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Sulfur mustard is a blister agent prohibited by the Chemical Weapons Convention, and the detection of its hydrolysis product, thiodiglycol (TDG), is an important indicator of blister agent contamination. Due to the poor volatility and low extraction efficiency of TDG, derivatization gas chromatography or liquid chromatography is required for conventional methods, and the detection process is cumbersome and time-consuming. A microextraction by packed sorbent (MEPS) device and a nano-electrospray ionization (nano-ESI) device were used. The