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Abstract: A quick and direct method for identifying organic components of papers in library and archival collections with minimal destructive sampling is needed for preservation, forensic, and general purposes. Direct analysis in real time mass spectrometry (DART-MS) is used for characterizing 16 reference papers of known manufacture in terms of their pulp composition and pitch contaminants. Unique mass spectra are obtained from bleached kraft, chemithermomechanical, and stone groundwood pulp papers in real time without extractions, derivatizations, chromatographic separations, and other time- and chemical-consuming sample preparations. Phytosteroids are volatilized from bleached hardwood kraft but not from bleached softwood kraft papers, which differentiates the two of them. The kraft papers are in turn differentiated from chemithermomechanical pulp papers by lignin-derived thermolyis products: syringyl products arise from hardwood, but guaiacyl and coumaryl products arise from softwood, chemithermomechanical pulp papers. Stone groundwood papers contain a number of extractives that are volatilized, which serve to differentiate them from all the other papers. Papers that contain rosin vs. alkyl ketene dimer (AKD) sizings are immediately differentiated. The DART-MS methodology is fast and simple, and the spectra are repeatable. Microsamples as small as ∼10μg tweezed from the paper surface may be analyzed. These benchmark spectra are the prelude to further applications of DART-MS in paper research and the beginning of the development of a searchable library of DART-MS spectra of printing and writing papers by the Library of Congress. [Copyright &y& Elsevier]