When you throw darts with the crossbow equipped, its special effect takes place. You just use the darts like you would any other throwing weapon. IIRC every shop should have at least a couple darts for sale.
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But how to use darts during boss fights, specifically the King fight? I tried the Crossbow once as the Freerunner and it ended miserably because I ran out of my six darts quickly after the fight started. It felt like I was using a Spirit Bow but with very limited ammo. Surely I'm missing something here?
You also don't need all that many to be helpful. Set him on fire, poison him, maybe blind if you fancy, but then focus on minions (or whatever else damaging you have for the last phase, then invis until deferred happens)
That's my usual strategy w/ other weapons, but the crossbow kinda sucks as a melee weapon even after upgrading it to like +5 or something, so I can't even clear the ghoul swarm with it in melee.
Put a thrown weapon in an alchemy pot, receive Liquid Metal.
Put Liquid Metal in alchemy pot, spend some energy, get a stack of spells that grab ranged weapons back from enemies and the ground.
Every shop has two randomly tipped darts, and that's the only way to acquire them.