Prime Minister Scott Morrison has condemned Russia's "brutal" and "unprovoked" invasion of Ukraine following reports of hundreds of casualties and missiles being launched into the country's capital.
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Targeted sanctions announced earlier on members of Russia's Security Council, which are at the centre of "perpetrating" the Ukrainian invasion, will come into effect from midnight.
Mr Morrison said Russia has "chosen war" but his thoughts were with those on the frontline in the eastern European country.
"Those who are enduring [this] terrible invasion as the bombs fall and the shelling continues and the bullets are fired, as special forces from Russia are moving towards Kyiv, and tanks are rolling in all around their borders," he said on Thursday evening.
"This is a chilling reminder of the world that we live in."
The Prime Minister said acting Foreign Minister Scott Birmingham had completed the process of applying sanctions to an additional 25 people, including army commanders, deputy defence ministers and Russian mercenaries involved in the conflict.
Further sanctions will be considered, Mr Morrison warned, adding the more than 300 members of the Russian Parliament were being looked at.
Assistant Defence Minister Andrew Hastie earlier cautioned "sanctions are just the start" after initial reports indicated Russia had launched a "full-scale invasion" of Ukraine by Thursday afternoon, Australian time.
Russian forces fired missiles at Ukrainian cities and landed troops on its south coast, officials and media say, following President Vladimir Putin's authorisation of a "special military operation" in the east.
Mr Hastie said the Morrison government's decision to rule out the deployment of Australian troops to the region remained but said it could assist Ukraine in other ways.
"We're just getting warmed up," he told Sky News on Thursday after reports Russian troops had shelled the country's capital city, Kyiv.
"You don't have to bomb a city to bring it to its knees if you can hack its critical services and infrastructure, which is what we saw the Russians doing.
"It's really important that we provide whatever support we can and sanctions, graduated sanctions, are just one of the things that we can do to demonstrate our resolve standing with other democracies around the world and supporting Ukraine."
As of Friday, Australia will slap additional economic sanctions on Russia, targeting eight Russian security council members, banks, transport, energy and telecommunication companies.
Sanctions imposed by Australia follow similar moves by the United States and the United Kingdom and come after Russia's earlier decision to move troops into the eastern Ukrainian region of Luhansk and Donetsk.
Mr Morrison said there has to be a price for "unprovoked, unlawful, unwarranted, unjustified attacks" on another nation's sovereignty.
"This goes direct to those individuals who are at the heart of this bullying and aggressive behaviour," he said on Thursday morning.
"Any country that is allowing those who are at the heart of perpetrating this to be able to go about their lives and spend their money and make investments and do all of that is only encouraging this behaviour and they will get no comfort here in Australia."
The sanctions will be legislated on Friday and come into full effect at the end of March.
Mr Morrison said Ukrainians in Australia would have their visas extended and Ukrainians awaiting visa approval would have an expedited process.
The Prime Minister also denounced the Russian ambassador's comments that the sanctions were xenophobic.
"The suggestion that somehow Russian soldiers crossing the border and entering Ukraine is deeply offensive to anyone who has pulled on a uniform as a peacekeeper across the world," Mr Morrison said.
"They are not peacekeepers. They are invaders."
Mr Morrison conceded the first tranche of sanctions placed up on Russia by western allies would likely not be enough to prevent further invasion into Ukraine.
President Vladimir Putin signed a decree on the deployment of troops to the breakaway enclaves in eastern Ukraine in a move he said is aimed at keeping the peace.
Russian embassy responds
The Russian embassy has responded at the new measures, accusing Australia of turning a blind eye to discrimination by "the radical nationalistic regime in Ukraine and to the plight of civilians in Donbas living for years under blockade and constant shelling from the Ukrainian military."
"In alignment with its key partners, Canberra has played its part in supporting and encouraging the xenophobic bullies based in Kyiv."
In a statement, the embassy said the decision to "recognise" the Donetsk and Luhansk regions on humanitarian grounds to protect civilians, including hundreds of thousands of Russian nationals.
"[Russia] will from now on guarantee the right of [Donetsk and Luhansk] residents to live in peace and preserve their language and cultural identity."
