Story related, unmissable.
Obtained after defeating Scorpion on the docks during Chapter 6: Spidey to the Rescue!
Scorpion is a bit harder here than his first appearance, but still fairly straightforward. Pummel him to start with, dodging his tail and claw attacks with when your spider-sense goes off. Watch out for when he covers the dock in acid – jump onto the crates at the end to avoid being hurt by this. When he leaps out onto the wooden poles in the water, dodge the acid spray with a combination of web swinging and jumping, and then web strike him with to knock him down. Keep up the pressure, and he’ll crumble.