The accident took place around 8 AM when the van, carrying students of DD Convent School, Hajipur, was hit by Tamsa passenger train on its way to Varanasi from Azamgarh at an unmanned crossing in Ranipur area.
Officials said that at the time of the mishap the driver had earphones plugged.
Superintendent of Police A K Shukla said that four children were killed on the spot and another child later succumbed to injuries in a hospital. Earlier, he had said that six children were killed on the spot and nine injured.
There were 13 children in the van besides the driver, who also got injured.
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Terming as "unfortunate" the death of the children in the mishap, Railway Minister Suresh Prabhu announced a compensation of Rs 2 lakhs for the next of the kin of the deceased.
"A big accident has happened as a van carrying school kids collided with a train....It is unfortunate that the driver didn't stop to see as is expected of him at an unmanned level crossing and this led to the tragedy," the Minister told reporters outside Parliament before rushing to the accident site.
Uttar Pradesh government has also announced an exgratia of Rs 2.5 lakh to the kin of the children killed while sanctioned Rs 50 thousand for those injured in the incident.
Taking note of the incident, the state government immediately sent Transport Minister Durga Prasad Yadav on the spot to know the ground reality and ensure proper medical care of those injured.
With the accident once again bringing into focus, the problem of unmanned level crossing, the Minister said the government was taking all steps to man them.