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Acquire all pyromancies.

There are 27 Pyromancy spells in the game and you will need to buy and find most, as well as getting one from a Covenant. To get them all you will need two specific vendors, Cornyx of the Great Swamp and Karla the Witch.

Cornyx is in a cage on a building near the Cliff Underside bonfire in the Undead Settlement. Talk to him to get him to relocate to Firelink Shrine. Karla is found in Irythrill Dungeon, in the room with a host of jailers, but you need to get the Jailers Key from the Profaned Capital. In the toxic swamp area climb the ladder up the building here and follow the roof to the left and up some stairs, then follow this path ahead to find the key on a corpse. Go back and free her to make her move to Firelink Shrine.

You then need to find the following tomes and give them to the relevant vendor:

Great Swamp Pyromancy Tome - From the Halfway Fortress bonfire in Road of Sacrifices go straight forward and into the water, ahead with be a bunch of giant crabs and the scroll is on a corpse by a tree near to the entrance to Farron Keep. Give to Cornyx.

Carthus Pyromancy Tome - As you enter the Catacombs of Carthus you'll cross a bridge, on the left side is a ledge you can drop to (watch out for the enemies down here) then enter the next room to find the tome on a corpse. Give to Cornyx.

Izalith Pyromancy Tome - From the Old King's Antechamber bonfire, head down the left hand hallway to a room with a Ghru caster ahead (and two other enemies either side of the door) kill them and grab the tome in here. Give to Cornyx.

Quelana Pyromancy Tome - From the Demon Ruins bonfire go straight and down the stairs ahead of you. Go right as you exit and take the next door on your right. You'll enter a hallway with a rat ahead of you. Take the next right to a room with two rats - smack the illusionary wall ahead of you and grab the tome from the corpse. Give to Karla.

Grave Warden Pyromancy Tome - As soon as you start the boss fight with High Lord Wolnir it will be on a corpse just ahead of you, so be sure to grab it. Give to Karla.

The spells you need are as follows:

Fireball - Start with this if you're a Pyromancer or purchased from Cornyx of the Great Swamp for 1000 souls.

Fire Orb - Purchased from Cornyx of the Great Swamp for 3000 souls (Requires Great Swamp Pyromancy Tome).

Bursting Fireball - Purchased from Cornyx of the Great Swamp for 5000 souls (Requires Great Swamp Pyromancy Tome).

Great Chaos Fire Orb - Purchased from Cornyx of the Great Swamp for 10000 souls.

Chaos Bed Vestiges - Transposed from Soul of the Old Demon King for 5000 souls.

Fire Surge - Purchased from Cornyx of the Great Swamp for 1000 souls.

Fire Whip - Purchased from Karla for 10000 souls (Requires Quelana Pyromancy Tome).

Firestorm - Purchased from Karla for 15000 souls (Requires Quelana Pyromancy Tome).

Chaos Storm - Purchased from Cornyx of the Great Swamp for 12000 souls (Requires Izalith Pyromancy Tome)

Great Combustion - Purchased from Cornyx of the Great Swamp for 3000 souls.

Sacred Flame - In Smouldering Lake after you go through the Basilisk area look for a hole in the wall on your left, it leads to some stairs down and a tough fight with Knight Slayer Tsorig. The spell is in the lava just past him.

Profaned Flame - In Irythyll Dungeon you'll come to a room containing a giant, kill him (preferably from afar) and you can then drop down to where he was to loot this from a corpse. Watch out for all the rats.

Poison Mist - Purchased from Cornyx of the Great Swamp for 2000 souls (Requires Great Swamp Pyromancy Tome).

Toxic Mist - Found on corpse in lava area of Smouldering Lake. From the Demon Ruins bonfire go straight and down the stairs ahead of you. Go right as you exit and take the next door on your right. You'll enter a hallway with a rat ahead of you. Take the next right to a room with two rats - smack the illusionary wall ahead of you and then head through and down some stairs on your left. The spell is in the lava ahead so stock up on flame resistant gear.

Acid Surge - Purchased from Cornyx of the Great Swamp for 6000 souls (Requires Carthus Pyromancy Tome).

Flash Sweat - Purchased from Cornyx of the Great Swamp for 1000 souls.

Profuse Sweat - Purchased from Cornyx of the Great Swamp for 2000 souls (Requires Great Swamp Pyromancy Tome).

Iron Flesh - Found in the Farron Keep swamp. Go right from the first bonfire to find it on a corpse by a tree.

Power Within - In the Grand Archives you'll come to a pool of wax, surrounded by mages, on the first floor. Dip your head and then go into the next dark room. Pull the lever in the back left corner to open a bookcase and get this spell.

Carthus Beacon - Purchased from Cornyx of the Great Swamp for 8000 souls (Requires Carthus Pyromancy Tome).

Carthus Flame Arc - Purchased from Cornyx of the Great Swamp for 10000 souls (Requires Carthus Pyromancy Tome).

Warmth - Reward for reaching rank 2 in the Mound Makers covenant. The Covenant is located by sneaking up on the large undead with a cage in the Undead Settlement. Go over the stone bridge to the right of the large gathering of hollows, up the path to the right of the next building and over the roofs to the right to find him. This MUST be done before the Rotting Greatwood is killed. Alternatively complete the complete quest for Sirris to get access too. Then you need 30 Vertebrae Shackles - they can be acquired by invading as a covenant member OR farmed from the Red Eyed Skelton Swordsmen in the Catacombs of Carthus. From the Catacombs bonfire go forward then right (watch out for the boulder) then immediately left, at the end of this corridor will be two swordsmen to kill. Use the Covetous Gold Serpent Ring, Symbol of Avarice (found from minics) and Rusted Coins. Drop rate is roughly one in thirty with this combo.

Rapport - Purchased from Karla for 7000 souls (Requires Quelana Pyromancy Tome).

Boulder Heave - Obtained from the Soul of a Stray Demon Transposition.

Black Flame - Purchased from Karla for 10000 souls (Requires Grave Warden Pyromancy Tome).

Black Fire Orb - Purchased from Karla for 10000 souls (Requires Grave Warden Pyromancy Tome).

Black Serpent - Obtained from the Soul High Lord Wolnir Transposition.