The present invention provides IMS analyzers and methods for detecting, identifying, and characterizing (e.g., measuring the concentration of) peroxides in samples. Methods and systems of the present invention utilize sample inlet conditions and dopant strategies providing an enhancement in selectivity and sensitivity for the detection of peroxide compounds relative to conventional IMS analyzers. Dopants of the present invention include, but are not limited to, substituted aryl compounds or substituted cyclic dienes; wherein the substituted aryl compound or the substituted cyclic diene has at least one substituent selected from the group consisting of a hydroxyl group, a carbonyl group, an aldehyde group, an ester group, a carboxylic acid group and a carbonate ester group. The present IMS analyzers and methods are versatile and enable selective detection of a broad class of peroxides and derivatives thereof, including hydrogen peroxide, hydroperoxides, organic peroxides and derivatives thereof.