterization using the soot particle aerosol mass spectrometer (SP-AMS)

Abstract. Understanding the impact of atmospheric black carbon (BC) containing particles on human health and radiative forcing requires knowledge of the mixing state of BC, including the characteristics of the materials with which it is internally mixed. In this study, we demonstrate for the first time the capabilities of the Aerodyne Soot-Particle Aerosol Mass Spectrometer equipped with a light scattering module (LS-SP-AMS) to examine the mixing state of refractory BC (rBC) and other aerosol components in an urban environment (downtown Toronto). K-means clustering analysis was used to classify single particle mass spectra into chemically distinct groups. One resultant cluster is dominated by rBC mass spectral signals (C1+ to C5+) while the organic signals fall into a few major clusters, identified as hydrocarbon-like organic aerosol (HOA), oxygenated organic aerosol (OOA), and cooking emission organic aerosol (COA). A nearly external mixing is observed with small BC particles only thinly coated by HOA (∼28% by mass on average), while over 90% of the HOA-rich particles did not contain detectable amounts of rBC. Most of the particles classified into other inorganic and organic clusters were not significantly associated with BC. The single particle results also suggest that HOA and COA emitted from anthropogenic sources were likely major contributors to organic-rich particles with low to mid-range aerodynamic diameter (dva). The similar temporal profiles and mass spectral features of the organic clusters and the factors from a positive matrix factorization (PMF) analysis of the ensemble aerosol dataset validate the conventional interpretation of the PMF results.

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Mixing state of carbonaceous aerosol in an urban environment: single particle characterization using the soot particle aerosol mass spectrometer (SP-AMS)

Atmospheric Chemistry and Physics ◽

10.5194/acp-15-1823-2015 ◽

2015 ◽

Vol 15 (4) ◽

pp. 1823-1841 ◽

Cited By ~ 52

Author(s):

A. K. Y. Lee ◽

M. D. Willis ◽

R. M. Healy ◽

T. B. Onasch ◽

J. P. D. Abbatt

Keyword(s):

Cluster Analysis ◽

Urban Environment ◽

Mass Spectrometer ◽

Single Particle ◽

Soot Particle ◽

Organic Aerosol ◽

Mixing State ◽

Aerosol Mass Spectrometer ◽

Mass Spectral ◽

Aerosol Mass

Abstract. Understanding the impact of atmospheric black carbon (BC)-containing particles on human health and radiative forcing requires knowledge of the mixing state of BC, including the characteristics of the materials with which it is internally mixed. In this study, we examine the mixing state of refractory BC (rBC) and other aerosol components in an urban environment (downtown Toronto) utilizing the Aerodyne soot particle aerosol mass spectrometer equipped with a light scattering module (LS-SP-AMS). k-means cluster analysis was used to classify single particle mass spectra into chemically distinct groups. One resultant particle class is dominated by rBC mass spectral signals (C1&plus; to C5&plus;) while the organic signals fall into a few major particle classes identified as hydrocarbon-like organic aerosol (HOA), oxygenated organic aerosol (OOA), and cooking emission organic aerosol (COA). A gradual mixing is observed with small rBC particles only thinly coated by HOA (~ 28% by mass on average), while over 90% of the HOA-rich particles did not contain detectable amounts of rBC. Most of the particles classified into other inorganic and organic particle classes were not significantly associated with rBC. The single particle results also suggest that HOA and COA emitted from anthropogenic sources were likely major contributors to organic-rich particles with vacuum aerodynamic diameter (dva) ranging from ~ 200 to 400 nm. The similar temporal profiles and mass spectral features of the organic classes identified by cluster analysis and the factors from a positive matrix factorization (PMF) analysis of the ensemble aerosol data set validate the interpretation of the PMF results.

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Quantitative determination of carbonaceous particle mixing state in Paris using single particle mass spectrometer and aerosol mass spectrometer measurements

Atmospheric Chemistry and Physics Discussions ◽

10.5194/acpd-13-10345-2013 ◽

2013 ◽

Vol 13 (4) ◽

pp. 10345-10393

Author(s):

R. M. Healy ◽

J. Sciare ◽

L. Poulain ◽

M. Crippa ◽

A. Wiedensohler ◽

...

