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I think that vampire venom is not unlike human saliva, as in Midnight Sun, Edward describes the 'excess flow of venom' to his mouth when he is thirsty and a human walks by. It could be compared to a human 'drooling' when they are hungry and something delicious walks by.

Meyer's vampires do not have fangs, only extremely sharp teeth coated in the venom, so it would be impossible to collect the venom from the teeth.

This considered, taking the venom would be like collecting spit from a human.

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