Nanospray Laser-Induced Plasma Ionization Mass Spectrometry for Sensitive and High-Coverage Analysis of Broad Polarity Organic Pollutants

Accurate, sensitive, and high-coverage analysis of various organic pollutants in complex samples and single cells is significant in investigating their environmental behaviors and toxic effects. Here we proposed a nanospray laser-induced plasma ionization mass spectrometry (nLIPI-MS) method for sensitive and high-coverage analysis of broad polarity organic pollutants under ambient and open-air conditions. The nLIPI-MS method combines nanospray with laser-induced plasma ionization, enabling direct analysis without sophisticated sample pretreatment. For the analysis of nonpolar and very weakly polar organic pollutants such as polycyclic aromatic hydrocarbons (PAHs) and alkyl-PAHs, the nLIPI-MS method showed desirable analytical performance, with limits of detection of as low as the μg/L level. For moderately polar organic pollutants such as <i>p</i>-phenylenediamine quinones (PPD-Qs), nLIPI-MS displayed significant enhanced sensitivity by 1 to 2 orders of magnitude in comparison to nanoelectrospray ionization (nESI)-MS. For more polar organic pollutants such as per- and polyfluoroalkyl substances (PFASs), nLIPI-MS also showed good analytical performance, with a sensitivity improvement of 1.3- to 2.7-fold over that of nESI-MS. The sensitivity of nLIPI-MS for the analysis of PPD-Qs and PFASs reached as low as the ng/L level, enabling the analysis of ultratrace levels of these pollutants in complex samples and even single cells. Our experimental results demonstrated that nLIPI-MS was an extensive ambient MS method, showing desirable analytical performance for the analysis of organic pollutants with broad polarity ranges.