Spofforth, who beat Simmonds to the European title, qualified as the sixth-fastest swimmer, with GeorgiaDavies of Wales through in eighth, but Simmonds missed out.
James won men's 100m butterfly silver and Simmonds was pipped to women's 200m backstroke gold, as was Spofforth over the 50m backstroke distance - a race in which Wales' GeorgiaDavies tied for bronze.