scholarly journals Elemental analysis of aerosol organic nitrates with electron ionization high-resolution mass spectrometry

2010 ◽  
Vol 3 (1) ◽  
pp. 301-310 ◽  
Author(s):  
A. W. Rollins ◽  
J. L. Fry ◽  
J. F. Hunter ◽  
J. H. Kroll ◽  
D. R. Worsnop ◽  
...  
Keyword(s):  
High Resolution ◽  
Elemental Analysis ◽  
High Resolution Mass Spectrometry ◽  
Oxidation Products ◽  
Organic Nitrates ◽  
Resolution Time ◽  
Aerosol Mass Spectrometer ◽  
Aerosol Mass ◽  
Volatile Organic ◽  
Resolution Mass

Abstract. Four hydroxynitrates (R(OH)R'ONO2) representative of atmospheric volatile organic compound (VOC) oxidation products were synthesized, nebulized and sampled into an Aerodyne High Resolution Time of Flight Aerosol Mass Spectrometer (HR-ToF-AMS). The resulting mass spectrum was used to evaluate calibration factors for elemental analysis of organic nitrates by AMS, and to determine the distribution of nitrogen in the detected fragments in a search for an AMS signature of organic nitrates. We found that 30% of the detected nitrogen mass is in the NO+ and NO2+ fragments, 12% at NHx+ fragments, 5% at CxHyOzN+ fragments, and 53% at various CxHyN+ fragments. Elemental analysis indicated that nitrogen was detected with higher efficiency than carbon and hydrogen, but oxygen was detected with reduced efficiency compared to previously reported results for a suite of organics which did not include organic nitrates. The results are used to suggest the maximum corrections to ambient O:C and N:C ratios based on AMS measurements.

scholarly journals Elemental analysis of aerosol organic nitrates with electron ionization high-resolution mass spectrometry

2009 ◽  
Vol 2 (5) ◽  
pp. 2781-2807
Author(s):  
A. W. Rollins ◽  
J. L. Fry ◽  
J. F. Hunter ◽  
J. H. Kroll ◽  
D. R. Worsnop ◽  
...  
Keyword(s):  
High Resolution ◽  
Elemental Analysis ◽  
High Resolution Mass Spectrometry ◽  
Oxidation Products ◽  
Organic Nitrates ◽  
Resolution Time ◽  
Aerosol Mass Spectrometer ◽  
Aerosol Mass ◽  
Volatile Organic ◽  
Resolution Mass

Abstract. Four hydroxynitrates (R(OH)R'ONO2) representative of atmospheric volatile organic compound (VOC) oxidation products were synthesized, nebulized and sampled into an Aerodyne High Resolution Time of Flight Aerosol Mass Spectrometer (HR-ToF-AMS). The resulting mass spectrum was used to evaluate calibration factors for elemental analysis of organic nitrates by AMS, and to determine the distribution of nitrogen in the detected fragments in a search for an AMS signature of organic nitrates. We find that 30% of the detected nitrogen mass is in the NO+ and NO2+ fragments, 12% at NHx+ fragments, 5% at CxHyOzN+ fragments, and 53% at various CxHyN+ fragments. Elemental analysis indicated that nitrogen was detected with higher efficiency than carbon and hydrogen, but oxygen was detected with reduced efficiency compared to previously reported results for a suite of organics which did not include organic nitrates. The results are used to suggest the maximum corrections to ambient O:C and N:C ratios based on AMS measurements.

scholarly journals Characterization of the sources and processes of organic and inorganic aerosols in New York City with a high-resolution time-of-flight aerosol mass spectrometer

2010 ◽  
Vol 10 (10) ◽  
pp. 22669-22723 ◽  
Author(s):  
Y.-L. Sun ◽  
Q. Zhang ◽  
J. J. Schwab ◽  
K. L. Demerjian ◽  
W.-N. Chen ◽  
...  
Keyword(s):  
New York ◽  
New York City ◽  
High Resolution ◽  
Mass Spectrometer ◽  
York City ◽  
Time Of Flight ◽  
Resolution Time ◽  
Aerosol Mass Spectrometer ◽  
Spectral Pattern ◽  
Aerosol Mass