Keyword(s):

Chemical Composition ◽

Mass Spectrometer ◽

Single Particle ◽

Organic Aerosol ◽

Particle Mass ◽

Mixing State ◽

Aerosol Mass Spectrometer ◽

Aerosol Mass ◽

Particle Mixing ◽

Mixing States

Abstract. Single particle mixing state information can be a powerful tool for assessing the relative impact of local and regional sources of ambient particulate matter in urban environments. However, quantitative mixing state data are challenging to obtain using single particle mass spectrometers. In this study, the quantitative chemical composition of carbonaceous single particles has been estimated using an aerosol time-of-flight mass spectrometer (ATOFMS) as part of the MEGAPOLI 2010 winter campaign in Paris, France. Relative peak areas of marker ions for elemental carbon (EC), organic aerosol (OA), ammonium, nitrate, sulphate and potassium were compared with concurrent measurements from an Aerodyne high resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS), a thermal/optical OCEC analyser and a particle into liquid sampler coupled with ion chromatography (PILS-IC). ATOFMS-derived mass concentrations reproduced the variability of these species well (R2 = 0.67–0.78), and ten discrete mixing states for carbonaceous particles were identified and quantified. Potassium content was used to identify particles associated with biomass combustion. The chemical mixing state of HR-ToF-AMS organic aerosol factors, resolved using positive matrix factorization, was also investigated through comparison with the ATOFMS dataset. The results indicate that hydrocarbon-like OA (HOA) detected in Paris is associated with two EC-rich mixing states which differ in their relative sulphate content, while fresh biomass burning OA (BBOA) is associated with two mixing states which differ significantly in their OA/EC ratios. Aged biomass burning OA (OOA2-BBOA) was found to be significantly internally mixed with nitrate, while secondary, oxidized OA (OOA) was associated with five particle mixing states, each exhibiting different relative secondary inorganic ion content. Externally mixed secondary organic aerosol was not observed. These findings demonstrate the heterogeneity of primary and secondary organic aerosol mixing states in Paris. Examination of the temporal behaviour and chemical composition of the ATOFMS classes also enabled estimation of the relative contribution of transported emissions of each chemical species and total particle mass in the size range investigated. Only 22% of the total ATOFMS-derived particle mass was apportioned to fresh, local emissions, with 78% apportioned to regional/continental scale emissions.

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Quantitative determination of carbonaceous particle mixing state in Paris using single-particle mass spectrometer and aerosol mass spectrometer measurements

Atmospheric Chemistry and Physics ◽

10.5194/acp-13-9479-2013 ◽

2013 ◽

Vol 13 (18) ◽

pp. 9479-9496 ◽

Cited By ~ 80

Author(s):

R. M. Healy ◽

J. Sciare ◽

L. Poulain ◽

M. Crippa ◽

A. Wiedensohler ◽

...

Keyword(s):

Chemical Composition ◽

Mass Spectrometer ◽

Single Particle ◽

Organic Aerosol ◽

Particle Mass ◽

Mixing State ◽

Aerosol Mass Spectrometer ◽

Aerosol Mass ◽

Particle Mixing ◽

Mixing States

Abstract. Single-particle mixing state information can be a powerful tool for assessing the relative impact of local and regional sources of ambient particulate matter in urban environments. However, quantitative mixing state data are challenging to obtain using single-particle mass spectrometers. In this study, the quantitative chemical composition of carbonaceous single particles has been determined using an aerosol time-of-flight mass spectrometer (ATOFMS) as part of the MEGAPOLI 2010 winter campaign in Paris, France. Relative peak areas of marker ions for elemental carbon (EC), organic aerosol (OA), ammonium, nitrate, sulfate and potassium were compared with concurrent measurements from an Aerodyne high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS), a thermal–optical OCEC analyser and a particle into liquid sampler coupled with ion chromatography (PILS-IC). ATOFMS-derived estimated mass concentrations reproduced the variability of these species well (R2 = 0.67–0.78), and 10 discrete mixing states for carbonaceous particles were identified and quantified. The chemical mixing state of HR-ToF-AMS organic aerosol factors, resolved using positive matrix factorisation, was also investigated through comparison with the ATOFMS dataset. The results indicate that hydrocarbon-like OA (HOA) detected in Paris is associated with two EC-rich mixing states which differ in their relative sulfate content, while fresh biomass burning OA (BBOA) is associated with two mixing states which differ significantly in their OA / EC ratios. Aged biomass burning OA (OOA2-BBOA) was found to be significantly internally mixed with nitrate, while secondary, oxidised OA (OOA) was associated with five particle mixing states, each exhibiting different relative secondary inorganic ion content. Externally mixed secondary organic aerosol was not observed. These findings demonstrate the range of primary and secondary organic aerosol mixing states in Paris. Examination of the temporal behaviour and chemical composition of the ATOFMS classes also enabled estimation of the relative contribution of transported emissions of each chemical species and total particle mass in the size range investigated. Only 22% of the total ATOFMS-derived particle mass was apportioned to fresh, local emissions, with 78% apportioned to regional/continental-scale emissions.

