Are you using any field in the table other than 'county'? If not, don't waste the database's and PHP's time by asking for all of them. SELECT * is generally nasty.
"SELECT DISTINCT * ... " is unlikely to work, because it looks at every field in each row - it's quite likely that every pair of rows differs in one field or another, so they're all distinct.
Short answer: To select distinct counties,
SELECT DISTINCT county ...