The cause of the pain is actually twofold. First, the fire ant bites you with their pinchers to get a good grip on you. Then, they will sting you from their abdomen and inject a toxic venom called solenopsin. As they hold on with their pinches, they go in a circle and stinging you as much as 10 stings. This leads to the welt that you see.
Because their venom is toxic to the skin — the alkaloids in their venom react with the skin, leading to pain and the growth of pustules. Here’s a scientific breakdown of their venom: http://emedicine.medscape.com/article/1089027-overview#a0104
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