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Meanwhile, in what was seen a possible slight de-escalation in tensions, Russia accepted a plan to send an international fact-finding team of at least 100 members into Ukraine to assess security in the country.
For more than a week, Russia had stonewalled the push by other members of the 57-nation Organization for Security and Cooperation in Europe to send in monitors. OSCE hopes the mission will prevent an escalation of tensions in Ukraine's east and south — regions with large Russian-speaking populations.
U.N. Secretary-General Ban Ki-moon, visiting Ukraine's capital, urged talks between Kiev and Moscow.
"At times like this, it is vital that all parties refrain from any provocative actions that could exacerbate an already very tense and very volatile situation," he said.
The EU hit 12 more people with sanctions Friday over Russia's annexation of Crimea, bringing its list of those facing visa bans and asset freezes to 33. They include one of Russia's deputy prime ministers, a Putin adviser and the speaker of Russia's upper house of Parliament, according to a document obtained by The Associated Press.
Annexing Crimea "is a flagrant breach of international law and something we will not recognize. This behavior belongs to the Europe of the last century not this one," Cameron said.
Still, the EU roster fell short of the high-powered U.S. list, in an apparent reflection of European wariness of going as far as Washington to punish Russia — Europe's neighbor, energy supplier and trade partner.
President Barack Obama on Thursday ordered a second round of sanctions against 20 members of Putin's inner circle and a major bank supporting them. The list included four businessmen considered to be Putin's lifelong friends.
Moscow retaliated by banning nine U.S. officials and lawmakers from entering Russia.
Putin tried to play down the sanctions at Friday's televised session of the presidential Security Council.
"We should keep our distance from those people who compromise us," he said, a jocular reference to the officials on the sanctions list, some of whom attended the meeting.
Putin added sardonically that he would open an account to keep his salary in the targeted Bank Rossiya, owned by Yuri Kovalchuk, considered to be Putin's longtime friend.
At the same time, Putin said he sees no immediate need for further Russian retaliation over the U.S. sanctions, adding that Russia will keep funding a program jointly with NATO to service Afghan helicopters and train their crews.
However, just a few hours later, the Russian Foreign Ministry said Moscow will "harshly" respond to the latest round of U.S. sanctions, and Putin's spokesman, Dmitry Peskov, said Russia will retaliate.
Russian Defense Minister Sergei Shoigu told Putin on Friday that 72 Ukrainian military units in Crimea have decided to join the Russian military. His claim couldn't be independently confirmed.
At the Ukrainian military air base in Belbek, outside the Crimean port of Sevastopol, Col. Yuly Mamchur told reporters he was still waiting for orders from his commanders on whether to evacuate.
Casert reported from Brussels, Belgium. Maria Danilova in Kiev, John-Thor Dahlburg in Sevastopol, Crimea, Nataliya Vasilyeva in Moscow, Mike Corder in Brussels, Cassandra Vinograd in London and Angela Charlton in Paris contributed to this report.