Comparison of Plasma Ionization- and Secondary Electrospray Ionization- High-resolution Mass Spectrometry for Real-time Breath Analysis


  • Jiafa Zeng University Children's Hospital Basel, University of Basel
  • Alexandra Christen University of Applied Sciences Northwestern Switzerland
  • Kapil Dev Singh University Children's Hospital Basel, University of Basel
  • Urs Frey University Children's Hospital Basel, University of Basel
  • Pablo Sinues University Children's Hospital Basel



Breath analysis, Mass spectrometry, Plasma ionization, secondary electrospray ionization


Real-time breath analysis by high-resolution mass spectrometry (HRMS) is a promising method to noninvasively retrieve relevant biochemical information. In this work, we conducted a head-to-head comparison of two ionization techniques: Secondary electrospray ionization (SESI) and plasma ionization (PI), for the analysis of exhaled breath. Two commercially available SESI and PI sources were coupled to the same HRMS device to analyze breath of two healthy individuals in a longitudinal study. We analyzed 58 breath specimens in both platforms, leading to 2,209 and 2,296 features detected by SESI-HRMS and by PI-HRMS, respectively. 60% of all the mass spectral features were detected in both platforms. However, remarkable differences were noted in terms of the signal-to-noise ratio (S/N), whereby the median (interquartile range, IQR) S/N ratio for SESI-HRMS was 115 (IQR = 408), whereas for PI-HRMS it was 5 (IQR = 5). Differences in the mass spectral profiles for the same samples make the inter-comparability of both techniques problematic. Overall, we conclude that both techniques are excellent for real-time breath analysis because of the very rich mass spectral fingerprints. However, further work is needed to fully understand the exact metabolic insights one can gather using each of these platforms.




How to Cite

J. Zeng, A. Christen, K. Dev Singh, U. Frey, P. Sinues, Chimia 2022, 76, 127, DOI: 10.2533/chimia.2022.127.