What causes an ant that is crawling along your skin to suddenly bite you?

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What causes an ant that is crawling along your skin to suddenly bite you?

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Biological ‘instinct’. A lot of ants are programmed to defend the colony with no regard for self preservation. Some ants are just assholes in this regard like fire ants that will bite and sting you just because they are on you.

As for you getting seemingly randomly bit while nowhere near the colony (as far as you’re aware), the ant isn’t necessarily aware of its proximity to the colony so it can have ‘defense mode’ triggered for little to no reason once it realizes it’s crawling on a living thing.