I've got the log queries that dont use indexes set in my MySQL config file and it keeps logging one which I've tracked down to functions.php
if ( !$options = $wpdb->get_results( "SELECT option_name, option_value FROM $wpdb->options WHERE autoload = 'yes'" ) )
$options = $wpdb->get_results( "SELECT option_name, option_value FROM $wpdb->options" );
(its in the get_alloptions function).
Well autoload doesn't actually have an index on it.
Now you could argue that there aren't enough rows for it to matter but I'm interested in what anyone else thinks.