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The incident took place near Chotila around 10:30 pm on Monday, said inspector Asi Odedara of the local police station.
The van was carrying 20 passengers. Two of them died on the spot following the collision while two more died in hospital, she said.
The van was heading for Somnath from Shiyani village in Limbdi taluka of the district. The truck, coming from the opposite direction, turned right to halt at a roadside hotel and it led to the collision, the official said.
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All the 16 injured persons were receiving treatment at the Rajkot civil hospital.
The deceased, who were related to each other, were identified as Magjiben Rethariya (72), Galalben Rethariya (60), Manjuben Rethariya (65) and Gauriben Rethariya (68).