They sniff for a variety of explosives. Explosives, which often take the form of liquids or semi-solids, emit molecules with a particular scent. As this Salon article notes, dogs have 20 to 40 times more smell receptors than people do, and can be trained to react to specific scents.
Much of the science and training behind bomb-sniffing dogs is classified by the government. We do know that most of these dogs are trained at Lackland Air Force Base in San Antonio, Texas. We also know that bomb-sniffing dogs are " passive response" workers -- if they smell an explosive, they're trained to immediately sit and wait for their reward.
Dogs can identify dozens of mixed scents within a 5-foot radius. This helps trained dogs work effectively in environments that feature all kinds of curious odors, such as airport runways, indoor stadiums, border checkpoints, etc. Since the dogs rarely come across actual explosives, they're often given "dummy scents" to keep them attentive.
Perhaps the most famous bomb-sniffing dog of all was a brave pooch by the name of Sirius. Sadly, Sirius died in the September 11 attacks on New York City.
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