Abstract. Submicron aerosol particles (PM1) were measured in-situ using a High-Resolution Time-of-Flight Aerosol Mass Spectrometer (HR-ToF-AMS) during the summer 2009 Field Intensive Study at Queens College in New York City. Organic aerosol (OA) and sulfate are the two dominant species, accounting for 54% and 24%, respectively, of total PM1 mass on average. The average mass size distribution of OA presents a small mode peaking at ~150 nm (Dva) in addition to an accumulation mode (~550 nm) that is internally mixed with sulfate, nitrate, and ammonium. The diurnal cycles of sulfate and OA both show pronounced peaks between 01:00–02:00 p.m. EST due to photochemical production. The average (±1σ) oxygen-to-carbon (O/C), hydrogen-to-carbon (H/C), and nitrogen-to-carbon (N/C) ratios of OA in NYC are 0.36 (±0.09), 1.49 (±0.08), and 0.012(±0.005), respectively, corresponding to an average organic mass-to-carbon (OM/OC) ratio of 1.62(±0.11). Positive matrix factorization (PMF) of the high resolution mass spectra identified five OA components: a hydrocarbon-like OA (HOA), two types of oxygenated OA (OOA) including a low-volatility OOA (LV-OOA) and a semi-volatile OOA (SV-OOA), a cooking-emission related OA (COA), and a unique nitrogen-enriched OA (NOA). HOA appears to represent primary OA (POA) from urban traffic emissions. It comprises primarily of reduced species (H/C=1.83; O/C=0.06) and shows a mass spectral pattern very similar to those of POA from fossil fuel combustion, and correlates tightly with traffic emission tracers including elemental carbon and NOx. LV-OOA, which is highly oxidized (O/C=0.63) and correlates well with sulfate, appears to be representative for regional, aged secondary OA (SOA). SV-OOA, which is less oxidized (O/C=0.38) and correlates well with non-refractory chloride, likely represents less photo-chemically aged, semi-volatile SOA. COA shows a similar spectral pattern to the reference spectra of POA from cooking emissions and a distinct diurnal pattern peaking around local lunch and dinner times. In addition, NOA is characterized with prominent CxH2x+2N+ peaks likely from amine compounds. Our results indicate that cooking-related activities are a major source of POA in NYC, releasing comparable amounts of POA as traffic emissions. POA=HOA+COA) on average accounts for ~30% of the total OA mass during this study while SOA dominates the OA composition with SV-OOA and LV-OOA on average accounting for 34% and 30%, respectively, of the total OA mass. The chemical evolution of SOA in NYC involves a~continuous oxidation from SV-OOA to LV-OOA, which is further supported by a gradual increase of O/C ratio and a simultaneous decrease of H/C ratio in total OOA. Detailed analysis of NOA (5.8% of OA) presents evidence that nitrogen-containing organic species such as amines might have played an important role in the atmospheric processing of OA in NYC, likely involving acid-base chemistry. Analysis of air mass trajectories and satellite imagery of aerosol optical depth (AOD) indicates that the high potential source regions of secondary sulfate and aged OA are mainly located in regions to the west and southwest of the city.

scholarly journals Investigations of primary and secondary particulate matter of different wood combustion appliances with a high-resolution time-of-flight aerosol mass spectrometer

2011 ◽  
Vol 11 (12) ◽  
pp. 5945-5957 ◽  
Author(s):  
M. F. Heringa ◽  
P. F. DeCarlo ◽  
R. Chirico ◽  
T. Tritscher ◽  
J. Dommen ◽  
...  
Keyword(s):  
High Resolution ◽  
Mass Spectrometer ◽  
Organic Aerosol ◽  
Smog Chamber ◽  
Resolution Time ◽  
Aerosol Mass Spectrometer ◽  
Aerosol Mass ◽  
Wood Burning ◽  
Primary Emissions ◽  
Stable Burning

