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The EU said it is moving to freeze assets of 18 people considered responsible for misusing Ukraine's state funds.
Foreign ministers for the 28 member states approved a list of individuals, who will have their funds and economic resources including cash, cheques, bank deposits, stocks, shares in Europe blocked.
"The Council today adopted EU sanctions focussed on the freezing and recovery of misappropriated Ukrainian state funds," the EU council said.
"Today's decision targets 18 persons identified as responsible for such misappropriation whose assets within the European Union will be frozen.
"The sanctions also contain provisions facilitating the recovery of the frozen funds, once certain conditions are met."
The sanctions will enter into force on Thursday 6 March and remain effective for the next 12 months.
The identities of those targeted are to be released after the measures are operational, as EU officials feared naming the 18 beforehand will give them a chance to pull their assets out of Europe.
The freeze also includes a ban on providing resources to the targeted individuals, which means EU citizens and companies should not any make payment or supply goods and other assets to the targeted 18.
Similar measures were implemented by Liechtenstein and Switzerland last week.
An unnamed senior Liechtenstein government source told Reuters that Liechtenstein was freezing the assets of former officials with the Ukrainian administration after other jurisdictions launched a wide-scale investigation into former president Viktor Yanukovich, his son, and 18 other individuals.
Ukraine is facing a financial crisis as the newly installed prime minister, Arseny Yatseniuk, revealed that $70bn (£42bn) has gone missing from the public's balance sheets after the government of ousted President Yanukovich hid the cash away in offshore bank accounts.
"The sum of $70bn was paid out of Ukraine's financial system into offshore accounts," he said in parliament this week.
"I want to report to you - the state treasury has been robbed and is empty. $37bn of credit received has disappeared in an unknown direction. The situation was so grave that there was no other alternative but to take extraordinarily unpopular measures."
In another development, the President of the EU Commission, Jose Barroso, has announced a €11bn aid package to Kiev.