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Pauline Smith was driving a blue car that collided with a white Holden Vectra on the Western Highway in Great Western near the Grampians before 8am today.
She was pronounced dead at the scene.
The second driver was taken to hospital with non-life threatening injuries.
He is assisting police with their investigation.
Ambulance Victoria Acting CEO Libby Murphy this evening released a statement to mourn Smith’s death.
“We stand united in shock and sadness as an organisation today after the sudden passing of our paramedic colleague Pauline Smith,” Murphy said.
“Our deepest sympathies are with Pauline’s husband, Stephen, and her three children, her family, friends and close colleagues.
“Pauline was a much loved and respected member of the Grampians community and will be greatly missed.”
Police are calling for anyone who saw the Holden before the crash to contact them.
Part of the highway is expected to be closed for the rest of the day.
Drivers are encouraged to take alternative routes.