Well, they do and they don’t. It depends on the animal.
But at the end of the day, hunger is a huge motivator. If an animal is hungry, it is going to try eating ANYTHING in front of them and see if it’s good/satiating.
In fact, more often then not animals DONT know what is safe if their normal food isn’t around, and just eat whatever they can.
So people actually have to make sure they walk any new pasture area or walk any area they are leaving animals to make sure there aren’t any plants there that are toxic that they may actually eat.
So, TL:DR, animals will eat whatever they can when hunger drives them to, including both safe and unsafe food.
Animals will usually try eating most things that look or smell even remotely food-like. They may learn to avoid certain scents, colours, patterns etc relating to toxic foods native to their natural habitat, but as long as the new food does not have any of those markers, they will generally give it a try.
This of course presents a problem if the non-native food contains some unfamiliar toxin, as the animals may not have developed the instincts to avoid it.
Same way humans learned. Trial and error. If it didn’t kill the person that ate it first, it must be safe to eat. Now, ask yourself how many people died eating stuff like mushrooms before they found the safe ones.
Higher animal’s can tell what’s safe by learning or knowing from evolution of smell. Others….are still evolving.
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