Nanospray Laser-Induced\nPlasma Ionization Mass Spectrometry\nfor Sensitive and High-Coverage Analysis of Broad Polarity Organic\nPollutants

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