The Divine Public School van was carrying almost 25 students that were passing through the railway crossing in Thursday early morning when the incident took place.
An official said that the Chief Minister ordered that school vehicles across the state be checked on whether they were following the guidelines prescribed for such vehicles.
The train involved in the incident when it was on its way from Sivan to Gorakhpur.
Adityanath announced an ex-gratia of Rs 2-lakh each for the bereaved families of the victims.
"It was an unmanned level crossing gate at Behpurva, with Gate Mitra (rail volunteer) deployed there. He tried to stop but unfortunate incident happened at unmanned gate 45 near Dudhi station in Banaras division", the spokesperson said in New Delhi. The chief minister was visiting the accident spot where he was met with angry protesters shouting slogans against the railway and local administration.
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The unmanned railway crossing is one of the major problems of India where many Indians lost their lives.
Eight children and the driver were injured and taken to hospital, police said.
The Chief Minister also ordered to register an FIR against the principal of the school. "Kindly let us go through the area and inspect the accident site", he said. India has vowed to upgrade unattended railway crossings next year to reduce fatal accidents. "My thoughts are with families of the deceased and I pray for the early recovery of the injured", Railway Minister Piyush Goyal said in a statement. At least 24 children and three adults were killed when a school bus plunged off a mountain road in northern India on April 9.
There were unconfirmed reports that perhaps van driver was listening to music using earphones and the accident took place.