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Single-particle measurements of bouncing particles and in situ collection efficiency from an airborne aerosol mass spectrometer (AMS) with light-scattering detection

Atmospheric Measurement Techniques ◽

10.5194/amt-10-3801-2017 ◽

2017 ◽

Vol 10 (10) ◽

pp. 3801-3820 ◽

Cited By ~ 6

Author(s):

Jin Liao ◽

Charles A. Brock ◽

Daniel M. Murphy ◽

Donna T. Sueper ◽

André Welti ◽

...

Keyword(s):

Light Scattering ◽

Mass Spectrometer ◽

Single Particle ◽

Total Mass ◽

Mass Spectra ◽

Collection Efficiency ◽

Aerosol Mass Spectrometer ◽

Mass Spectral ◽

Aerosol Mass ◽

Spectral Signal

Abstract. A light-scattering module was coupled to an airborne, compact time-of-flight aerosol mass spectrometer (LS-AMS) to investigate collection efficiency (CE) while obtaining nonrefractory aerosol chemical composition measurements during the Southeast Nexus (SENEX) campaign. In this instrument, particles scatter light from an internal laser beam and trigger saving individual particle mass spectra. Nearly all of the single-particle data with mass spectra that were triggered by scattered light signals were from particles larger than ∼ 280 nm in vacuum aerodynamic diameter. Over 33 000 particles are characterized as either prompt (27 %), delayed (15 %), or null (58 %), according to the time and intensity of their total mass spectral signals. The particle mass from single-particle spectra is proportional to that derived from the light-scattering diameter (dva-LS) but not to that from the particle time-of-flight (PToF) diameter (dva-MS) from the time of the maximum mass spectral signal. The total mass spectral signal from delayed particles was about 80 % of that from prompt ones for the same dva-LS. Both field and laboratory data indicate that the relative intensities of various ions in the prompt spectra show more fragmentation compared to the delayed spectra. The particles with a delayed mass spectral signal likely bounced off the vaporizer and vaporized later on another surface within the confines of the ionization source. Because delayed particles are detected by the mass spectrometer later than expected from their dva-LS size, they can affect the interpretation of particle size (PToF) mass distributions, especially at larger sizes. The CE, measured by the average number or mass fractions of particles optically detected that had measurable mass spectra, varied significantly (0.2–0.9) in different air masses. The measured CE agreed well with a previous parameterization when CE > 0.5 for acidic particles but was sometimes lower than the minimum parameterized CE of 0.5.

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The real part of the refractive indices and effective densities for chemically segregated ambient aerosols in Guangzhou measured by a single-particle aerosol mass spectrometer

Atmospheric Chemistry and Physics ◽

10.5194/acp-16-2631-2016 ◽

2016 ◽

Vol 16 (4) ◽

pp. 2631-2640 ◽

Cited By ~ 6

Author(s):

Guohua Zhang ◽

Xinhui Bi ◽

Ning Qiu ◽

Bingxue Han ◽

Qinhao Lin ◽

...

Keyword(s):

Mass Spectrometer ◽

Atmospheric Aerosols ◽

Single Particle ◽

Refractive Indices ◽

Chemical Compositions ◽

Aerosol Mass Spectrometer ◽

The Real ◽

Aerosol Mass ◽

Wide Range ◽

The Impact

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.

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Quantitative single particle analysis with the Aerodyne aerosol mass spectrometer: development of a new classification algorithm and its application to field data

Atmospheric Measurement Techniques Discussions ◽

10.5194/amtd-6-5653-2013 ◽

2013 ◽

Vol 6 (3) ◽

pp. 5653-5691 ◽

Cited By ~ 1

Author(s):

F. Freutel ◽

F. Drewnick ◽

J. Schneider ◽

T. Klimach ◽

S. Borrmann

Keyword(s):

