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The unique analytical capabilities of SIFT-MS for ambient analysis are stressed that allow quantification of volatile organic and inorganic compounds directly from the measurement of physical parameters without the need for regular instrumental calibration using internal or external standards. Then, emphasis is placed on the challenging real-time accurate analysis of single exhalations of humid breath, which is now achieved and readily facilitates wider applications of SIFT-MS in other fields where trace gas analysis has value. The quality of the data obtained by SIFT-MS is illustrated by the quantification of some exhaled breath metabolites that are of immediate relevance to physiology and medicine, including that of hydrogen cyanide in the breath of patients with cystic fibrosis. 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