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Unlock Arachnoman
Complete 90 City Events, Collect 90 Tokens & Complete 48 Combat Tours

Unlock Parker Hoodie
Complete 75 City Events, Collect 75 Tokens & Complete 32 Combat Tours

Unlock Peter Parker
Complete 50 City Events, Collect 50 Tokens & Win 4th Race against Johnny Storm

Unlock Spidey Wrestling
Complete 30 City Events & Collect 30 Tokens

Unlock Switch Hero Option on Pause Menu
Complete all Story Missions

Unlock Symbiote Spider-Man (Black Costume)
Complete 100 City Events, Get all Tokens, and finish all Combat Tours

Unlock Venom Races
Complete all Story Missions

Unlock Hard Difficulty
Complete 20 City Events and Complete "Class Trip" Chapter 8.

Unlock Medium Difficulty
Complete 10 City Events and Complete "inexpugnable" Chapter 6.

Unlock Health Bonus & Hard Difficulty Combat Tours
Complete 12 Medium Combat Tours.

Unlock Health Bonus & Medium Difficulty Combat Tours
Complete 8 Easy Combat Tours After Chapter 4 Hell of a Mess.

Unlock Insane Difficulty Combat Tours
Complete all Hard Combat Tours

Medium city event difficulty:
Complete 10 city events and "Inexpugnable" (Chapter 6).

Hard city event difficulty:
Complete 20 city events and "Class Trip" (Chapter 8).

Medium combat tour difficulty:
Complete 8 easy combat tours after "Hell of a Mess" (Chapter 4).

Hard combat tour difficulty:
Complete 12 medium difficulty combat tours.

Insane combat tour difficulty:
Complete all hard difficulty combat tours.

Fight Shocker again:
You can see Shocker even after you have defeated him. Sometimes in a City Event, Shocker will appear and you must fight him. It will not be a Boss battle, though -- just a fight against a street thug, who has some very powerful blasters. Note: He is also stronger than all street thugs.

See Boomerang:
Boomerang can also appear in a City Event.