The CCTV of Mr Rowley who is said to be on the brink of death has been obtained. His girlfriend Dawn Sturgess, 44, however passed away in Salisbury Sunday night.
Mr Rowley, who had the highest concentrations of the nerve agent on his hands, is seen buying cans of super-strong lager in Salisbury and sharing a laugh with the cashier, who takes his money and packs up the alcohol for him.
The couple, who were heavy drinkers and drug takers, are believed to have picked up a syringe or vial of the nerve agent dumped by the assassins sent to kill Sergei Skripal and his daughter Yulia.
It came as Scotland Yard said it 'cannot offer any guarantees' that others won't be poisoned and revealed a red Transit van travelled in by Mr Rowley on the day he fell ill has been sent to Porton Down for testing.
Assistant Commissioner Neil Basu, the head of Britain's counter-terror police, said that Miss Sturgess' death is being treated as murder but admitted they still haven't found the vessel containing one of the world's deadliest poisons.
Wearing jeans, a cheque shirt and cream coloured baseball cap, 45-year-old Mr Rowley buys four cans of 9 per cent Karpackie Polish lager from Best 1 Local in Salisbury city centre at 10.06am on June 29.
The next day he would be fighting for life after being exposed to the deadly nerve agent with partner Dawn.
Shop assistant Kamal Goodall, 55, said: 'He didn't like to say much when he came in.
'That particular morning was no different, I think he may have made a comment about the hot weather.
'Physically he looked ok, he was always quite slow, thin and fragile-looking.
'He paid for his lager and left and that was the last time we saw him as he collapsed the following day.
'Dawn usually came in to the shop more often and would buy Charlie stuff. He'd come in now and again.
'She seemed more healthier than him. It's really sad that she has passed away. We're hoping Charlie pulls through'.
Ms Sturgess and her partner Charlie Rowley, 45, collapsed and began foaming at the mouth on Saturday after finding the Novichok in Queen Elizabeth Gardens, Salisbury.
The mother-of-three suffered a heart attack after coming into contact with the nerve agent and perished late yesterday.
Giving the latest update on the investigation on Monday, Assistant Commissioner Basu said: 'The investigation is being led by detectives from the UK's counter-terrorism poliocing network, and they are unable to say at this moment whether or not the nerve agent found in this incident is linked to the attack on Sergei and Yulia Skripal, however this remains our main line of inquiry.
'Our focus and priority at this time is to indentify and locate any container that we believe may be the source of the contamination. In the four months since the Skripals and Nick Bailey were posioned, no other people besides Dawn and Charlie have presented with symptoms. But their reaction was so severe it resulted in Dawn's death and Charlie being critically ill.
'This means they must have had a high dose and our hypotheseis is that they must have handled a container that we are now seeking.'
A red Ford Transit van in which Mr Rowley was a passenger on June 30 has been recovered and sent for testing at the Government laboratory at Porton Down.
Three other men who also travelled in the van have been tested and show no signs of having been exposed to Novichok, Mr Basu said.
Praising the 'tremendous stoicism' of people of Wiltshire, he told journalists outside Scotland Yard that 21 people have raised concerns about being exposed but have been given the all clear.
Only three of these are members of the public - the people in red Transit with Mr Rowley - with the rest being police and health workers.
Mr Rowley remains critically ill in hospital and doctors told his close family he has 'just days to live'.
Dawn's grieving mother Caroline confided in the hours after her daughter's death: 'It's not looking good for Charlie either. Maybe a few days. He won't pull out of this either. He's just alive with the machines.'
She told her family: 'Dawn died before 10pm. Her body just shut down. With her drink and drug addiction, her body wasn't strong enough to deal with this.'
Today anti-Putin campaigner Bill Browder, who is consider the Kremlin's top foreign enemy, warned 'many more will die' unless Government gets tough with Russia.
He tweeted: 'Tragic news as the Putin regime's terrorism on U.K. soil has claimed another innocent life. It's beyond time for British government to get tough with Russian state actors and their oligarch trustees in London or many more people will die'.
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