You cannot do it in HQL as the join table is not mapped as an entity. You can do it using an SQL query easily enough:
Code:
<sql-query name="RemoveAssocFromUnloadedEntities">
delete from User_Group where userid = :userid and groupid = :groupid
</sql-query>
Then load this query and call executeUpdate. I can't remember if one of the <return*> tags is mandatory or not, but you should be able to get it working quite quickly.
Note that if you do this and you have either the user or the group in memory at the time, you'll have to refresh them afterwards, essentially wasting the performance benefit of running the query. So I suggest using the normal technique (group.getUsers().remove(user), etc.) when you have one or more of the relevant entities loaded, and only resort to the sql-query when neither entity is in memory.