The convoy was carrying 2,000 tons of humanitarian aid, according to the Itar-Tass news agency. It included 400 tons of cereals, 100 tons of sugar, 62 tons of baby food, 54 tons of medical equipment and medicine, 12,000 sleeping bags and 69 generators of various sizes, the agency reported.
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In talking about the convoy on Monday, Sergey V. Lavrov, the Russian foreign minister, said he hoped the humanitarian effort by Russia would not be blocked by Kyiv or its Western allies.
The secretary general of NATO, Anders Fogh Rasmussen, estimated that there was a "high probability" that Russia could attack, and Ukraine announced that even more Russian troops than previously thought were massed along the borders.
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Speaking by telephone on Monday, Mr. Putin told the president of the European Commission, José Manuel Barroso, that the convoy was being dispatched. Mr. Barroso responded by warning "against any unilateral military actions in Ukraine, under any pretext, including humanitarian," the European Union said in a statement.
The Ukrainian government approved the aid convoy, but only if it was delivered under the auspices of the International Committee of the Red Cross. The office of President Petro O. Poroshenko issued a statement saying that he had spoken Monday with President Obama, who also welcomed the decision to allow humanitarian aid into the city of Luhansk under Red Cross auspices.