I just upgraded from OS X Lion to OS X Mountain Lion. My rails environment for the most part stayed in tact.
The only steps I had to do to get things back to a good
Reinstalling ruby fixed a similar issue I was having after upgrading to Mountain Lion
rvm reinstall 1.9.3
Note: also run the following as it seems the default version resets
rvm --default 1.9.3
For reference I posted the error I was seeing below
gem install pg
Building native extensions. This could take a while...
ERROR: Error installing pg:
ERROR: Failed to build gem native extension.
/System/Library/Frameworks/Ruby.framework/Versions/1.8/usr/bin/ruby extconf.rb --with pg=/usr/local/Cellar/postgresql/9.1.4/bin
checking for pg_config... yes
Using config values from /usr/local/bin/pg_config
checking for libpq-fe.h... no
Can't find the 'libpq-fe.h header
*** extconf.rb failed ***