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This can be a useful skill for any Healing or Protection monk who has some spare points to go on Smiting Prayers. Since Zealot's Fire will do damage to any foes adjacent to your target it's often best to concentrate on healing warriors and pets, since they will most likely be closest to your foes.
To trigger Zealot's Fire rapidly, use skills such as Reversal of Fortune and Draw Conditions that have short activation and recharge times.