I don't quite know where this error is coming from. The ActiveRecord source doesn't seem to have it, and I'm not familiar enough with Rails or ActiveRecord to track definitively whether the failing function is actually performing a DB operation. Moreso I cannot seem to find any mentions (post 9.0 at least) of Hstore size limitations, either key/val pairs (which 8.x docs said was 65k) or the hstore field in its entirety.
I should note there is no error thrown into my postgres log at all.