Mass Spectrometer ◽

Single Particle ◽

Field Data ◽

Classification Algorithm ◽

Particle Mass ◽

Submicron Particles ◽

Particle Analysis ◽

Mixing State ◽

Aerosol Mass Spectrometer ◽

Aerosol Mass

Abstract. Single particle mass spectrometry has proven a valuable tool for gaining information on the mixing state of aerosol particles. With the Aerodyne aerosol mass spectrometer (AMS) equipped with a light scattering probe, non-refractory components of submicron particles with diameters larger than about 300 nm can even be quantified on a single particle basis. Here, we present a new method for the analysis of AMS single particle mass spectra. The developed algorithm classifies the particles according to their components (e.g., sulphate, nitrate, different types of organics) and simultaneously provides quantitative information about the composition of the single particles. This classification algorithm was validated by applying it to data acquired in laboratory experiments with particles of known composition, and applied to field data acquired during the MEGAPOLI summer campaign (July 2009) in Paris. As shown, it is not only possible to directly measure the mixing state of atmospheric particles, but also to directly observe repartitioning of semi-volatile species between gas and particle phase during the course of the day.

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Quantitative single-particle analysis with the Aerodyne aerosol mass spectrometer: development of a new classification algorithm and its application to field data

Atmospheric Measurement Techniques ◽

10.5194/amt-6-3131-2013 ◽

2013 ◽

Vol 6 (11) ◽

pp. 3131-3145 ◽

Cited By ~ 21

Author(s):

F. Freutel ◽

F. Drewnick ◽

J. Schneider ◽

T. Klimach ◽

S. Borrmann

Keyword(s):

Mass Spectrometer ◽

Single Particle ◽

Field Data ◽

Classification Algorithm ◽

Particle Mass ◽

Submicron Particles ◽

Particle Analysis ◽

Mixing State ◽

Aerosol Mass Spectrometer ◽

Aerosol Mass

Abstract. Single-particle mass spectrometry has proven a valuable tool for gaining information on the mixing state of aerosol particles. With the Aerodyne aerosol mass spectrometer (AMS) equipped with a light-scattering probe, non-refractory components of submicron particles with diameters larger than about 300 nm can even be quantified on a single-particle basis. Here, we present a new method for the analysis of AMS single-particle mass spectra. The developed algorithm classifies the particles according to their components (e.g. sulphate, nitrate, different types of organics) and simultaneously provides quantitative information about the composition of the single particles. This classification algorithm was validated by applying it to data acquired in laboratory experiments with particles of known composition, and applied to field data acquired during the MEGAPOLI summer campaign (July 2009) in Paris. As shown, it is not only possible to directly measure the mixing state of atmospheric particles, but also to directly observe repartitioning of semi-volatile species between gas and particle phase during the course of the day.

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Single particle characterization using a light scattering module coupled to a time-of-flight aerosol mass spectrometer

Atmospheric Chemistry and Physics ◽

10.5194/acp-9-7769-2009 ◽

2009 ◽

Vol 9 (20) ◽

pp. 7769-7793 ◽

Cited By ~ 75

Author(s):

E. S. Cross ◽

T. B. Onasch ◽

M. Canagaratna ◽

J. T. Jayne ◽

J. Kimmel ◽

...

Keyword(s):

Light Scattering ◽

Mass Spectrometer ◽

Single Particle ◽

Collection Efficiency ◽

Time Of Flight ◽

Chemical Compositions ◽

Single Particles ◽

Mixing State ◽

Aerosol Mass Spectrometer ◽

Aerosol Mass

Abstract. We present the first single particle results obtained with an Aerodyne time-of-flight aerosol mass spectrometer coupled with a light scattering module (LS-ToF-AMS). The instrument was deployed at the T1 ground site approximately 40 km northeast of the Mexico City Metropolitan Area as part of the MILAGRO field study in March of 2006. The LS-ToF-AMS acquires both ensemble average and single particle data. Over a 75-h sampling period from 27–30 March 2006, 12 853 single particle mass spectra were optically-triggered and saved. The single particles were classified based on observed vaporization histories and measured chemical compositions. The single particle data is shown to provide insights on internal AMS collection efficiencies and ambient mixing state information that augments the ensemble data. Detection of correlated light scattering and chemical ion signals allowed for a detailed examination of the vaporization/ionization process for single particles measured with the AMS instrument. Three particle vaporization event types were identified as a fraction of the total number of particles detected: (1) 23% with prompt vaporization, (2) 26% with delayed vaporization, and (3) 51% characterized as null. Internal consistency checks show that average single particle nonrefractory mass and chemical composition measurements were in reasonable agreement with ensemble measurements and suggest that delayed and null vaporization events are the dominant source of the nonunit collection efficiency of the AMS. Taken together, the simultaneous prompt single particle and aerosol ensemble measurements offer insight into the mixing state and atmospheric transformations of ambient aerosol particles.

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