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

2013 ◽  
Vol 13 (18) ◽  
pp. 9479-9496 ◽  
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.

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

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.

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

2013 ◽  
Vol 6 (3) ◽  
pp. 5653-5691 ◽  
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.

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

2015 ◽  
Vol 15 (4) ◽  
pp. 1823-1841 ◽  
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+ to C5+) 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.

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

2013 ◽  
Vol 6 (11) ◽  
pp. 3131-3145 ◽  
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.

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

2014 ◽  
Vol 14 (10) ◽  
pp. 15323-15361 ◽  
Author(s):  
A. K. Y. Lee ◽  
M. D. Willis ◽  
R. M. Healy ◽  
T. B. Onasch ◽  
J. P. D. Abbatt
Keyword(s):  
Mass Spectrometer ◽  
Single Particle ◽  
Soot Particle ◽  
Organic Aerosol ◽  
Anthropogenic Sources ◽  
Mixing State ◽  
Aerosol Mass Spectrometer ◽  
Mass Spectral ◽  
Aerosol Mass ◽  
The Impact

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.

scholarly journals Measurements of the aerosol chemical composition and mixing state in the Po Valley using multiple spectroscopic techniques

2014 ◽  
Vol 14 (22) ◽  
pp. 12109-12132 ◽  
Author(s):  
S. Decesari ◽  
J. Allan ◽  
C. Plass-Duelmer ◽  
B. J. Williams ◽  
M. Paglione ◽  
...  
Keyword(s):  
Chemical Composition ◽  
Black Carbon ◽  
Mass Spectrometer ◽  
Organic Aerosol ◽  
Spectroscopic Techniques ◽  
Mixing State ◽  
Mass Spectrometers ◽  
Aerosol Mass Spectrometer ◽  
Po Valley ◽  
Aerosol Mass

Abstract. The use of co-located multiple spectroscopic techniques can provide detailed information on the atmospheric processes regulating aerosol chemical composition and mixing state. So far, field campaigns heavily equipped with aerosol mass spectrometers have been carried out mainly in large conurbations and in areas directly affected by their outflow, whereas lesser efforts have been dedicated to continental areas characterised by a less dense urbanisation. We present here the results obtained at a background site in the Po Valley, Italy, in summer 2009. For the first time in Europe, six state-of-the-art spectrometric techniques were used in parallel: aerosol time-of-flight mass spectrometer (ATOFMS), two aerosol mass spectrometers (high-resolution time-of-flight aerosol mass spectrometer – HR-ToF-AMS and soot particle aerosol mass spectrometer – SP-AMS), thermal desorption aerosol gas chromatography (TAG), chemical ionisation mass spectrometry (CIMS) and (offline) proton nuclear magnetic resonance (1H-NMR) spectroscopy. The results indicate that, under high-pressure conditions, atmospheric stratification at night and early morning hours led to the accumulation of aerosols produced by anthropogenic sources distributed over the Po Valley plain. Such aerosols include primary components such as black carbon (BC), secondary semivolatile compounds such as ammonium nitrate and amines and a class of monocarboxylic acids which correspond to the AMS cooking organic aerosol (COA) already identified in urban areas. In daytime, the entrainment of aged air masses in the mixing layer is responsible for the accumulation of low-volatility oxygenated organic aerosol (LV-OOA) and also for the recycling of non-volatile primary species such as black carbon. According to organic aerosol source apportionment, anthropogenic aerosols accumulating in the lower layers overnight accounted for 38% of organic aerosol mass on average, another 21% was accounted for by aerosols recirculated in residual layers but still originating in northern Italy, while a substantial fraction (41%) was due to the most aged aerosols imported from transalpine areas. The different meteorological regimes also affected the BC mixing state: in periods of enhanced stagnation and recirculation of pollutants, the number fraction of the BC-containing particles determined by ATOFMS was 75% of the total, while in the days of enhanced ventilation of the planetary boundary layer (PBL), such fraction was significantly lower (50%) because of the relative greater influence of non-BC-containing aerosol local sources in the Po Valley. Overall, a full internal mixing between BC and the non-refractory aerosol chemical components was not observed during the experiment in this environment.

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

2008 ◽  
Vol 8 (6) ◽  
pp. 21313-21381 ◽  
Author(s):  
E. S. Cross ◽  
T. B. Onasch ◽  
M. Canagaratna ◽  
J. T. Jayne ◽  
J. Kimmel ◽  
...  
Keyword(s):  
Light Scattering ◽  
Chemical Composition ◽  
Single Particle ◽  
Mass Spectra ◽  
Sampling Period ◽  
Particle Mass ◽  
Aerosol Mass Spectrometer ◽  
Aerosol Mass ◽  
Mass Fractions ◽  
Mixing States

