Optimization and Application of Paper-Based Spray Ionization Mass Spectrometry for Analysis of Natural Organic Matter

In this study, paper-based ionization techniques - paper spray ionization (PSI) and paper spray chemical ionization (PSCI) - were evaluated and applied for high-resolution mass spectrometry (MS)-based analysis of natural organic matter (NOM). Methanol:isopropyl alcohol (50:50, v/v) and ethanol emerged as good spray solvents for PSI, and hexane:dichloromethane (50:50, v/v) was a good spray solvent for PSCI. PSI-MS spectra could be obtained with NOM samples on the microgram scale, which is a critical advantage over conventional electrospray ionization (ESI)-MS when the amount of available sample is limited. In addition, PSI is more tolerant to salt contamination than ESI for NOM analysis. PSCI preferentially ionized less polar compounds, which may not be ionized well using ESI. Therefore, PSCI can be used as a complementary method to ESI or PSI. Comparison of the numbers of peaks obtained with ESI-, PSI-, and PSCI-MS showed that employing PSI and PSCI can increase the number of compounds that can be detected by high-resolution MS. In conclusion, the data presented in this study showed that PSI and PSCI are suitable ionization techniques for NOM analysis. To the best of our knowledge, this is the first study evaluating and applying PSI and PSCI for NOM analysis.