“Radioactive” is not the same thing as “can sustain a nuclear chain reaction”. Very very few radioactive materials can do that, and those are the ones we use in a reactor.
Spent nuclear fuel is what’s left after you’ve burned off a lot of the material that *can* sustain a chain reaction. It’s still decaying, but it’s not decaying at a rate you can run a power plant off of. Unfortunately, there’s a very wide gap between “safe for life” and “can power a city”, and spent fuel spends a long time in between the two.
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