The poisoned Amesbury couple were exposed to Novichok – the same substance that almost killed a Russian spy and his daughter.
Charlie Rowley, 45, and 44-year-old Dawn Sturgess were named by friends as the pair who fell critically ill after being exposed to the nerve agent.
In a press conference this evening, Metropolitan Police Assistant Commissioner Neil Basu confirmed the substance was Novichok.
He said there was no intelligence to say the pair were "targeted" but that links to Sergei Skripal and his daughter Yulia was "a line of inquiry".
Charlie and Dawn were found unconscious at a property on Saturday, with one friend describing Charlie as "garbling" and acting like a "zombie".
Home Secretary Sajid Javid will chair a meeting of the Government’s Cobra emergencies committee on Thursday, Downing Street said.
The couple’s flat is around eight miles from where the Skripals were poisoned in March earlier this year.
In a press statement this evening, Mr Basu said there had been a "significant development" in the investigation and confirmed counter-terror cops are now leading the probe.
"This evening we have received test results from Porton Down that show the two people have been exposed to the nerve agent Novichok," he said.
"At approximately 10.15am on June 30, the South West Ambulance Service was called to a residential address in Amesbury, where a 44-year-old woman had collapsed. She was subsequently taken to hospital.
"At around 3.30pm that day, the ambulance service was called back to the same address, where a 45-year-old man had also fallen ill. The man was taken to hospital and Wiltshire Police were informed."
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From initial assessment, it was thought that the two patients had fallen ill after using drugs from a potentially contaminated batch.
But on Monday, due to concerns over the symptoms the man and woman were displaying, samples from both patients were sent to Porton Down laboratory for analysis.
"Following the detailed analysis of these samples, we can confirm that the man and woman have been exposed to the nerve agent Novichok, which has been identified as the same nerve agent that contaminated both Yulia and Sergei Skripal," Mr Basu said.
"The latest update we have from the hospital is that both patients remain in a critical condition. Both are British nationals and are local to the area. Officers are still working to identify their next of kin.
"At this stage, no-one else has presented with the same symptoms linked to this incident."
The Met Police said the priority for the investigation team is to establish how Charlie and Dawn came into contact with the nerve agent.
There are around 100 detectives from the Counter Terrorism Policing Network working on the investigation, alongside officers from Wiltshire Police.
Five sites in the Amesbury and Salisbury areas have been cordoned off as police believe Charlie and Dawn visited them in the period before they fell ill.
"This is a precautionary measure while we continue to investigate how they came into contact with the substance," Mr Basu said.
"I do want to reassure the public, however, that there is no evidence that either the man or woman recently visited any of the sites that were decontaminated following the attempted murders of Sergei and Yulia Skripal.
"Looking ahead over the coming days, people in the area can expect to see an increased police presence, which will include officers wearing protective equipment as they carry out activity at a number of sites. This will look similar to some of the activity that took place in Salisbury earlier this year.
"Again, this is a precautionary, but necessary measure that allows officers to safely carry out meticulous and systematic searches for evidence to support the investigation. This must be done with great care as you will appreciate, to ensure there is no outstanding risk to both those brave officers and the public.
"I appreciate that there will be a great deal of speculation as to whether this incident is linked to the events in Salisbury in March.
"I would add that the complex investigation into the attempted murders of Yulia and Sergei remains ongoing and detectives continue to sift through and assess all the available evidence and are following every possible lead to identify those responsible, for what remains a reckless and barbaric criminal act.
"However, I must say that we are not in a position to say whether the nerve agent was from the same batch that the Skripals were exposed to. The possibility that these two investigations might be linked is clearly a line of enquiry for us.
"It is important, however, that the investigation is led by the evidence available and the facts alone and we don’t make any assumptions."
Both Charlie and Dawn were carried from their flat on stretchers by paramedics in hamzat suits.
Footage from the scene of the incident showed one of the victims being lifted into an ambulance by medics in the protective equipment.
Hazmat suits consist of an impermeable whole-body garment worn as protection against hazardous materials.
A neighbour who lives in the same block of flats as the couple described how he saw each of them being stretchered from their flat into waiting ambulances.
The man in his 30s, who did not want to be named, described Dawn and Charlie as ‘lovely people’.
Speaking through the window of his ground floor flat, which is inside the police cordon, he said: "It was about 10.30am on Saturday when I saw Dawn being taken out on a stretcher.
"Then later that evening, Charlie was also taken out and put into an ambulance.
"There were lots of emergency vehicles about and we were all told to stay in our homes.
"Charlie and Dawn haven’t been living at the flat long at all, and I’ve only met them a couple of times but they seem like lovely people. They seem decent."
Chloe Edwards, a 17-year-old college student who lives opposite the flat, said: "I was looking out of the window having my dinner when I saw emergency vehicles were all lined up down the road outside my house.
"There were ambulances, fire engines, lorries, and the people that got out were wearing yellow and green suits.
"It’s really nerve wracking. It’s quite scary."
Home Secretary Sajid Javid said: "I want to express my thanks to the emergency services and staff at the Salisbury District Hospital for their tireless professionalism in dealing with the incident in Amesbury.
"It follows the reckless and barbaric attack which took place in Salisbury in March.
"The Amesbury investigation is ongoing and the police must be given the space they need to continue establishing the full facts.
"My thoughts at this time are with the two individuals affected.
"The Government’s first priority is for the safety of the residents in the local area but as Public Health England has made clear, the risk to the general public is low.
"Tomorrow I will chair a meeting of the Government’s emergency committee COBR in relation to the ongoing investigation."
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