This disinformation from the Russian government, amplified through Kremlin-controlled media, has been condemned by the US and other governments, while social media platforms have been on high alert for misleading statements, headlines and images that violate the online platforms' policies.
Separatists control only a portion of the Donetsk and Luhansk regions, but Russia's claims otherwise have been used as its pretext for creating the current tensions.
Peacekeeper label 'obscene'
Foreign Minister Marise Payne said it was an "obscene perversion" for Russian President Vladimir Putin to speak of Russian soldiers acting as "peacekeepers" in Ukraine.
"Any suggestions that there is a legitimate basis for Russia's actions are pure propaganda and disinformation," Senator Payne told reporters during a visit to the Czech capital Prague.
She added Australia would not hesitate to impose more sanctions if Russia escalated tensions.
'Full-scale invasion' of Ukraine after Putin orders 'special military operation'
The Ukrainian Foreign Minister Dmytro Kuleba tweeted on Thursday afternoon Russia has launched a "full-scale" invasion, including missile strikes in Kyiv.
"Putin has just launched a full-scale invasion of Ukraine. Peaceful Ukrainian cities are under strikes," he said.
"This is a war of aggression. Ukraine will defend itself and will win. The world can and must stop Putin. The time to act is now."
Ukraine's military command centres in Kyiv and the city of Kharkiv in the northeast had been struck by missiles, a Ukrainian news site cited an official as saying, while Russian troops had landed in the southern port cities of Odessa and Mariupol, Interfax Ukraine reported.
Explosions also rocked the breakaway eastern Ukrainian city of Donetsk and civilian aircraft were warned away from the region.
It followed an authorisation from Putin for a special military operation in breakaway areas of eastern Ukraine after Russia had been left with no choice but to defend itself against what he said were threats emanating from modern Ukraine.
"Russia cannot feel safe, develop, and exist with a constant threat emanating from the territory of modern Ukraine," Putin said.
"All responsibility for bloodshed will be on the conscience of the ruling regime in Ukraine."
The full scope of the Russian military operation was not immediately clear but Putin said: "Our plans do not include the occupation of Ukrainian territories. We are not going to impose anything by force."
PM calls Ukraine
Mr Morrison spoke with his Ukrainian counterpart Denys Shmyhal on Wednesday night to inform him of the sanctions.
Mr Morrison told Mr Shmyhal that Russia's behaviour towards Ukraine was "unacceptable, unprovoked and unwarranted".
Australia has ruled out direct military assistance and is supporting Ukraine's cyber capability.
Russia's ambassador to Australia, Alexey Pavlovsky, was also hauled in to meet with the secretary of the Department of Foreign Affairs and Trade on Wednesday afternoon following the announcement of the sanctions.
The diplomat has not been expelled from the country.
Data-wiping software hits Ukraine websites
A newly discovered piece of destructive software found circulating in Ukraine has hit hundreds of computers, according to researchers at the cybersecurity firm ESET, part of what Ukrainian officials say is an intensifying wave of hacks aimed at the country.
In a series of statements posted to Twitter, the company said the data-wiping program had been "installed on hundreds of machines in the country," an attack it said had likely been in the works for the past couple of months.
Vikram Thakur of cybersecurity firm Symantec, which is also looking into the attacks, told Reuters that infections had spread widely.
"We see activity across Ukraine and Latvia," Thakur said. A Symantec spokesperson later added Lithuania.
Who is responsible for the wiper is unclear, although suspicion immediately fell on Russia, which has repeatedly been accused of launching data-scrambling hacks against Ukraine and other countries. Russia has denied the allegations.
No specific cyber threat in Aust
Australian authorities are not aware of any current or specific cyber threats against businesses or critical infrastructure, such as banks or telcos, after imposing sanctions on Russia.
But Mr Morrison says the most likely retaliation against Australia would be cyber attacks, as malicious cyber activities against Ukraine continues alongside Russia's military build-up on the border.
Mr Morrison urged Australian businesses to immediately review and adopt enhanced cybersecurity measures such as malware detection, mitigation and response.
"It's an issue in which we need to be constantly vigilant," he told reporters in Sydney on Thursday.