Abstract. We present the first single particle results obtained using 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 (MCMA) as part of the MILAGRO field study in March of 2006. The instrument was operated as a standard AMS from 12–30 March, acquiring average chemical composition and size distributions for the ambient aerosol, and in single particle mode from 27–30 March. Over a 75-h sampling period, 12 853 single particle mass spectra were optically triggered, saved, and analyzed. The correlated optical and chemical detection allowed detailed examination of single particle collection and quantification within the LS-ToF-AMS. The single particle data enabled the mixing states of the ambient aerosol to be characterized within the context of the size-resolved ensemble chemical information. The particulate mixing states were examined as a function of sampling time and most of the particles were found to be internal mixtures containing many of the organic and inorganic species identified in the ensemble analysis. The single particle mass spectra were deconvolved, using techniques developed for ensemble AMS data analysis, into HOA, OOA, NH4NO3, (NH4)2SO4, and NH4Cl fractions. Average single particle mass and chemistry measurements are shown to be in agreement with ensemble MS and PTOF measurements. While a significant fraction of ambient particles were internal mixtures of varying degrees, single particle measurements of chemical composition allowed the identification of time periods during which the ambient ensemble was externally mixed. In some cases the chemical composition of the particles suggested a likely source. Throughout the full sampling period, the ambient ensemble was an external mixture of combustion-generated HOA particles from local sources (e.g. traffic), with number concentrations peaking during morning rush hour (04:00–08:00 LT) each day, and more processed particles of mixed composition from nonspecific sources. From 09:00–12:00 LT all particles within the ambient ensemble, including the locally produced HOA particles, became coated with NH4NO3 due to photochemical production of HNO3. The number concentration of externally mixed HOA particles remained low during daylight hours. Throughout the afternoon the OOA component dominated the organic fraction of the single particles, likely due to secondary organic aerosol formation and condensation. Single particle mass fractions of (NH4)2SO4 were lowest during the day and highest during the night. In one instance, gas-to-particle condensation of (NH4)2SO4 was observed on all measured particles within a strong SO2 plume arriving at T1 from the northwest. Particles with high NH4Cl mass fractions were identified during early morning periods. A limited number of particles (~5% of the total number) with mass spectral features characteristic of biomass burning were also identified.

scholarly journals CHEMICAL COMPOSITION OF AEROSOLS IN THE WEST COAST OF TAIWAN STRAIT, CHINA

2019 ◽  
Vol XLII-3/W9 ◽  
pp. 233-237
Author(s):  
L. Zhao ◽  
C. Yang
Keyword(s):  
Chemical Composition ◽  
Mass Spectrometer ◽  
Single Particle ◽  
Inorganic Ions ◽  
Water Soluble ◽  
Ion Concentration ◽  
Aerosol Mass Spectrometer ◽  
Average Mass ◽  
Inorganic Ion ◽  
Aerosol Mass

Abstract. The chemical composition of aerosols was investigated using regular environmental air quality observation, a single particle aerosol mass spectrometer (SPAMS 0515) and an ambient ion monitor (URG 9000D) in Xiamen in 2018. The results showed that the annual average mass concentrations of PM2.5 was 22 μm/m3, and concentrations of water-soluble inorganic ions was 9.94 μm/m3 which accounted for 45.2% of PM2.5. SO42−, NO3− and NH4+ were main components of secondary reactions which contributed more than 77 percent of water-soluble inorganic ion concentration. As a coastal city, Cl− and Na+ contributed 13.9 percent of water-soluble inorganic ion concentration. Based on single particle aerosol mass spectrometer analysing, mobile sources emission was the most important sources of particle matter which contributed over 30%.

scholarly journals Single particle diversity and mixing state measurements

2014 ◽  
Vol 14 (12) ◽  
pp. 6289-6299 ◽  
Author(s):  
R. M. Healy ◽  
N. Riemer ◽  
J. C. Wenger ◽  
M. Murphy ◽  
M. West ◽  
...  
Keyword(s):  
Species Diversity ◽  
Ammonium Nitrate ◽  
Black Carbon ◽  
Mass Spectrometer ◽  
Single Particle ◽  
Organic Aerosol ◽  
Particle Mass ◽  
Mixing State ◽  
Mass Fractions ◽  
State Index

Abstract. A newly developed framework for quantifying aerosol particle diversity and mixing state based on information-theoretic entropy is applied for the first time to single particle mass spectrometry field data. Single particle mass fraction estimates for black carbon, organic aerosol, ammonium, nitrate and sulfate, derived using single particle mass spectrometer, aerosol mass spectrometer and multi-angle absorption photometer measurements are used to calculate single particle species diversity (Di). The average single particle species diversity (Dα) is then related to the species diversity of the bulk population (Dγ) to derive a mixing state index value (χ) at hourly resolution. The mixing state index is a single parameter representation of how internally/externally mixed a particle population is at a given time. The index describes a continuum, with values of 0 and 100% representing fully external and internal mixing, respectively. This framework was applied to data collected as part of the MEGAPOLI winter campaign in Paris, France, 2010. Di values are low (~ 2) for fresh traffic and wood-burning particles that contain high mass fractions of black carbon and organic aerosol but low mass fractions of inorganic ions. Conversely, Di values are higher (~ 4) for aged carbonaceous particles containing similar mass fractions of black carbon, organic aerosol, ammonium, nitrate and sulfate. Aerosol in Paris is estimated to be 59% internally mixed in the size range 150–1067 nm, and mixing state is dependent both upon time of day and air mass origin. Daytime primary emissions associated with vehicular traffic and wood-burning result in low χ values, while enhanced condensation of ammonium nitrate on existing particles at night leads to higher χ values. Advection of particles from continental Europe containing ammonium, nitrate and sulfate leads to increases in Dα, Dγ and χ. The mixing state index represents a useful metric by which to compare and contrast ambient particle mixing state at other locations globally.

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

2009 ◽  
Vol 9 (20) ◽  
pp. 7769-7793 ◽  
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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