Abstract. A series of photo-oxidation smog chamber experiments were performed to investigate the primary emissions and secondary aerosol formation from two different log wood burners and a residential pellet burner under different burning conditions: starting and flaming phase. Emissions were sampled from the chimney and injected into the smog chamber leading to primary organic aerosol (POA) concentrations comparable to ambient levels. The composition of the aerosol was measured by an Aerodyne high resolution time-of-flight aerosol mass spectrometer (HR-TOF-AMS) and black carbon (BC) instrumentation. The primary emissions were then exposed to xenon light to initiate photo-chemistry and subsequent secondary organic aerosol (SOA) production. After correcting for wall losses, the average increase in organic matter (OM) concentrations by SOA formation for the starting and flaming phase experiments with the two log wood burners was found to be a factor of 4.1±1.4 after five hours of aging. No SOA formation was observed for the stable burning phase of the pellet burner. The startup emissions of the pellet burner showed an increase in OM concentration by a factor of 3.3. Including the measured SOA formation potential, average emission factors of BC+POA+SOA, calculated from CO2 emission, were found to be in the range of 0.04 to 3.9 g/kg wood for the stable burning pellet burner and an old log wood burner during startup respectively. SOA contributed significantly to the ion C2H4O2+ at mass to charge ratio m/z 60, a commonly used marker for primary emissions of wood burning. This contribution at m/z 60 can overcompensate for the degradation of levoglucosan leading to an overestimation of the contribution of wood burning or biomass burning to the total OM. The primary organic emissions from the three different burners showed a wide range in O:C atomic ratio (0.19−0.60) for the starting and flaming conditions, which also increased during aging. Primary wood burning emissions have a rather low relative contribution at m/z 43 (f 43) to the total organic mass spectrum. The non-oxidized fragment C3H7+ has a considerable contribution at m/z 43 for the fresh OA with an increasing contribution of the oxygenated ion C2H3O+ during aging. After five hours of aging, the OA has a rather low C2H3O+ signal for a given CO2+ fraction, possibly indicating a higher ratio of acid to non-acid oxygenated compounds in wood burning OA compared to other oxygenated organic aerosol (OOA).

scholarly journals Electrochemistry-High Resolution Mass Spectrometry to Study Oxidation Products of Trimethoprim

Environments ◽  
2018 ◽  
Vol 5 (1) ◽  
pp. 18 ◽  
Author(s):  
Marc-André Lecours ◽  
Emmanuel Eysseric ◽  
Viviane Yargeau ◽  
Jean Lessard ◽  
Gessie Brisard ◽  
...  
Keyword(s):  
Mass Spectrometry ◽  
High Resolution ◽  
High Resolution Mass Spectrometry ◽  
Oxidation Products ◽  
High Resolution Mass ◽  
Resolution Mass

scholarly journals Factor analysis of combined organic and inorganic aerosol mass spectra from high resolution aerosol mass spectrometer measurements

2012 ◽  
Vol 12 (5) ◽  
pp. 13299-13335
Author(s):  
Y. L. Sun ◽  
Q. Zhang ◽  
J. J. Schwab ◽  
T. Yang ◽  
N. L. Ng ◽  
...  
Keyword(s):  
High Resolution ◽  
Ammonium Nitrate ◽  
Mass Spectrometer ◽  
Mass Spectra ◽  
Organic Nitrates ◽  
Aerosol Mass Spectrometer ◽  
Inorganic Aerosols ◽  
Aerosol Mass ◽  
Inorganic Species ◽  
Mixing Characteristics

Abstract. The high resolution mass spectra of organic and inorganic aerosols from aerosol mass spectrometer (AMS) measurements were first combined into positive matrix factorization (PMF) analysis to investigate the sources and evolution processes of atmospheric aerosols. The new approach is able to study the mixing of organic aerosols (OA) and inorganic species, the acidity of OA factors, and the fragment ion patterns related to photochemical processing. In this study, PMF analysis of the unified AMS spectral matrices resolved 8 factors for the submicron aerosols measured at Queens College in New York City in summer 2009. The hydrocarbon-like OA (HOA) and cooking OA (COA) contain very minor inorganic species, indicating the different sources and mixing characteristics between primary OA and secondary species. The two factors that are primarily ammonium sulfate (SO4-OA) and ammonium nitrate (NO3-OA), respectively, are overall neutralized, of which the OA in SO4-OA shows the highest oxidation state (O/C = 0.69) among OA factors. The semi-volatile oxygenated OA comprises two components, i.e., a less oxidized (LO-OOA) and a more oxidized (MO-OOA). The MO-OOA represents a local photochemical product with the diurnal profile exhibiting a pronounced noon peak, consistent with those of formaldehyde (HCHO) and Ox (= O3+NO2). The much higher NO+/NO2+ fragment ion ratio in MO-OOA than that from ammonium nitrate alone provides evidence for the formation of organic nitrates. The amine-related nitrogen-enriched OA (NOA) contains ~25% of acidic inorganic salts, elucidating the formation of secondary OA from amines in acidic environments. The size distributions derived from 3-dimensional size-resolved mass spectra show distinct diurnal evolving behaviors for different OA factors, but overall a progressing evolution from smaller to larger particle mode as a function of oxidation states. Our results demonstrate that PMF analysis by incorporating inorganic aerosols is of importance for gaining more insights into the sources and processes, mixing characteristics, and acidity of OA.

