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The pools cooling system can fail, the water evaporate, the un cooled fuel rods then heat and as they melt they can catch fire. The exact chain of events varies with the types of fuel rods stored and exactly how they are engineered. Regardless, cooling pools can be a bigger source of potential catastrophe than the reactor core.
Spent fuel pools don't stop cooling the fuel, ever. If fuel is in the pool, it receives cooling. There are active cooling systems that provide cooling to the pool water, and these can fail. In this instance, the pool water does warm up, but the fuel is still being cooled by natural convection. If left completely unattended, eventually the pool will reach 212°F and begin boiling. No further temperature rises occurs while the water is boiling. Once the water boils away, only then does temperature rises further and create a risk of fuel melt.
During refuel outages, some plants will move all of their fuel to the spent fuel pool prior to reload. During this time frame, with loss of forced cooling to the pool, it would reach 200°F in about 8 hours. During normal operations, this would take around 2 days. If somehow the normal fuel pool cooling was not restored, the pool would be allowed to approach boiling and a separate source of water would be supplied to the pool to makeup the evaporative losses.
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