This question is similar to: What is the purpose of tilde character ~ in YAML?. If you believe it’s different, please edit the question, make it clear how it’s different and/or how the answers on that question are not helpful for your problem.
The actual meaning in Symfony 2 depends on what you are configuring. Most likely it will mean "use defaults" or it will be used where it is needed to put a configuration key but there is nothing to actually configure for that key (as in the NotBlank example).