Probably volatile does not make much difference with gcc -O0 -for GCC 4.7 or earlier. However, this is probably changing in the next version of GCC (i.e. future 4.8, that is current trunk). And the next version will also provide -Og to get debug-friendly optimization.
In GCC 4.7 and earlier no optimizations mean that values are not always kept in registers from one C (or even Gimple, that is the internal representation inside GCC) instruction to the next.
Also, volatile has a specific meaning, both for standard conforming compilers and for human. For instance, I would be upset if reading some code with a sig_atomic_t variable which is not volatile!
BTW, you could use the -fdump-tree-all option to GCC to get a lot of dump files, or use the MELT domain specific language and plugin, notably its probe to query the GCC internal representations thru a graphical interface.