The volunteer firefighter killed on Monday while fighting the Green Valley Fire in the Jingellic Talmalmo area has been identified as Samuel McPaul.
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NSW Rural Fire Service said Mr McPaul was involved in a freakish weather event with extreme strong winds lifting the 10 tonne fire truck off the ground, landing on its roof.
This trapped all three members of the crew and one sustained fatal injuries.
The truck had three men on board, with a second passenger, aged 39, airlifted to The Alfred Hospital in Melbourne in a serious condition suffering burns.
The driver, 52, was treated at the scene then taken to Holbrook hospital with minor injuries. He has since been released.
"It's believed the two passengers were firefighting from the refuge area behind the main cabin when the vehicle rolled," a police statement said.
Murray River Police District officers established a crime scene, which was examined by specialist forensic officers.
A report will be prepared for the coroner and inquiries continue.
NSW RFS Superintendent Patrick Westwood confirmed the fatality.
"I am sure that the community of the Southern Border team area will understand that we have support under way for the firefighter's family at present," he said.
"The crew decided to move away from that area and, quite unexpectedly, very suddenly, they experienced extreme winds and what could only be described as a fire tornado that lifted the back of the truck, fully inverted it and landed it on its roof, trapping three people, three crew that is, and unfortunately, one of them fatally.
"The driver was a veteran captain of 35 years-plus experience.
"He thought he was in the right spot, as he was, from what I can understand, and just this freakish weather event that would have to be seen to be believed.
"Even then, other veteran firefighters don't believe what they saw, (it) engulfed that vehicle with flame, fire, and strong winds and literally picked up an eight-tonne truck and flipped it over."
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NSW RFS Commissioner Shane Fitzsimmons and the RFS Senior Chaplain Ian Spall joined Superintendent Westwood spending time overnight with Mr McPaul's family.
"As everyone would understand this is a very, very sad day for the NSW Rural Fire Service family locally and across the state," Superintendent Westwood said.
"Four of our firefighters have received burns and have been transported to Albury Base and major hospitals in Sydney and Melbourne for treatment and at least two of our appliances have been damaged on the fire ground."
The fire has crossed the Murray River and the RFS will be assisting the Country Fire Authority with the continuing firefight over the coming days.
An Albury Rural Fire District deputy group captain suffered a torn leg muscle and concussion when his four-wheel drive flipped on River Road, east of Jingellic.
In the same area, two firefighters from the Back Creek brigade suffered facial burns after fire hit their truck.
They were taken to Concord hospital in Sydney.
A fundraising page for the family of Mr McPaul was being set up on the RFS website on Tuesday.
Prime Minister Scott Morrison said he had spoken to Mr McPaul's wife Megan following the tragic incident.
"I cannot imagine the terrible sense of loss and grief that Sam's family are now feeling," he said.
"Sam McPaul was a brave firefighter.
"I have spoken to Megan to extend my deepest sympathies and our love and support at this terrible time and express that same sentiment on behalf of the entire country.
"Sam McPaul was the best of us.
"This is devastating news and I also extend my sincere condolences to his entire family, friends and fellow brigade members.
"It is an unimaginable loss and one felt by the entire country."