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#77: Star Trek: The Animated Series, season 2, episode 1 "The Pirates of Orion"
Written by Howard Weinstein, directed by Bill Reed.
Stardate 5527.3 (early 2269)
(Using the novelization Stardate)
"Blasted Vulcan! Why can't you have red blood like any normal Human?" - Doctor McCoy
Commander Spock has contracted an illness that is nothing to humans, but fatal to Vulcans due to their blood containing copper instead of iron. Since the Enterprise is warping away on mission, Captain Kirk contacts Starfleet and arranges for life-saving drugs to be handed off from the USS Potemkin to the USS Huron which will then rendezvous with the Enterprise with only days to spare. However, the Huron is ambushed by Orion pirates and their entire cargo of Dilithium (including the medicine meant for Spock) is taken and the ship left adrift. The Enterprise picks up their distress call and double backs to rescue the crew of the Huron. Now Kirk has the Enterprise chasing the emissions of the pirate ship in a desperate attempt to recover the medicine before Spock's organs give out.
Originally released: 7 September 1974
"The Pirates of Orion" on Memory Alpha (mirror)
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What did you think?
The cargo ship is verbally misidentified as the SS Huron, even though it has a USS prefix and a crew wearing Starfleet uniforms.
And the Orions... just aren't Orions. And they are mispronounced as well. I think they were originally meant to be unique aliens, but Kirk referencing their attempt to sabotage the Babel Peace Conference back in Journey to Babel removes all doubt. Future Star Trek incorporates this unique appearance into the species, suggesting there are multiple races of Orion coexisting.
There's a great Lower Decks episode that mocks/celebrates the Green Orions and the Blue Or-ee-ons and sort of retcons it to make sense - but I don't think I've seen the Blue Or-ee-ons in any other series.