Field-Deployable, High-Resolution, Time-of-Flight Aerosol Mass Spectrometer

2006 ◽  
Vol 78 (24) ◽  
pp. 8281-8289 ◽  
Author(s):  
Peter F. DeCarlo ◽  
Joel R. Kimmel ◽  
Achim Trimborn ◽  
Megan J. Northway ◽  
John T. Jayne ◽  
...  
Keyword(s):  
High Resolution ◽  
Mass Spectrometer ◽  
Time Of Flight ◽  
Resolution Time ◽  
Aerosol Mass Spectrometer ◽  
Aerosol Mass

scholarly journals Factor analysis of combined organic and inorganic aerosol mass spectra from high resolution aerosol mass spectrometer measurements

2012 ◽  
Vol 12 (18) ◽  
pp. 8537-8551 ◽  
Author(s):  
Y. L. Sun ◽  
Q. Zhang ◽  
J. J. Schwab ◽  
T. Yang ◽  
N. L. Ng ◽  
...  
Keyword(s):  
High Resolution ◽  
Ammonium Nitrate ◽  
Mass Spectrometer ◽  
Mass Spectra ◽  
Organic Aerosol ◽  
Organic Nitrates ◽  
Spectral Matrix ◽  
Aerosol Mass Spectrometer ◽  
Aerosol Mass ◽  
Inorganic Species

Abstract. Positive matrix factorization (PMF) was applied to the merged high resolution mass spectra of organic and inorganic aerosols from aerosol mass spectrometer (AMS) measurements to investigate the sources and evolution processes of submicron aerosols in New York City in summer 2009. This new approach is able to study the distribution of organic and inorganic species in different types of aerosols, the acidity of organic aerosol (OA) factors, and the fragment ion patterns related to photochemical processing. In this study, PMF analysis of the unified AMS spectral matrix resolved 8 factors. The hydrocarbon-like OA (HOA) and cooking OA (COA) factors contain negligible amounts of inorganic species. The two factors that are primarily ammonium sulfate (SO4-OA) and ammonium nitrate (NO3-OA), respectively, are overall neutralized. Among all OA factors the organic fraction of SO4-OA shows the highest degree of oxidation (O/C = 0.69). Two semi-volatile oxygenated OA (OOA) factors, i.e., a less oxidized (LO-OOA) and a more oxidized (MO-OOA), were also identified. MO-OOA represents local photochemical products with a diurnal profile exhibiting a pronounced noon peak, consistent with those of formaldehyde (HCHO) and Ox(= O3 + NO2). The NO+/NO2+ ion ratio in MO-OOA is much higher than that in NO3-OA and in pure ammonium nitrate, indicating the formation of organic nitrates. The nitrogen-enriched OA (NOA) factor contains ~25% of acidic inorganic salts, suggesting the formation of secondary OA via acid-base reactions of amines. The size distributions of OA factors derived from the size-resolved mass spectra show distinct diurnal evolving behaviors but overall a progressing evolution from smaller to larger particle mode as the oxidation degree of OA increases. Our results demonstrate that PMF analysis of the unified aerosol mass spectral matrix which contains both inorganic and organic aerosol signals may enable the deconvolution of more OA factors and gain more insights into the sources, processes, and chemical characteristics of OA in the atmosphere.

Sign in / Sign up

Export Citation Format

Share Document