"As a close security and trade partner of the USA, the European Union must be excluded from the announced measures", she tweeted after bilateral and trilateral meetings.
Speaking live on Denmark's TV2, Samuelsen said U.S. President Donald Trump's proposed trade tariffs are "a bad call".
But U.S. President Donald Trump is expected to sign on Thursday or Friday a proclamation to establish tariffs on steel and aluminium imports.
"This is not a trade negotiation", he said.
The European steel association Eurofer in Brussels today warned the US President's new import tariffs were "harmful and counterproductive" and could lead to the loss of tens of thousands of jobs in Europe.
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Mr Trump's announcement of duties of 25% on imported steel and 10% on aluminium has stung the European Union and triggered warnings of an all-out worldwide trade war.
There was still "no immediate clarity on the exact US procedure on exemption", Malmstrom, the 28-nation bloc's trade commissioner, said after the meeting that also included Japanese trade minister Hiroshige Seko.
"Moving away from WTO dispute settlement means that retaliation can easily escalate and we might find ourselves in the middle of a trade war between the two most important trade regions in the world", he said.
But Brussels reacted with fury to the tariff - seen by EU Commission boss Jean-Claude Juncker as a "blatant intervention to protect United States domestic industry".
The EU is also maintaining a threat of counter-measures that would target USA imports ranging from maize to motorcycles, and may publish its list next week to allow industry and other interested parties to give their input. "We cannot see how the European Union, friends and allies in North Atlantic Treaty Organisation, can be a threat to global security in the U.S".
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"We want Congress to understand that this would be a lose-lose situation", he said.
Any Japanese response, he said, would be in line with World Trade Organization rules: "If there is a violation, then we will seek consultations", Seko said.
She did not say what level of tariffs the European Union would set, leaving it unclear what the economic impact would be.
The White House said the move will help the United States protect industries and jobs from unfair competition and that across-the-board tariffs are needed because countries like China use third countries for shipping steel to the United States, disguising its origin.
Brussels wants to maximise the political impact of its reprisals on the U.S. while minimising the impact of a trade war on European consumers.
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"NATO related issues and trade are completely separate issues", European Commission official Jyrki Katainen told reporters.