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You can probably jump on wherever you like if you have numbers and stuff, but there isn't that much waiting around at Olympic park, just enough to pop to the loo, and the setting off is pretty cool. And you come down is it the A12 or something? A road you can't/wouldn't normally. Oh, also you can give them your bag at the start and pick it up at the end, is useful...
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Sorry that was a bit blunt!
If you are unlikely to ride it again in the future I would just go for it, but I can understand if you normally work weekends it makes the few you have off more valuable (I work a fair few myself).
It's an event I didn't think I would enjoy but riding the closed roads is ace, and going to the Olympic Park for a mass start was one of the really enjoyable bits.
Thanks for the info. The difference of a few hours means quite a lot to my partner! Especially on a weekend when I'm not working (she's looking after a 3 month old as well as a toddler) and she usually welcomes the break from doing things on her own.