The move is aimed at maintaining pressure on Russia, the sources said.
Russia says it is preparing a response “commensurate with the economic losses” caused by the EU sanctions.
NATO says Russia still has about 1,000 heavily armed troops in eastern Ukraine – where pro-Russian rebels are fighting – and about 20,000 near the border.
The new sanctions are expected to tighten access to Western loans, especially for big Russian state oil companies, and expand a blacklist of Russian officials subject to visa bans and asset freezes. More rebel leaders will also go on that list.
Russian Foreign Ministry spokesman Alexander Lukashevich called the new sanctions “an absolutely unfriendly step”.
The EU decision followed a conference call involving a number of European leaders.
The member states struggled to agree on how to factor in the fragile truce between Ukrainian troops and pro-Russian rebels. It took effect on September 5 and appears to be holding despite some sporadic shooting.
The rouble fell to a new low of 37.57 to the dollar on September 11, after news about the EU sanctions broke. It also fell against the euro.
Western leaders and Kiev accuse Russia of helping the separatists in eastern Ukraine with regular troops and sophisticated weapons including tanks. Moscow denies the allegations.
The separatists have recently made big gains in the eastern Donetsk and Luhansk regions. The fighting has killed at least 3,000 people since April.
At urgent talks among 28 member states in Brussels on Wednesday, Germany pressed for the sanctions to be put into effect.
Other countries said they wanted to wait while the cease-fire continued to hold.
The EU leaders agreed on Thursday that the sanctions should take effect “by the end of the week”, according to Reuters.
They will be published in the official journal of the EU, which puts them into effect.
The package was finalized on September 5, but its implementation was delayed because of the cease-fire agreed on the same day.
The new sanctions will target Russian oil companies Rosneft and Transneft and the petroleum unit of state gas monopoly Gazprom.
Their access to financial markets will be restricted – a serious matter for Rosneft, which last month asked the Russian government for a $42 billion loan.
The measures also cover dual-use goods which can be used for military purposes, defense equipment and some other sensitive technologies.
Russian PM Dmitry Medvedev has warned that Russia might shut its airspace to European passenger planes, a move that “could drive many struggling airlines into bankruptcy”.
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