This skill has no prerequisites. As with Hydra, it's not available until clvl 30, so that pretty much means it's a skill for Nightmare and beyond, not for Normal.
Fire Mastery adds bonus damage to all your fire skills -- or at least it's supposed to. In v1.06 and earlier, it is bugged and does not boost Hydra damage.
Of all three Mastery skills, this one makes the most sense to pump the highest (except Cold Mastery for PvP operations, but that's another story). In general, Fire Mastery breathes new life into your fire skills, juicing up their damage rates without increasing mana cost or further affecting framerates.
Clearly, the most benefit is to be found at the earliest levels. Taking the skill to slvl 5, either naturally or with help from +skills items, gets you an extra 60% damage. If you are using fire skills as a situational attack with a versatile sorcie, you will still want at least five points in Fire Mastery, eventually. Fire Sorcies and particularly Hot Babes will benefit from more. How much more depends on the rest of your character. You will have to make your own choice here.
Some target numbers for Fire Mastery include slvl 2 (32%), slvl 5 (60%), slvl 6 (66%), slvl 9, (79%), and slvl 11 (85%). After that, the returns diminish severely, and would only be worthwhile for a very high level sorcie who has maxed everything else of interest (maxed not necessarily meaning slvl 20, depends on the skill and its applications).
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