Kaja Kallas, the EU's foreign policy chief, said the bloc has "no interest to pick a fight, but we will hold our ground".
Pedro Sanchez announces three days of mourning after at least 40 people died in Sunday's collision in southern Spain.
What caused the train to derail remains unclear but officials say an investigation has been launched.
The BBC's Guy Hedgecoe visited the scene, where a large police cordon is in place.
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