Two people were injured and a clean-up operation was underway in Berrima after a fuel tanker rolled onto its side on the Hume Highway on Tuesday night.
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The Mercury understands the tanker spilled diesel over the major highway after an accident involving another truck around 6pm.
"There was a large fuel spill, about 500 litres, which Fire and Rescue NSW were containing and cleaning up using absorbent material," a FRNSW spokesman said.
"They were monitoring run off-in conjunction with EPA."
The RFS assisted with fire protection.
An Ambulance NSW spokeswoman said one driver, a 48-year-old male, was conscious, breathing and had a possible injured leg when he was assessed by paramedics.
Another person who was trapped inside one of the trucks was freed by SES, before being transported by ambulance to hospital.
Police were in attendance.
As of 8.40pm, Live Traffic advised one of two southbound lanes were closed to salvage the truck.
Northbound lanes are affected by moderate traffic conditions.
Live Traffic advises motorists to exercise caution and allow extra travel time. See Live Traffic for updates.