Interactive comment on “Development of an Automatic Linear Calibration Method for High Resolution Single Particle Mass Spectrometry...”

Abstract. The mass resolution of laser desorption ionization (LDI) single-particle aerosol mass spectrometry (SPAMS) is usually low (∼500), which has been greatly improved by the recent development of the delayed ion extraction technique. However, due to large fluctuations among LDI processes during each laser shot, accurate calibration of the mass-to-charge ratio for high-resolution SPAMS (HR-SPAMS) spectra is challenging. Here we developed an automatic linear calibration method to improve the accuracy of mass-to-charge (m∕z) measurement for single atmospheric aerosol particles. Laboratory-generated sea spray aerosol and atmospheric ambient aerosol were tested. After the calibration, the fluctuation ranges of the reference ions' (e.g., Pb+ and SO4+) m∕z reaches ±0.018 for sea spray aerosol and ±0.024 for ambient aerosol in average mass spectra. With such m∕z accuracy, the HR-SPAMS spectra of sea spray aerosol can easily identify elemental compositions of organic peaks, such as Cx, CxHy and CxHyOz. While the chemical compositions of ambient aerosols are more complicated, CxHy, CxHyOz and CNO peaks can also be identified based on their accurate mass. With the improved resolution, the time series of peaks with small m∕z differences can be separated and measured. In addition, it is also found that applying high-resolution data with enhanced mass calibration can significantly affect particle classification (identification) using the ART-2a algorithm, which classify particles based on similarities among single-particle mass spectra.

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Development of an Automatic Linear Calibration Method for High Resolution Single Particle Mass Spectrometry: Improved Chemical Species Identification for Atmospheric Aerosols

10.5194/amt-2019-489 ◽

2020 ◽

Author(s):

Shengqiang Zhu ◽

Lei Li ◽

Shurong Wang ◽

Mei Li ◽

Yaxi Liu ◽

...

Keyword(s):

Mass Spectrometry ◽

High Resolution ◽

Single Particle ◽

Mass Spectra ◽

Calibration Method ◽

Particle Mass ◽

Sea Spray ◽

Linear Calibration ◽

Ambient Aerosol ◽

Sea Spray Aerosol

Abstract. The mass resolution of laser desorption ionization (LDI) single particle aerosol mass spectrometry (SPAMS) is usually low (~500), which has been greatly improved by recent development of delayed ion extraction technique. However, due to large fluctuations among LDI processes during each laser shot, accurate calibration of mass-to-charge ratio for high resolution SPAMS spectra is challenging. Here we developed an automatic linear calibration method to improve the accuracy of mass-to-charge (m/z) measurement for single atmospheric aerosol particles. Laboratory generated sea spray aerosol and atmospheric ambient aerosol were tested. After the calibration, the fluctuation ranges of the reference ions (e.g. Pb+ and SO4+) m/z reaches ±0.018 for sea spray aerosol and ±0.024 for ambient aerosol in average mass spectra. With such m/z accuracy, the HR-SPAMS spectra of sea spray aerosol can easily identify elemental compositions of organic peaks, such as Cx, CxHy and CxHyOz. While the chemical compositions of ambient aerosols are more complicated, CxHy, CxHyOz and CNO peaks can also be identified based on their accurate mass. With the improved resolution, the time series of peaks with small m/z differences can be separated and measured. In addition, it is also found that applying high resolution data with enhanced mass calibration can significantly affect particle classification (identification) using the ART-2a algorism, which classify particles based on similarities among single particle mass spectra.

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Characterization of vertical aerosol flows by single particle mass spectrometry for micrometeorological analysis

Atmospheric Research ◽

10.1016/j.atmosres.2011.05.017 ◽

2011 ◽

Vol 102 (1-2) ◽

pp. 49-56 ◽

Cited By ~ 2

Author(s):

Elmar Gelhausen ◽

Klaus-Peter Hinz ◽

Andres Schmidt ◽

Bernhard Spengler

Keyword(s):

Mass Spectrometry ◽

Single Particle ◽

Particle Mass ◽

Single Particle Mass Spectrometry

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Supplementary material to "Understanding of atmospheric aerosol particles with improved particle identification and quantification by single particle mass spectrometry"

10.5194/amt-2018-362-supplement ◽

2018 ◽

Author(s):

Xiaoli Shen ◽

Harald Saathoff ◽

Wei Huang ◽

Claudia Mohr ◽

Ramakrishna Ramisetty ◽

...

Keyword(s):

Mass Spectrometry ◽

Single Particle ◽

Atmospheric Aerosol ◽

Aerosol Particles ◽

Particle Mass ◽

Particle Identification ◽

Atmospheric Aerosol Particles ◽

Single Particle Mass Spectrometry ◽

Supplementary Material ◽

Identification And Quantification

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Single-Particle Mass Spectrometry of Metal-Bearing Diesel Nanoparticles

Nanotechnology and the Environment - ACS Symposium Series ◽

10.1021/bk-2005-0890.ch017 ◽

2004 ◽

pp. 142-151

Author(s):

Donggeun Lee ◽

Art Miller ◽

David Kittelson ◽

Michael R. Zachariah

Keyword(s):

Mass Spectrometry ◽

Single Particle ◽

Particle Mass ◽

Single Particle Mass Spectrometry

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Resonance-Enhanced Detection of Metals in Aerosols using Single Particle Mass Spectrometry

10.5194/acp-2020-25 ◽

2020 ◽

Author(s):

Johannes Passig ◽

Julian Schade ◽

Ellen Iva Rosewig ◽

Robert Irsig ◽

Thomas Kröger-Badge ◽

...

Keyword(s):

Mass Spectrometry ◽

Excimer Laser ◽

Single Particle ◽

Aerosol Particles ◽

Ambient Air ◽

Particle Mass ◽

Anthropogenic Aerosols ◽

Single Particle Mass Spectrometry ◽

Krf Excimer Laser ◽

The Impact

Abstract. We describe resonance effects in laser desorption/ionization (LDI) of particles that substantially increase the sensitivity and selectivity to metals in single particle mass spectrometry (SPMS). Within the proposed scenario, resonant light absorption by ablated metal atoms increases their ionization rate within a single laser pulse. By choosing the appropriate laser wavelength, the key micronutrients Fe, Zn and Mn can be detected on individual aerosol particles with considerably improved efficiency. These ionization enhancements for metals apply to natural dust and anthropogenic aerosols, both important sources of bioavailable metals to marine environments. Transferring the results into applications, we show that the spectrum of our KrF-excimer laser is in resonance with a major absorption line of iron atoms. To estimate the impact of resonant LDI on the metal detection efficiency in SPMS applications, we performed a field experiment on ambient air with two alternately firing excimer lasers of different wavelengths. Herein, resonant LDI with the KrF-excimer laser (248.3 nm) revealed Fe signatures for many more aerosol particles compared to the more common ArF-excimer laser line of 193.3 nm. Moreover, resonant ionization of iron appeared to be less dependent on the particle matrix than conventional non-resonant LDI, allowing a more universal and secure detection of Fe. Our findings show a way to improve the detection and source attribution capabilities of SPMS for particle-bound metals, a health-relevant aerosol component and an important source of micronutrients to the surface oceans affecting marine primary productivity.

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