You might already know this, you might not, but I'm going to lay the groundwork for the Captain's backstory.
He was raised by his mother with Bianca, before they went to Polar Scouts, which acted as a sort of accommodations-and-education for the two of them, amongst other polar scouts. After a while, Barnacles was taken on board by Professor Natquik, who trained him with all the skills for his eventual job, Captain on Inkling's crew.
There you go. Anyways, I'll tell you about the polar scouts that trained alongside the Captain.
You already know Barnacles and Bianca, so I'll skip over them.
There's Alexander, or Xand as he was known as. He was quite like Kwazii, daring and at times quite impulsive. This, uh, led to quite a few little accidents and a whole lot of what he called "battle scars" and what the others called "hospital visits." He loved to explore, and would get quite annoyed at Barnacles or anyone else if they went caving without him.
Isla. Isla was strange. She definitely had a crush on the Captain, and she definitely let everyone know about it. Some of you will know this, but she decided one day to announce that the two of them were getting married. He is still quite embarrassed about it to this day. She was the definition of energetic, Dashi but more Dashi-y.
Anastasia! (insert the choral voices and the little cupids flying around). Now this is Barnacles' true love. They bonded over looking after the rest of the polar Scouts and lying in the Arctic summer talking about anything and everything. Bianca was effectively doing what Tweak did when Dashi and Shellington weren't official, giving both teams a little push to try and see them together. Didn't work, unfortunately. The Captain left to study under Natquik, and they didn't see each other again.
UNTIL... My Q&A book. Perhaps you should read it now if you haven't already coz this is your SPOILER ALERT. I brought Anastasia into the questioning room and... well, let's just say that the Captain spends a lot of time chatting to a certain someone on the phone late at night.
Tracker came later. His parents died in a blizzard, and he came knocking at the scouts' doorstep. They took him in, and when he opened up to Isla, she told him to bottle up his trauma hooray. However SPOILER ALERT FOR Q&A BOOK Dashi lets him open up about it when Tracker spills to her, showing him that the Octonauts really care about him.
Little Nell. She was really quiet, and she wouldn't say anything all that much. Turns out, she'd... seen things in her past. Things that gave her trauma, just like Tracker, and because she was quiet she was teased quite a bit.
Ivan. The gentle giant. He was big, he was strong, but he preferred to lie in the fields and watch the Arctic flowers float in the wind, or to watch animals. Actually, he loved watching animals.
Well, there you go. Maybe I'll do the leaders one day.

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Crash's book of Captain Barnacles
FanfictionEverything Captain Barnacles; headcanons, oneshots, art etc.