Dogs have an incredibly well developed sense of smell - much better than people do. They have about 25 times the number of smell receptors in their nose as people - and that means they can detect smells even with very tiny concentrations of stuff there. Dogs have to sniff to be able to smell that well - normal breathing doesn't do it as the air won't go far enough back into the nose to hit all the receptors.
The sense of smell dogs have has been used by people for all sorts of applications - from drug-sniffing dogs, who can accurately figure out whether someone has drugs even when it's well-hidden, to rescue dogs, who in the case of earthquakes or collapses of buildings are able to smell out the location of both bodies and survivors. There is even recent scientific research showing that dogs can smell when a person gets cancer - essentially, they notice a tiny difference in the scent of the person indicating that they're sick. As shown here, we might one day have cancer sniffing dogs trained to give people a check-up.
In the wild, dogs mainly use their sense of smell to hunt. They can tell easily when prey is around or when a potential rival or predator is nearby.
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