We hear talk of players who wanted to sign up for a mission, but decided not to because it was "already full". Please hear this as lovingly as possible:
THAT'S NOT THE WAY IT WORKS!
The person who puts up the mission chooses which volunteers they want to take with them. If there are only just enough volunteers to field the mission, there's no choice to be made, but otherwise there are three major factors to consider:
1) Party composition. One volunteer might be preferable over another because they add something vital to the group - a skill that will be particularly useful (such as Navigation for an exploratory mission), for example, or a combat role (a party without any close combat characters is likely to struggle, so if you're the only close combat person signed up amidst a slew of spellcasters and ranged combatants, you're likely an attractive option!)
2) Opportunity. A player who is only available on Tuesdays will almost always get preferential placement on a mission over a player who is available to play six days a week. Similarly, primary characters tend to get preference over secondary characters. (That is, a player who is volunteering their only character is most likely to be chosen than a player who has a higher-tier character already and is volunteering their alt.)
3) Experience level. A Second Circle character volunteering for a Hard Third Circle mission might not be chosen, simply because their likelihood of survival is less good - and Hard missions are the ones that risk true fatality.
So, should you sign up for that mission?
Yes! Yes, you should! If you want to play, say so. And if you wanted to play but didn't get chosen, talk to a GM and schedule a game at a time and power level convenient to you.