Russia, which is backing the Syrian regime in the five-year war, announced plans to set up four corridors for civilians and fighters to leave Aleppo, which has been under heavy assault for weeks.
The proposal however raised concerns that the corridors could be used to flush out Aleppo before a final push by the Syrian regime forces to take the city.
"No one can be forced to flee, by any specific route or to any particular location," said Stephen O'Brien, the under-secretary general for humanitarian affairs.
The Syrian opposition condemned Russia's proposal, saying the exit corridors would be used to empty the city.
"If the corridors could be used to allow aid into Aleppo, then that would be welcome," said British Ambassador Matthew Rycroft.
"But clearly the UN and the rest of us cannot be complicit in anything else -- for instance, any form of emptying of Aleppo, or preparing for an onslaught in Aleppo, or indeed any continuation of this medieval siege of Aleppo which is going on."
The UN aid chief renewed his call for a 48-hour weekly humanitarian truce for Aleppo, saying this "is what we as humanitarians require."
Syrian regime forces seized the last remaining supply route to Aleppo this month and all humanitarian and commercial movements came to a halt on July 7.
Government forces have surrounded rebel-held districts in eastern Aleppo since July 17, sparking fears for at least 200,000 people who live there.
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