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The analytical capabilities associated with the use of silylation reactions have been extended to a new class of organic molecules, nitroaromatic compounds (NACs). These compounds are a possible contributor to urban particulate matter of secondary origin which would make them important analytes due to their (1) detrimental health effects, (2) potential to affect aerosol optical properties, and (3) and usefulness for identifying PM2.5 from biomass burning. The technique is based on derivatization of the parent NACs by using N,O-bis-(trimethylsilyl)-trifluoro acetamide, one of the most prevalent derivatization reagent for analyzing hydroxylated molecules, followed by gas chromatography-mass spectrometry using electron ionization (El) and methane chemical ionization (CI). This method is evaluated for 32 NACs including nitrophenols, methyl-/methoxy-nitrophenols, nitrobenzoic acids, and nitrobenzyl alcohols. Electron ionization spectra were characterized by a high abundance of ions corresponding to [M+] or [M+ - 15]. Chemical ionization spectra exhibited high abundance for [M+ + 1], [M+- 15], and [M++ 29] ions. Both EI and CI spectra exhibit ions specific to nitro group(s) for [M+- 31], [M+ - 45], and [M+- 60]. The strong abundance observed for [M+] (El), [M+ - 15] (El/CI), or [M+ + 1] (CI) ions is consistent with the high charge stabilizing ability associated with aromatic compounds. The combination of EI and CI ionization offers strong capabilities for detection and identification of NACs. Spectra associated with NACs, containing hydrogen, carbon, oxygen, and nitrogen atoms only, as silylated derivatives show fragment/adduct ions at either (a) odd or (b) even masses that indicate either (a) odd or (b) even number of nitro groups, respectively. Mass spectra associated with silylated NACs exhibited 3 distinct regions where characteristic fragmentation with a specific pattern associated with (1) -OH and/or -COOH groups, (2) -NO2 group(s), and (3) benzene ring(s). These findings were confirmed with applications to chamber aerosol and ambient PM2.5.