The two children in the other car were not seriously injured, but one of two adults in the car suffered a broken arm, according to State Police Spokesman Julian Castellanos.
She was identified as Marina Morales, 30, of Manahawkin.
Walker, 41, a canine officer with the Passaic Sheriff's Department, was traveling with his dog to a training session in Little Egg Harbor. Neither Walker nor his dog were injured in the collision.
The accident happened in Bass River Township, near his final destination.
Initial reports indicate Walker was driving with his emergency lights on when he hit the rear of the Suburban, forcing it off the highway and into some trees.
Castellanos says he was taken to a local hospital for a blood test, the was released from the state police station at Bass River, where Internal Affairs officers from the Passaic Sheriff's Department were headed to investigate.
A spokesman for the Passaic Sheriff's Department, Bill Maer, said Walker "The public deserves better."
Maer said the incident "was very disappointing, a disgrace and will not be tolerated."
Walker "will be immediately suspended without pay," according to Maer. His current salary is approximately $79,000 a year.