There's lots of old lolcows but the one i best remember is Raksha, a grown woman who had a weird obsession with the 80s Transformers cartoons. I mean we're a bit obsessed with our particular fandoms but this lady took it to the next level. She has an ED page but you have to read the Usenet posts on her drama and remember this was a few years before 9-11.
There's also the tfwiki.net crowd but the one that stands out is David Willis aka It's Walky because he had a temper tantrum every time a talented fan artist successfully transitioned to official paid comics work and he did not (because he's not as good as he thinks he is as evidenced by his failed webcomics).
Now that I think about it this is all rather tame by today's standards.