Created attachment 316597 [details] screenshot of error On a new rawhide 20080912 installation, if I go to 'System/Preferences/Look and Feel/Appearance' the attached error message appears, and then the appearance applet appears.
Created attachment 316599 [details] ps auxww from machine
Try launching /usr/libexec/gnome-settings-daemon by hand with --sync. I'm pretty sure this is the same problem as bug 466206.
Rawhide has a fix for that, thanks Ray! *** This bug has been marked as a duplicate of bug 466206 ***